CA1311238C - Non-digestible fat substitutes of low-caloric value - Google Patents
Non-digestible fat substitutes of low-caloric valueInfo
- Publication number
- CA1311238C CA1311238C CA000536602A CA536602A CA1311238C CA 1311238 C CA1311238 C CA 1311238C CA 000536602 A CA000536602 A CA 000536602A CA 536602 A CA536602 A CA 536602A CA 1311238 C CA1311238 C CA 1311238C
- Authority
- CA
- Canada
- Prior art keywords
- acid
- food composition
- polyol
- reduced calorie
- epoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/33—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with hydroxy compounds having more than three hydroxy groups
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/20—Reducing nutritive value; Dietetic products with reduced nutritive value
- A23L33/21—Addition of substantially indigestible substances, e.g. dietary fibres
- A23L33/25—Synthetic polymers, e.g. vinylic or acrylic polymers
- A23L33/26—Polyol polyesters, e.g. sucrose polyesters; Synthetic sugar polymers, e.g. polydextrose
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/115—Fatty acids or derivatives thereof; Fats or oils
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/20—Reducing nutritive value; Dietetic products with reduced nutritive value
- A23L33/21—Addition of substantially indigestible substances, e.g. dietary fibres
- A23L33/25—Synthetic polymers, e.g. vinylic or acrylic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S426/00—Food or edible material: processes, compositions, and products
- Y10S426/804—Low calorie, low sodium or hypoallergic
Abstract
Abstract Esterified epoxide-extended polyols (EEEPs) of the formula P(OH)a+c(EPO)n(FE)b where P is a polyol having a = 2 - 8 primary hydroxyls, c = 0 - 8 secondary and tertiary hydroxyls, a + c is in the range of 3 - 8, EPO is a C3-C6 epoxide, FE is a fatty acid acyl moiety, n is the minimum epoxylation index average number having a value generally equal to or greater than a and is a number sufficient that greater than 95% of the primary hydroxyls of the polyol are converted to secondary or tertiary hydroxyls, and 2 < b ? a + c, methods of preparation thereof, and their use as non-digestible fat substitutes (fat mimatics) having non-caloric food values, which have good organoleptic characteristics, are substantially resistant to intestinal absorption, and do not appreciably hydrolyze in the digestive tract. Suitable polyols include sugars, glycerides or saccharides which are reacted (etherified) with C3-C6 epoxides such as propylene oxide, butylene oxide, isobutylene oxide, pentene oxide, and the like to produce epoxide-extended polyols (EEPs) having an epoxylation index number, n, generally in the range of 2 - 8. Acylation with C8-24 fatty acids such as octanoic, stearic, palmitic, oleic, and/or heptadecanoic, or fatty acids from soybean oil, fish oil, coconut oil, cotton seed oil, corn oil, sunflower oil, safflower oil, jojoba oil and the like, produce the end product ester with physical properties ranging from a liquid oil, through fats and greases, and ultimately to waxes. Best mode example are acylated propoxylated glycerol compound mixtures (APGs) which are resistant to pancreatic lipase in vitro, and feeding studies show them to be suitably resistant to overall digestion. The resultant EEPEs are useful in food formulations and for cooking as they have a good mouth feel and characteristics similar to vegetable oils and fats. Being relatively non-absorbable, non-digestible, and non-toxic they may be substituted for natural or processed oils and fats, but have low caloric value.
Description
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This invention relate~ to esteri~ied epoxide-extended polyols (EE~s), methods o~ preparation thereo~, a~ thei.r use as non~digestible, non-caloric ~at su~stitutes (~at ~imetics~ ~or cooking and in ~ood compo~itions. The EE~P3 have good organoleptia characteristics, have acceptable lev~l~ o~
lo resistance to overall digestib~lity as measured ~y rat feeding studies. More particularly, the invantion relate~ to acylated epo~ylated glycerol compound mixture~ (A~Gs) o~ th~ formula : [P(OH)a+C(EPO)n(F~)~], where P is a polyol havi~g a ~
: primary hydroxyls, and C - O - 8 secondary plus tsrtiary hydroxyls, with a ~ c boing in tha rangs o~ 3 - 8, EPO is a C3 ~ C6 epoxida, FE is a ~atty acid acyl moiQty, n is the minimum epo~yl~tion indQx averaga num~er having a valua g~nerally equal to or great~r than a and i8 a nu~bar ~u~cient that greater than 95% o~ the pri~ary hydroxyls of thQ polyol are converted to secondary or tertiary hydroxyls, and 2 ~ b C a + c, which are resistant to hydEoly~is by pancreatic lipase. The ; rasuI~ant E~EPs may have physic~l prop~rtie~ ranging from a liquid oil, through ~t and gr~a~e~. Th~y are us~ul in ~ood formulations and cooking as ~hey havq good mouth ~esl and characterist~ C9 ~imilar to v~g~ta~l~ oil~ and fats. Being relativ~ly non-absorbabl~, non-dig~stible, and non-toxic they may be sub~ u~ed ~or natural or process~d 9il9 and fat~, but have low caloria value.
8ack round:
T~e accumulation of medlcal eviden~a in recent years r~garding tha ad~ers~ health implication~ o~ high ~at diats, prinolpally heart attackQ, atherio~cl~rosis and ov~rweight, has caus~d con~u~rs to b~co~ axtr~msly concarn~d about their dl~ts~ It i~ e~timat~d that between 70 - 80% of U.S. adult ~emale~ follow a weight reducing di~t at lea~t onca a year. Men , -2- ~
, . . .
~L C~ r3~
are also concerned about their weight and cholesterol levels.
The concerns of both men and women have given rise to diet fads, diet drlnks e~pecially in the so~t drink, wine and beer indu~try, and exercise programs and health club8, Common obesity is one of tha mosk prevelant metabolic problems among people today. Fate and oils are n~cessary ~or balanced nutritlon. Howe~er, he average consumer simply con~umes more than is needed for proper nutrition. Fat, at 9 calories per gram, as compared to 4 calories p~r gram ~or carbohydrates or proteins, i9 tha mo~t concentrated dietary energy formO It is estimated that ~at c:onstitute~ about 40~ of the total calories in the typical western diet. Fats are consumed directly in mea~s, spreads, salad oils, and in natural produce such as nuts and avocados. Fats and oils arQ consumed as a re~ult of absorption or incorporation in the ~oods during baXing and frying. The vast incr~ase in consu~ption of fast foods i5 a major contributor to tho increa~ in the a~ount of dietary ~at sincQ ~ast foods rely ext~nsively on f~ying processes employing ~at~ and oils. In addition, the snack food industry : 20 uses larg~ a~ount~ of fats and oils in the production of potato chips, corn chips and other ~nack items. For example, in 1981 the USDA ~stl~ated approximately 12 billion pounds of fat and oil w3re ussd in sdibl~ products, predominately baking, frying fats, maryarina, salad oil and/or cooking oil.
Ther~ is thus a clear i~dication that there i~ an snormous potential h~alth ~ood mar~et ~or a ~at s~bstitut~ or fat mimet1c that i~ eith~r ~ntiraly non-dig~stibls, or ha~ reduced caloric value. Man~ nutxitionists b~liev~ that ~mericans typically rely on fats for too large a proportion of calorias in th~ir diet.
Th~ National ResQarch Council, for example, has recormended that ~ Americane redur0 the proportion of th~ir di~taxy calories coming : from fats ~ro~ 40% to at }ea t 30~. Replacement o~ ~ats in the diet with non caloric sub~titu~es i8 a ~ore ~fficient way of reducing caloric intake than r~placing sugar or carbohydrates b~cause gram ~or gram, th~ substitutlon o~ non calorlc fat substitute~ is more than twioe as ~ective than reducing ~3-~ , 2 ~ '3 carbohydrate content with such things as saccharinP or Nutra-sweet.
One of the difficulties in ~li~inating fat from the diet is the fact that fats and oils are all-perva~ive in food products.
In part, this i~ b~cause th y play an i~portant role in the organoleptic acceptability of food products. For a fat substitut~ to bs acceptable, it must ba non-digestible, that is, not hydrolyzed in the digestive tract. In addition, it should not be dirQctly absorbed through the intestinal wall. While some t~pes of ~at substitutes may be non-digestible, they are not of su~ficiently high molecular weight to prevent them from being absorbed through tha intestinal wall. Tha thxeshold moleculax weight o~ non-ab~orbability for lipophilic molecules appears to be about 600.
In addition, the fat qubstitute mu3t it~el~ be non-toxic at high lev~ls o~ ing~stion. It mu~t contaln no toxic r~sidue or impuritie~. To th~ extent that a fat ~ubstitute may bQ partially hydrolyzed in the dige~tiv~ tract, any hydroly3is products must be non~toxic and/or ~etabolizable. I~ mQtabolizable, th6y should have very low caloric valu~ In g~naral, fat sub~titutes mu~t be without any seriou~ medical side a~ect~.
Th~ ~at ubstituts~ must al~o have good orga~oleptic gual$tie~ of mouth ~el and havs no taste. In addition, fat substitutes mu~t hav~ appropriate physical pro~Qrties ~or use in food composition~. That i~, thay should b~ liqutds or Yolids depen~ing on whether they ar~ ua~d a3 oil or ~hortening substitute~, and wher~ used for cooking, ~ust be thermally stabla. Whil~ certain pclysaccharide gums hav~ been used as thickening agents, bulking agsnts or fillers in low-calorie foods, they can give a pro~uct a "slimy" mouth ~e~l and are unsuita~la ~or cooking as they have no tharmal stability.
ACCQPtab1e synthatic fats would b~ add~d in large quantities (30 60~) to ~alad oil~, cooking oil~, ~argarine~, butter blends, ~ayonnaise, short~nings and the like to creata a new class o~
low-calorie product~. Whil~ "low caloria" mayonnaise and salad dressing~ are pr~s~ntly available, the reduction in calories is ~4-2 ~ ~
achieved by increasing the water content with a corr~sponding loss in the organolepkically '~rich" taste o~ such product~.
A currant review of the ~ield is found in a ~eature article entitled "Gett1a~ The Fat Out - Researcher~ Seek Substitutes For ~Yl~=Ea~ _Ea~" JAOCS, Vol. 63, No. 3, (March 1986) pp. 278-286, 2~8.
On~ prior ~rt proposed fat substitut~ i8 sucro~a polye~er (SPE), shown in UOS. patents 3,600,186 (Matson, et al. 1971), 3,521,827 and 3,963,699 (Rizzi, et al., 1976) of Proctor ~
Gamble. The SPEs are produced by kha reaction o~ a monosacch~ride, disaccharide or sugar alcohol having a minimum o~
~our hydroxyl groups with fatty acids ha~ing ~rom 8-22 carbon atoms. It was reported in "Chemical and Engineering News"
(July 26, 1982, page 32) that incorporating SPE aa a partial replacem~nt o~ tha fat~ in th~ diQt~ o~ ten obe~ patients dropped thQir caloric intake whils ~atis~ying thaix p~rceived need rOr ~ats. An additional ben~it was th~ lowering o~ serum chol2~tarol, low density lipo-prot~in and triglyceride~, all of which hav~ been imp].icated in artery hardening di~eases, 20 HOWQVer~ SPE has th~ s~rious di~advantag~ o~ cau~ing diarrhea, and pla~ma vlkamin A and vitamin ~ level~ ara d~rsa~ed.
The proces for production o~ SPE i~ ba~ically a m~thanoly~i.
~ollowQd by sst~ri~icakio~ and extraation. Th~ SPE proc~s require3 long rQactlon tim~ with alternating additions of fresh 2S tran5estQri~ication catalygt and ~xcss~ methyl ~oybean ~atty acid est2r (RCo2MQ)- Temparatura control is critical because sucrose will char at itR melting point of 185C. Further, in order t~ solubiliz~ sucros0 in ~he esterification solu~ion, it must be add~d 810wly as a micron-sized powder (produced by r~duction o~ ~ucros~ crystals in a hammermill) to a solution o~
RCO2Me containing hal~ as muGh alkali metal soap as sucrose.
A~t~r ~he ~ucrose is partially est2rified, exces~ RC02~e is added and th~ mixtur~ h~atad at 145C for ~-12 hours. The fatty e~ter starking mat~rial, RCO2M2, is ~ot mads in ~ continous process. Rather, it i~ made in a batch proc~ss and mu~t be washed with watox to recover all the glyc~rol. ~ommarcial cane ,, .
sugar must be reduced to a consist~ncy of fine talcum powder, on ths order of 50 microns or below i~ order to promote its disolution in the reaction solution. Two stage addition of RC02Me is necessary to prevant disproportionation to sucrose, which will char, and sucrose higher est:er3. For each pound of SPE made, one pound of RC02Me must b~ c:leaned up and recycled.
Because a large excess of RCO2~e is use~d, the isolation of SPE
is a complex process nea~ssitating liquid-liquid e~tractions at OC with methanol or ethanol to remov~ unreacted RCO2Me. A
lo ~inal extraction with hexane and clay bleaching is neceæsary to produce a li~ht colored p~oduct. The major yield loss occurs during the puriflcation process.
Patent 3,521,827 di~clo~as a preparation of SPE by means of a solvent~fre~ interest~rificatlon using phenyl est~rs. However, phenol is liberated during the reaction. Since phanol is extr~ly toxlc and cau~tic, lt contaminate the product and is vary di~ficult to separate. Accordingly, thi~ proces~ did not prove satis~actory ~or synthe~is o~ S~E~ ~or the ~ood industry.
Patent 3,963,699 call~ ~or ~olvent-fr~e transe terification involving heating a ~ixturQ o~ the polyol containing four hydroxyls, ~atty acid lower alkyl estQr, and alkali m~tal fatty acid ~oap in presenco o~ a ba~ic cataly~t to gorm a homogenous m~lt, and subse ~ en~ly adding to the r~ac~ion product o~ that heated mixture exc~s~ fatty acid lower alkyl ester~ to obtain the S~E.
U.S. patent 4,034,083 also to Proctor and Ga~blo discloses fortification o~ ~ha SPEs with fat-~oluble vita~in~ ~o form phar~a~utical ao~position~ ~or tx~ating or prQventing hyper-cole~t~role~ia in ani~al~, and Sor us~ in low calorie foods.
Thi~ mixtur~ i~ reguired because eatinq SPE causes vitamin depletion as noted above.
U.S. patent 3,818,089 indicates that the C12-~18 ether analogs o~ glyceride~, glycQrinQ al~yl ethers are not digestibl~
A~ shown ln C. U. Werl et al) Food ~osmet. Toxicol., 9 (1971) p. 479, ~onopropylen~ glycol (MPG) can be ingested with no .
s ~
harmful effects. It is metaboliz~d by thP same metabolic pathway~ us~d by carbohydrates. MPG is currently u ed a~ a humectant in shredd~d coconut and in moist cake mixes~ Ethylene oxide and propylen~ oxide-based food additives, such as propylene glycol mono-stearate, are recognize. ~ood additives, wikh allowable limit~ being prescribed by code.
Booth, A., and Gros, A., in a paper entitled Caloric Availability and_ Digestibility _of New-Tvpe Fats, Journal of the American Oil Che~ists Society, Vol. 40, October 1963, pp. 551-553, disclose that in rat ~e~ding studi~s amyloss palmitate,amylose stearate and amylose oleatQ are only 17 29~ digested. A
r~lated prior paper o~ Gros, A., and Feuga, R., entitled Propertie~ _of the FattY Acid Esters o~ Amylose, Journal of the ~merican Oil Che~ists Society, Vol. 39l January 1962, pp. 19-24 disclo~g that thas~ estars do not have sharp ~lting points and are extremely viscous when m~lted. The densiti3s wers so~ewhat greater than tho~e o~ corr~spondlng fr~e fatty acids and glycerides. While tha int~rQ~t was ~or us3 as dip-type coatings in both foods and non-~oods, no in~ormation app~ars to be available concerning the ability of the3~ compound~ to mimic sensory and ~unctional properki~q o~ triglyc~rido fat~ in foods.
~ angold and Paltau~ Qxt~nsiv~ly r~vlewed ethar lipid in th~ir book E~he~ p~ Acad~mic Pres~ 19~3. They report that trialkyl glycol having long alkyl chain~ ar~ not hydrolyzed or absorbed when ~ad to rats. The~e long chain trialkylat~d glycols ar~ reportedly non~toxic and do not int~r~ere with abs~rption of ~ f ats and f at ~olubl e vitamins . How~v0r, thsy ar~ oxidized much : ~ora oasily than normal ~ats having comparable acyl chains, so stability a~p~ars to b~ a problem. Furth~r, the e co~pounds are difficult and ~xp~n~iv~ to prapare.
Canadlan pa~nt 1,106,681 i3~u~d to Sw~t and Co~pany in 1981 relate~ to dialkyl glyc~rol e~hers wh$ch arQ ab~orbed only in s~all amount~ when ~d to rats. Blend~ ara said to exhibit the : phy~ical and organol~ptic propertias of conv~ntional ~at~.
U.S. Patent 2,962,419 di~closes ~sters of neopentyl type alcohol~ such as pentaerythritoltetracaprylate. Tha alcohols . . , contain from 1~8 hydroxyl radicals and include at lea~t one neopentyl nucleus while the fatty acids contain at least four carbon atom~. Thay were shown to b~ no~-hydrolyzable by pancreatic lipaseO Rat~ ~ed with the~e sstQrs had lower levels of lipids in there serum. HowQver, in demand ~eeding studies, rats which r~ceived these neopentyl alcohol e~tsrs ate more food than th~ control rats and thus there was no di~ferenc2 in weight gain a~ong tha two group Accordingly, it i~ possible khat ~at craving i~ ~timulated by these compound~ rather tha~ satis~ied.
Ratrofat~ are estera of fatty alsohols with tricarboxylic acid~. It is reported that they ar~ not hydrolyzed by pancreatic lipase and thus may have poten~ial as non-a~sorbable fat substitutes. However, increased stool bulX resulting ~rom ing~stion o~ tha non-absorbable retro~ats is reported to be a potential drawback.
Alkyl est~r~, such as dodecyl ester o~ 2,3-ditetradecyl-oxypropionic acld have been suggested as a fat substitute but were ~ound to b~ meta~olized and ab~orbed in in vivo rat ~tudy ~periments. The alkyl e~ter group was split o~f ~irst, followed by th~ alkyl ether groups.
A~ r~port d in JACS, Vol. 8 (1958) pp. 6338 f~ and JAOCS, Vol. 36 (1959) pp. 667 ff, th~ USDA ha~ synth~sized a number o~
d~glyceride e3ter5 0~ short chaln diba~ic acid~ ~or potential application in ~oods. Di~ arin glyc~ride esters of dicarboxcylic acid~ were found to b~ poorly dig~stad and utilized by rats. Disteari~ adipat~ was almo~t complet~ly non-digested while adipo~taarin wa~ only 58% digested in rat feeding trials.
In contrast, the ol~ost~arin and dolein estQr~ o~ dicar~oxylic acids w~re mor~ digestible and utilized. The symetrical diglyc~rlde e~ter~ of fumaric, succinic and adipic acid~ are more viscou~ th~ cottonsee~ oil and coconu~ oll. ~he~ may hav~ use a~ pan gr~ase~, slab drQs~ings or surfa~s coating~ ~or fosds.
U.SO Pat~nt 3,579,548 to Proct~r and Gamble in 1371 disclosas use5 0~ triglyceride ester~ o~ alpha-branch~d carboxylic acids as low calori~ ~a~s. The~e esters exhibit~d a coe~icient of absorbability ranging ~rom about 0-50 as compared to 90-100 for ; -8-ordinary triglyceride It is postulated that the alpha-branched carboxylate structure prevents the compounds ~rom being hydrolyzed by pancreatic enzyme~. Proposed use9 are as fat replacemQnt~ in salad oil, mayonnaise, margarine and dairy product~.
S PolyoxyethylQn~ stearate is an emul~i~y$ng agent with fat like properti~s that yield~ only 4.2 kcal/gra~ when ingest~d.
The molecule is hydrolyzed to stearic acid which is metabolizable, and to polyoxyethylenediol which i5 excreted unchanged. The use o~ fat-like ~mulsifying agents as low calorie ~at uhstitute has bQen suggested in the literature.
U.S. Patent 3,337,595, issued to Nalco Chemical in 1967, disclose a method o~ producing ~atty acid est~rs of polyoxypropylated glycerol o~ the ~ormula glycsrol (propylene ~ oxide~n(fatty acid~)m, which ~rom the molecular weisht values in the patent result ln n - 9 - 16 and m ~ l or 2. The~ esters ara disclosed to be useful ~or controlling, ~uppressing and/or preventing ~oaming o~ aqueous sy~tem3 having foa~ing tendencies in industrial proc~sse~. Illu3trative types o~ aqueous systems are cellulo~ic ~uspen~ion~ in~olved in the manu~actura o~ paper, s~wage disposal system~, detergent ~ontaining systems, saponin-containing systems, protaln containing ~y~te~3 and the like. 1,2-propyl~ne oxid~ is adducted on glycerol to produce a polyoxypropyla~ed glycerol (PO~) with a molecular weigh~ in the ranga of 600 l,000. Fatty acid est~r~ are pr~pared by stoichiomatric , e~tori~ication o~ the POG with saturated or unsatura~ed alphatic monocarboxlic acids having chain lengths o~
12-22 carbons. Th~ ~st0rification procQss occurs in ~ha range of 200-240C und~r a vacuuffl on the ord~r of 30-50 m~ mercury.
Sp~cific ~xamplQ~ ara dir~c~Qd ~o s~eariG acid dlesters of polyoxypropyl~tQd glyc~rol having a ~ol~cular w~i~ht o~ 700. An e~ulsi~ier i~ r~quired in tha an~ oa~ing formulations, the sp~cific ~xampla~ baing direct~d to polyo~yathylene glycol 400 : di-oleate. Th~ monocarboxylic acids u~ed to form tha diesters are those having Cl~_22 carbon~. There is no speci~ic disclosure o~ a triester or o~ completo etherification with _g _ . 9J ~ ~
propylene oxide. ThPre is also no disclosure o~ the use o~ the diester co~pounds as fat s~bstitutes in food products.
Gibson, U. H., and Quick, Q., in a paper entitled The Averaae olecular_ Structure of Base~3~_ed Low-Mole Adducts of S Pro~Ylene Oxide to _Glycerin, J. Applied Polymer Scl., Vol. 14 (1970) pp. 1059-1067 indicate that with a molar ratio of glycerin (G) to propylen~ oxlde (PO) of 1:3, 63% of the adduct product will have all three hydroxyls propo~ylated, with 1:4,92% are propoxylated, and with a ratio o~ 1:5 all the original hydroxyls will be propoxylated.
It is clear that there is a great need in the art for improved fat substitutes that are ea~y to synth~ize and do not have the disadvantages of tha prior art propos~d compounds.
The I~ventlon Obiects:
It is among the obiects of this invention to provide improved non-digestible fat substitute~ compri~iny e~erified epoxid~-sxtended polyol~ (EEEPs) whi~h may b~ used alone as cooking oils, ~ats or waxa~, or a. part o~ food compositions, as a partial or tot~l ~ub~titut~ ~or ~ats or oils.
It i a~other ob~ct oX this inv~ntion to provide a non-dige~tibls, non-ab30r~able, non-caloric fat substitut~ or fat mim~tic useful in ~ood compositions or for ~he prepaxation of food.
Anoth~r ob~ QCt 0~ this invention is to provide improved, sub ta~tially non-digestible ~at substitutes or partial substitut~, o~ ~ ~ epoxid~-extsnd~d polyols wherein tha epoxylation ind~x i~ su~cient to prev~nt a ~ubstantial degree : o~ hydroly~i~ by pancreatic lipas~:
~t i~ another ob;ac~ Or this invention i~ to provide improv~d, substan~ially non-digestibla fat 5ub~titute9 or partial substitute~, o~ esterified epoxide-extendad polyols o~ the J ~; Q) formula P (~) a I c (EPO) n (FE) b wherein ~he epos~ylation index, n, is above about 2, and preferably in he range of 2 - 8;
It is another obj ect of this invention to provide improved ~at ~ titutes which are peracylated epoxide-extended polyols in 5 which thQ polyol~ have 3 - 8 hydroxyl unit~;
It is another ob; QCt of this in~ention to provide improved fat substitutes compri~ing acylated epoxide-extended glycerols wherein the epoxide~ are C3-C6 epoxide~;
It ls another obj ect of thi~ invenltion to pxovi~e i~proved 10 fat substitute~ compri~ing acylated propylene oxide-extended glycerols wh~rein the propo~lation index, n, is above about 2, preferably in th~ range o~ 2 - 8;
It is another ob~ect o~ this invention to provide improved fat ~ubstitute~ comprising estQrifiad epoxide-axt~nded polyols, 15 and pre~erably acylated propyleno oxide exterld~d glyc~rols i which the acyl ~tex~ are CR-C24 compound~ and which have an in vitro pancraatic lipa e hydrolysis index r91ativ3 to olive oil o~ below about 10;
It i~ another ob~ ect o~ thi~ invention to provide acylated 2 0 epoxide-extended polyols in which the acyl groups are of sufficient size to prevent ab~orption through the walls of the digestlv2 ~y tem, the epox~lation index is suî~l~iently high to pr~v~t a subs~tantial desre~ o~ hydrolysi3, and which hav~ good organoleptic prop~rtie~ ~ and whicsh them~lves, and theix 25 hydroly~i~ product~, are non-toxic:;
Ik i~ anoth~r ob~ ~ct o~ thi~ invention to pxovid~ ~mproved fa~ substitute comprising triacylat~d polypropoxyla~ed glycarols in which ths propoxylation index i~ abov~ abcut 2 and prQferably about 5 or above and ~h6~ acyl group3 ars C8_24 compounds, 30 pre~erably C14~18~ and which have a lipase hydrolysl~ index of bQlow abs:~ut 10.
It i~ another ob~ ~ct af this in~Qntion to provide method~ of produc~ g the ~at ~ titut~ o~ this inventlon, and pr~i~erably which can u~ natu:rally availabla oils such a~ ~oyb~an oil as tha 35 sourc~ o~ th~ glycerol and fatty a~id moleties.
. .
It i~ another objPct of this invention to provide improved food composition and produ~ts employing the fat substitutes of this inventlon;
Still further and other ob~ ects will be evident ~rom the speci~ication and claims o~ thiq application.
Summarv:
~hi~ invention comprise3 est~ri~ied epoxide extended po}yol~
~EEEPs), method~ of preparation thereo~, and their use as non-digestlble ~at substitutes (fat mim~tics) having low-caloric ~ood value~, which have good organoleptic charact2ri~tics, are sub~tantially resistant to int2~tinal ab~orption, and do not appreciably hydrolyz~ in th~ digestive tract.
Tha structurQ o~ th~ non-digestibl~ ~at substltutes o~ this i~vention ~ay be generally charact~rized a~ P(~H)a+C
(EPO)n(RCOOH)b~ where: P(OH) is a polyol having a - 1 - 8 primary hydroxyl~ and c ~ O ~ 8 secondary plu~ tertiary hydroxyl~, with a ~ c bein~ in ~he rang~ o~ 3 - 8, EPO is a C3-C6 epoxidQ; ~ ig th~ minimu~ epoxylation index average nu~b~r having a valu~ genQrally equal to or great~r than a and is a n~ber ~u~icient that greater than 95% o~ the primary hydroxyl~ o~ th~ polyol arQ co~vort~d to ~condary or tartiary hydroxyls; and R OOH is a fatty acid acyl ~ai~ty in which R is an alkyl chain o~ 7 or mo~e carbon~, RCOO~ pr~erably b~ing C8_2~, and ~ i5 an av~ragQ nu~b~r ~n th~ rang~ o~ 2 < b ~ (a ~ c).
Suitable polyols include ~ugar~, glycQ~ides or sacaharides which ar~ raacted (eth~rift~d) with C3-C~ ~poxide~ such as propylen~ oxid~, butylene oxida, lsobutylene oxidQ, pentene oxid~ and ~he lik~ to produc~ ~oxid~-~xtended polyol~ (EEPsj h~ving an ~poxylatton index ~ini~um of 2, and gQn~rally in the rang~ 4~ 2 - 8. Sugar may b~ ~olect~d ~rom glucos~, mannose, galactose, arabino~a, xyl08e, ~orbitose, amylose, an~ the like.
-~12-? ~
We prefer ~he triol glycerol, with the resultant ~ormula bein~:
CH2 O-(CRlR2-Cg3~4-~)d~(CRs)X
S
CH-O-(C~lR2 CR3R4-O)9~(cO~s)y C~2-0--(CR1~2-CR3R~ OR~)z where d + e ~ ~ ~ n a~ da~ined abova, x + y ~ z = b as de~ined above, Rl ~ R2 ~ ~ R3 ~ ~ or alkyl, R4 - alkyl, and R5 - C7_23, preferablY C13-17. Where propylena oxide i5 employed a~ the epoxide Rl, R2 and R3 are ~, R4 i~ Me, and d + e ~ ~, the epoxylation (propo~ylation) index, is 2 ~, preferably about 3 - 5, based on in vitro pancreatic lipase acti~ity relativ2 to ol$v2 oilO
The epoxylation index i~ ~u~iclently high khat th~ resultant EEEP3 are resi~tant to digestive tract absorption and in vivo dige~tion by non-speci~ic diqestive or lingual lipa~es. There are ~wo fac~ors to be con~idersd. The ~irst i~ the apoxylation ~, index for non-digestability, th~ ~econd i~ acyl chain l~ngth for non absorption. ~hera n ~ 4 i~ ~ound to b~ the suitabla in vivo ~ thra~hold ~or non-dig~stability, then th~ cuto~f o~ th~ R5 acyl - chain l~ng~h ~or direct ab~orptio~ could be as low as C7 (the octanoatQ ester). Thi~ specia~ (using glycerol and propylene ~- oxid~) would have an average ~W Or 702, but since th~re is a MW
: di ribution in ~he mix~ure, spaci~a Or ~M o~ 586 and 644 would be pre~en~.
~he ~st~r~ o~ tertiary alcohol~ (R3 - ~4 alkyl) or secondary alcohols with bulky sub~tituont~ can provide good pro~ection fro~ lipasQ hydroly~ or example: 1,2-epoxybutane (R4 = ~k~, 2,3 epoxybutan~ (R2 ~ R4 a ~e) ~ both butylene oxid~; 1,2-epoxy-3-methylpr,opane (R3 - :R~ - Me), i~obutylene oxid~; l,2-epoxycyclohexana; and tha l$~, may be usQd.
;~ 35 It should bQ und~rstood that thQ apoxylation index encompas~es the mixtur~s produGed by the bas~ catalyzed reaction .
,,, ~ ,. . . .
, 2. ~i g of the polyol with the epoxide. Thus, where glycerol and propylena oxide are used with Cl6-Cl8 ~atty acids, we have found that a~ compared to olive oil as a representative substrate having a rate of in vitro lipase r~activity of 100, the propoxylation index of 2 or gr~ater has a hydrolysi~ rate value on the order o~ 20-30% of the olive oil. By nonrdigestability we mean a rate b~low about 20%, prQf2rably 10~. Thus, food products could be made or cooXed in a mixture o~ natural fats and the synthetic fat mimetics o~ thi~ invention blended in proportion to provide any predetermined amount o~ fat caloric value. Where n is 4-5, the relative lipasa rat~ is zero. Depending on the organoleptic qualitie~ desired, th~ amount of substitution would range ~rom a few percent, to giYe ~ractional redu~tion in caloric value, to entir~ sub~titituion ~or a non-Galoric product.
Conversely, wher~ th~ ~EE~ product has a relativs lipa~ rate clos~ to 20, di~erent amoun ~ ~ th~ EEEP ~t substitute of this invention could be us~d in the blend tG achieve a desired organolsptic quality or provid~ a paxticular cooking use, (e.g., oil v~. ~at).
zo For example, in ths case oS glycerol and propylene oxide where a - 2, c ~ l, n ~ 2 and b ~ 3, th~ resulting principal compound is triacyl-1,3-di-(2-hydroxypropyl) glycerol ~H3 fX-O-~OR
cH2-O-~2_fc~_o_co~
Conversely, wher~ n - a, e.g., n ~ 3 or ~ore ~or glycerol, the EEEP compound~ og this invention will includ8 polyepoxides in the expoxida-extsnded ink~rlinX between the polyol and th~ acyl ester moiQties. Thus, ~or propylen~ oxid~, ther~ will be present ~H-CH2-0~ and/or ~CH2~CH-O~ links, where ~ i~ 2 or C~3 C~3 more. ~h~ latter lin~a~es predomina~e. Whil~ we do not wish ~o be bound by theory, we b~liev~ that the non-digestibility of the ;3~
EEEPs of this invention is due to the alcohol ester linXage being se~ondaxy rather than primary.
Acylation with one or more C8_24 fatty acids produce an end product ester with physical properties ranging from a liquid oil, through fat~ and greases, and ultimately to wax@s. The resultant E~EP3 are useful in ~ood ~ormulations and for cooking as they hava good mouth feel and characterist:Lcs similar to vegetable oils and fats. Being relatively non-absorbable, non-digestible, and non-toxic they may be substituted :Eor natural or processed lo oils and fats, but have no caloric value.
Example of such fatty acid~ are c;~prylic, capric, lauric, myristic, ~yristoleic, ~t~aric, palmitlc, palmitoleic, rincinoleic, linoleic, linolenia, eleao~tearic, arachidic, behenic, erucic, oleic, and/or heptadecanoic acid. The fatty acids can b~ deri~ed from ~uitable naturally occ:urring or synthetio fatty acids a~d can be ~aturated or unsaturated, including positional and geometric isomers, d~pending on the desired physical propertlss, e.g., liquid or solid, of the fat compound.
Fatty acid~ por gQ or naturally occurring ~ats and oil3 can serve a~ the ~ource ~or the ~atty acid componQnt. For example, ~ rapeseed oil provid~ a good ~ource ~or C~2 ~atty acid.
:~ C16-C18 fatty acids can b~ provided by tallow, soybean oil, or co~ons~ed oil. Shorter chain ~at~y ac~d~ can be provided by coconut, palm kern~l oil, or baba~su oils~ Corn oil, fish oil, lard, olive oil, palm oll, peanut oil, saf~lower seed oil, sesame ; sesd oil, jo~oba oil and sun~lower ssed oil, ar~ example~ o~
other natural. oils which can serv~ a ths source of the fatty acid component. Among the fatty acids, ~hose that are preferred have from about 14 to about 18 carbon atom3~ and are most pre~erably selected ~rom the group con~i~ttng of myristic, pal~itic, stearic, oleic, and linoleic. Th~ pre~erred sourcPs ~or the ~atty acid compon~nt~ ara natural ~ats and oils which ha~e a high contant o~ thas~ fatty acids, a.g., ~oybaan oil, olive oil, cot~nse~d oil, corn oil, tallow and lard.
Best mode examples of the invention include acylated propoxylated glycerol compound mixture~ (APGs) of the ~ormula ~G(PO)n(FE)b], where G is glycerol (i.Q. a ~ 2 and c = 1 in the P(OH)a + c formula above), PO is Propylene Oxid~, FE is a S fatty acid ester moiety, the average propoxylatlon number n is in tha range of 2 - 5, and b i5 an average number between above 2 and 3. SuitablQ fatty acid~ ~nclud~ mixture~ o~ palmitlc acid or heptadecanoic acid with oleic acid. The~3e APGs are resistant to hydrolysi~ by porcine pancreatic lipasel the dominant enzyme in.
~at digestion, in vitro.
E~en where the fatty acid moietie~ are hydrolyzed of~ the EEEPs and APG3 o~ this invention, no outward slgn of toxicity of the resulting EEP wa~ observed in our study. I~deed, even propylene glycol which would be released on cleavag~ of the EEP
ether linkag~ i~ given GR~S (G2nerally Recognized as Sa~e) status by th~ FDA. Propylen~ glycol and its derivatlves are used at low levels in the ~ood industry, 3 .g. a~ ~olvents ~or ~lavors and pharmaceuticals, and in bak~d good~, salad drQ sings and ~auces.
ThQ proc~3~ o~ thi~ invention involves a base (pre~Qrably alkali metal) catalyzed reaction o~ th~ polyol with th~ epoxide.
As noted in the Gibson and Quick paper, supra, the base catalysis opens the oxiran~ ring of the propyl~n~ oxide in thQ addition : reaction to provid~ a predomi~ance of secondary hydrsxyl groups, on th~ order oP 98% sQcondary to 2% primary. We pref~r, in the case o~ gly~erol, to start with a ~at such as soybean oil, split it to form glycerol and RCO2H, and ~eparate th~ glycerol from the fatty acid. Thi~ provides the glyc~rol for th~ base catalyzed pr-~poxyla~ion addition r~action. The resultant G(PO~n~ pxe~erably n ~ ~ ~ 5, is th~n raacted rapidly at high 30 temperature, betw~Qn about 100 to 200~C, in the pre~ence of paratoluQn~ sulphonic acid (PTSA) with a stoichiomstric amount of th~ soybean oil ~atty acid to produc~ the r~sultant APGs mixture ; product. Tha APG~ product can b~ re~in~d a~d bleached in a conventional ~anner, ~.g. with alkali and clay, to pr~vide a cl~an product o~ low color and low acid valu~.
-16~
2 ~ ~
_tailed Description of the Best Mode The following detailed description is by way of example, not by way o~ limitation, of the principle~ of the invention to illustrate the be~t modQ of carrying out the invention.
In this example, the epoxida (EP0~ i~ represented by propylene oxide (PO), the polyol P(OH)a~C by glycerol (G), and the esteri~ied fatty acid acyl moiety (FE) by a mixture o~ either palmitic or heptadecanoir acids with ol~ic acid, to produce a food oil/fat sub3titute/~i~Qtic of the formula ~(PO)~(YE)b~, where n - 2 - 5 and b 3 3. Wlth the addition o~ 5 PO units, all the original polyol (in thi3 example a triol) hydroxyls will ha~e boen etheri~ied (in this exampl~ propoxylated)~
EX~P~ 1 I. Pro~o~ ed Gly~e~ nt~e~is A. Catalyst P~a~a~lon A catalyst solutlon ~or th~ propoxylation reaction is prepared to provide .25 wt % K+ in 6000 gm~ final propoxylat~d product. To prepar0 tha catalyst, 27.59 gram~ powdar~d potassium hydroxide a~d 300 gra~ glyc~rol, G, are charged to a 1000 cc rotary evaporation ~lask and heatsd undar nitrog~n at 75-80C with stirriny ~or about on~ hour. Th0 catalyst goe~ into ~olution leaving a clou~ product which is ~txipped on a rotary evaporator at 60-70C/5m~ ~g ~or one hour to remove water. Th~ theoretical wa~ar los~ i~ l2.38 gram~. The ca~alyst solution (314.62 gms) is added to a dry, nitrog~n ~lu hed 2-gallon stainle3s ~tael stirred reactor.
B. ProPox~l~tl~n Reaction, 1:3_G:pO
To prspare propoxylated glyaarol with thre~ oxypropylene units th~ initial glycorol charge i~ 2073.32 gms (i~a., 1773.32 gms charg~d as free glycerol, and 300 gms add~d with the c~talyst '.
,~ ., , charge). The remaining 1773~32 gm~ glycerol (~W = 92.1 gm/mole) was ~dded to the reactor under a continuou~ purge with dry nitrogen. The reactor was heated to 70-75C and nitrogen pressure was adjusted to 20 psig. An initial charge of 500 grams propylene oxide, P0, (MW 3 58.08 gm/mole) wa~ added to thP
reactor, and the reaction exotherm wa allowed ~o carry the temperature up to soc. A~ter th~ reaction was initiated, the temperature was adjusted to 90-95C and the remaining dry propylene oxide was added on a pressure demand basis over an 18 lo hour period. A pres~ure dema~d control valYa system was used to control the addition rate. A re~erence pressure was s~t at p~ig. If the reactor pressure dropped below this pre sure the control valve opened and more propyl~ne oxide wa~ charged to the reactor. When the pressure in~reased to ~reater than 60 psig, the valv~ clos~d. The propylene oxide wa~ contained in a yoke that wa~ suspended on a weight load cell, thareby permitt~ng the charging of the correct amount o~ propylene oxid~. To prepare propoxylated glycerol with three oxypropylene units the total propylene oxide charge i9 3926.68 gram3. Since th~ yoke had a psig nitrogen pre~ ur~ head, the overall reactor pressure increas~d to 80 psig when all the propylen~ oxide wa~ pu~hed out of th~ load cell yoko into the reactor. A~tQr all the propylene oxid~ had been added, the rQaction mixtur~ wa~ allow2d to cook out for an additional 4-6 hour~ to insure complQt~ reaction.
When th~ reaction wa~ c4mpl~ta, th~ product was removad hot from th~ reactor ~nd wa~ tr~ated with Magn~solR (4 grams per 2S0 ~rams product) ~or two hours at 100-llOC in order to remove the K+ catalyst. The r~sulting product was vacuum filtered through a C~lliteR (purified diatomacaou~ silica) bed at 60-~OC
to provide t~a pure olig~meric polyol. Hydroxyl Nu~ber, VPo molecular w~ight, G~l Per~ation Chromatography (GPC) analysis, and 13CNMR w~r~ used to charact rizs the hydroxy propoxylated glycerols mixture, HPGs. For thQ HPGs with thrbe oxypropylen~
unlts, polydispersity by GPC analy~i3 1~ 1.19 and the molac~lar weight calculat~d ~rom the Hydroxyl Numb~r is 266 gms/mola.
~18-II. Svnthesis_of APGs (Tri acylated HPGs).
In a typical ynthesis, a solution of 0.035 moles of redistilled acyl chlorides (a mlxture of a 1:5 molar ratio of either palmitoyl or heptadecanoyl chloride to oleeyl chloride) in dry chloro~orm (20 ml) is add~d dropwise to 2 stirred solution o~
O.01 mole of the HPGs in.dry chloroform (20 ml) and dry pyridine (6 ml). The addition is made at room temperature, under an atmosphere o~ dry nitrogen, and stirring is continu~d for a furth~r 24 hours. A phase separation occurs in the reaction vessel. At he end o~ the reaction, the mixture is added o water (500 ml) and extracted several times with pstroleum ether ~3 X 500 ml~. Tha comb$ned organic phase is than washed with water (2 X 500 ml), dilute aqueou~ HCl (2 X 500 ~l)~ water (2 X 500 ml~, a~ueous potassiu~ bicarbonatQ (2 X 500 ml), and then water (~ X 500 ml~, and dried ovQr anhydrous sodiu~ sulphate be~ore ~vaporation o~ th~ solv~nt. Prior to column chromatography, any free fatty acid~ still prQsent are methylat~d with ethereal diazomethane. Th~ crude acylat~d propoxylated glycerol mixtur~s (APGs) produc~ is puri~ied by passag~ down a silicic acid colu~n, eluting with a gradi~nt of di~thylether (O to lO0~ in petrol~u~ eth~r. Overall yield~ ~or th~ ~PGs s~nthe3i~ fall in ~ha rang~ o~ 5g-75%~ Puri~y and 3tructure of th2 APG ~roduat are confirmed by IR and lH N~R spectroscopy, and by Thin Layer Chro~atography (TLC~o The r~su}tant APG products are all oils at room temparature and generally vsry acceptable pal~ y~llow color, hut which can be easily bleachsd.or clari~ied by passing through char~oal. The APG~ exhibited raverse visco3ity, with tha n a 1 and n 3 2.2 productg (sea ~xa~pl~ 2 b~low) being slightly mor~ vi~cous than oliva oil, and th~ n ~ 5 and n ~ 8 products slightly l~s ~iscous than olive oil. Similarly the n 8 5 and n - 8 did not solidify at 5C wh~le th~ n ~ 1 and n ~ 2.2 exhibited partial crystallization at 5C. The molecular weight ranges are determined as ~ollows: n ~ 1, 884-1000, n ~ 2.2, 942-1116:
n - 5, 1058~1~90; and n - 8, lQ58-13~8 assuming th~ ~rioleoyl --19~
?~
derivatives and including 95% o~ the total mass of the polymeric mixtur~. All Exhibited organoleptically acceptable propQrties, having a bland oily mouth ~eel without belng slimy.
III~
Pancreatic Lipase EXAMPLE_2 Following the above procedur~ in Exa~ple 1, a number o~ APG
products o~ the EEEPs of this in~ention we.re prepar~d in which n was varied in the range of ~rom 1-8 by control o~ th~ amount of PO in th~ reaction. 100 mg of the APG Pat or oil o~ the in~ention to b2 tested is add~d to 10 ml o~ bu~fer containing 1 mM NaCl, 1 2M CaCl~, 3 ~ daoxycholate, 2 mM trl~, and 10 g/l o~ gum arabicO The mixtura is vigorou~ly shakan in a capped t2st-tube, and th~ e~ulsion is transf~rred to th~ pH stat r~action Ve~8~1. The pH i~ titratad to 8.0 using a Radiomater pH
stat (comprising a TTA80 titration assembly, a TTT80 titrator, and ABU80 autoburett~ and a pHM82 pH meter). Porcin~ pancreatic lipa~ (0.1 ml, equivalent ~o 1000 unit9 0~ QnZy~Q, at p~ 8.0) is added, th~ p~ rap~dly ra-~uilibrat~d to 8.0, and then the reaction ~ollow~d OVQr a 20'~inut~ period by autotitratio~ with m~ aqusou~ NaOH. m a initi21, linear rat~ i~ reported a~
2S micro ~ole3 Og NaO~ p~r hour requlred to ka~p ~h~ pH constant by neu~ralising th~ ~ree fat~y acid~ r~l~a.ad by th~ action o~
pancr~atic l~pa~e.
Tha r~ult ar~ givsn b~low in Tabla I, expras3ad as an average o~ 4 deter~inations, r~lati~a to oliv~ oil a~ a control 30 (100~3, wher~ the EPO i~ PO and thQ FE i9 as in Examp}2 I, part II.
, , .
2 ~ ~
Table I Di~stibility_(Lipase Activitv) ~y~ 3~~elative Rate*
Control: Olive Oil 100 Invention APG~ G(EPO)n(~E)b n - 0 76.2 ~ - 1 46.2 n = 2.2 1809 n = 5 0 n ~ 8 * Average o~ ~our determinations.
Bas~d on the above Tabl~ I data, at n - 3 th~ lipa e hydrolysis rate is about 10%, and at n 3 4 it is about 5%. W~ pre~r the lipase hydroly~$s rat~ to b~ below a~out 10~.
The corr~sponding ac~tat~ adducts of th~ te~ted ~PG~3 0~ Table I (n ~ 1, 2.2, S and R) w~ro assayed by Ga3 Liquid Chro~atography ~packQd column) to show th~ di tribution o~ polypropy:Len~ oxide units ln each. ~hQ re~ult~ are ~hown in Table II:
% Area by G~C (P2cX~d Colu~n) . ~, _ - G:F0 Adduct PG G I:l 1:2 1:3 1:4 1:5 1:6 1:7 1:8 1:9 l:lC
G(P0)1 ND 31.l 46.~ 19.9 2.7 _ _ _ _ _ .
__ __ _ _ _ . _ G(PO)a,~ ND 2.1 22.7 40.5 28.0 5.9 0.7 _ _ 30 GtP0)5 t ND ND 1.4 16.I 34.5 28.5 13.6 5.1 0.8 . _ _ _ _ _ _ G(PO)g t ND ND ND 4 9 13 3 22 3 25 8 22.6 8.3 2.7 ND
ND - Not detectabl~ t ~ tracQ P5 - propyleneglycol G = glycol Th~ above compon~n~s r~prese~t 90~ o~ ~he ~as~ ~rac~
in~egral, except for G(P0)8 where the valu~ was 67.8% du~ to ~ .. .. . .
~ ~ 2 ~ ~
presence of unknown additional components, (NOT triacetin). The area % not corrected to give mass or mole % (FID response factors unknown).
Where the APGs product averag~ molecular weight is too low, below about 600-900, it is not useful a~ a no~-digestible ~at substitute because it will be directly absorbed in the gut. We believe the non digestibility o~ ~h~ APG~ product o~ this invention is due primarily to t~e presence of secondary alcohol ester linkages.
IV. IN VIVO Testin.
EXAMPhE 3 FEEDING ST~DIES
Spra~u~ Dowley weanling rats (male) were ~ed a laboratory chow di~ containing 2.5% by weight o~ two di~ferent test com~ound~: ~ikhor th~ n ~ 2.2 conposition or th3 n - 5 compo~ltion o~ ~xample 2, each containing 18~ o~ heptadecanoic acid a~ a mark~r, the balance of the fatty acid ~acyl) ~oiaty in th~ EEEP t~t compound being oleic acid. Total dietary lipid ws kept at 10% (by wQight) with 2.75% added corn oil, the labo~atory chow alr2ady containing 4.5% lipid. Also, a known ncn dige~tibla mark~r compound, 1,2 didod~cyl-3-hexadecyl glycQrol, was add~d to tha diat~ at 0.25% (by w~ight) lav~l.
The ~eeding trial continuad ~or ~hree weeks, during which tim~ rat body wQight gain increas~d at a rata equal to that of control anlmal~. No outward 3igns o~ toxicity w2r~ obs~rved.
F~ce~ w~re collec~d and analys d for lipid cont~nt, u~ing a GLC
method basAd on heptadecanoic acid and 30 1,2-didod2cy1 3-h~xad~oylglycerol ~ark~r~. The data show the following percqntag~ recovQries o~ heptad~canoic acid (HDA) in the ~ces:
-~2-3 2, TAl~LE III Non-Digestability %HDA as Total Free Fatty%HDA Still Fecal Test Compound~ Acid Estsrified HDA%
n = 2.2 12 6 18 ~ - 5 13 31 4~
The percen~ages listed under %HDA a~ Free Fatty Acid3 xepre~ents tha percentage o~ the test compound that was not ab~orbed, but the HDA moiaty of which wa~ hydrolyzed in the ~ut or in th~
~eces by digestive enzymo3 or microbial action. ~h~ parcentages listed undar %HDA Still Esterified indicat~ th~ percentage 5till in original ~orm, not hydrolyzed in gut or ~ce~. ThQ last column shows the total o~ the two pr~ceeding columns, being the p~rcentage not absorbed or digested.
The data show that thæ t~st co~pounds, particularly the n - 5 compound~ (pentahydroxypropylglyc~rol), ar~ suitably resistant to overall digestion, which include~ hydrolysis and absorption in th~ upper intastine o~ the rat, and some hydrolysi~ and utilizatio~ by th~ microbial population o~ th cecum, colon, and fec~.
Th~ sy~th~ is above involvlng propyl~ne oxid~ can be employ~d ~or apoxylation with bu~yl~n~ oxid~ and isobutylene oxide~ to produco the corrosponding epoxld2 ext~ndad polyols which are then acylat~d, pra~erably p~racyla~ed as ab~ve~describe~.
It should be under~tood tha~ var~oll3 modifications within the ~cope o~ this inv~ntion can b~ mado by one of ordinary skill in the art ~i~hou~ d~parting ~ro~ ~he ~pirlt ~her~or. We there~or~ wi~h our invention to ba d~ined by the scope o~ the ap~ended clai~ as broadly as thQ prior art wlll per~it, and in view o~ thls ~pecification i~ n~ed b~.
~23--
~,:
This invention relate~ to esteri~ied epoxide-extended polyols (EE~s), methods o~ preparation thereo~, a~ thei.r use as non~digestible, non-caloric ~at su~stitutes (~at ~imetics~ ~or cooking and in ~ood compo~itions. The EE~P3 have good organoleptia characteristics, have acceptable lev~l~ o~
lo resistance to overall digestib~lity as measured ~y rat feeding studies. More particularly, the invantion relate~ to acylated epo~ylated glycerol compound mixture~ (A~Gs) o~ th~ formula : [P(OH)a+C(EPO)n(F~)~], where P is a polyol havi~g a ~
: primary hydroxyls, and C - O - 8 secondary plus tsrtiary hydroxyls, with a ~ c boing in tha rangs o~ 3 - 8, EPO is a C3 ~ C6 epoxida, FE is a ~atty acid acyl moiQty, n is the minimum epo~yl~tion indQx averaga num~er having a valua g~nerally equal to or great~r than a and i8 a nu~bar ~u~cient that greater than 95% o~ the pri~ary hydroxyls of thQ polyol are converted to secondary or tertiary hydroxyls, and 2 ~ b C a + c, which are resistant to hydEoly~is by pancreatic lipase. The ; rasuI~ant E~EPs may have physic~l prop~rtie~ ranging from a liquid oil, through ~t and gr~a~e~. Th~y are us~ul in ~ood formulations and cooking as ~hey havq good mouth ~esl and characterist~ C9 ~imilar to v~g~ta~l~ oil~ and fats. Being relativ~ly non-absorbabl~, non-dig~stible, and non-toxic they may be sub~ u~ed ~or natural or process~d 9il9 and fat~, but have low caloria value.
8ack round:
T~e accumulation of medlcal eviden~a in recent years r~garding tha ad~ers~ health implication~ o~ high ~at diats, prinolpally heart attackQ, atherio~cl~rosis and ov~rweight, has caus~d con~u~rs to b~co~ axtr~msly concarn~d about their dl~ts~ It i~ e~timat~d that between 70 - 80% of U.S. adult ~emale~ follow a weight reducing di~t at lea~t onca a year. Men , -2- ~
, . . .
~L C~ r3~
are also concerned about their weight and cholesterol levels.
The concerns of both men and women have given rise to diet fads, diet drlnks e~pecially in the so~t drink, wine and beer indu~try, and exercise programs and health club8, Common obesity is one of tha mosk prevelant metabolic problems among people today. Fate and oils are n~cessary ~or balanced nutritlon. Howe~er, he average consumer simply con~umes more than is needed for proper nutrition. Fat, at 9 calories per gram, as compared to 4 calories p~r gram ~or carbohydrates or proteins, i9 tha mo~t concentrated dietary energy formO It is estimated that ~at c:onstitute~ about 40~ of the total calories in the typical western diet. Fats are consumed directly in mea~s, spreads, salad oils, and in natural produce such as nuts and avocados. Fats and oils arQ consumed as a re~ult of absorption or incorporation in the ~oods during baXing and frying. The vast incr~ase in consu~ption of fast foods i5 a major contributor to tho increa~ in the a~ount of dietary ~at sincQ ~ast foods rely ext~nsively on f~ying processes employing ~at~ and oils. In addition, the snack food industry : 20 uses larg~ a~ount~ of fats and oils in the production of potato chips, corn chips and other ~nack items. For example, in 1981 the USDA ~stl~ated approximately 12 billion pounds of fat and oil w3re ussd in sdibl~ products, predominately baking, frying fats, maryarina, salad oil and/or cooking oil.
Ther~ is thus a clear i~dication that there i~ an snormous potential h~alth ~ood mar~et ~or a ~at s~bstitut~ or fat mimet1c that i~ eith~r ~ntiraly non-dig~stibls, or ha~ reduced caloric value. Man~ nutxitionists b~liev~ that ~mericans typically rely on fats for too large a proportion of calorias in th~ir diet.
Th~ National ResQarch Council, for example, has recormended that ~ Americane redur0 the proportion of th~ir di~taxy calories coming : from fats ~ro~ 40% to at }ea t 30~. Replacement o~ ~ats in the diet with non caloric sub~titu~es i8 a ~ore ~fficient way of reducing caloric intake than r~placing sugar or carbohydrates b~cause gram ~or gram, th~ substitutlon o~ non calorlc fat substitute~ is more than twioe as ~ective than reducing ~3-~ , 2 ~ '3 carbohydrate content with such things as saccharinP or Nutra-sweet.
One of the difficulties in ~li~inating fat from the diet is the fact that fats and oils are all-perva~ive in food products.
In part, this i~ b~cause th y play an i~portant role in the organoleptic acceptability of food products. For a fat substitut~ to bs acceptable, it must ba non-digestible, that is, not hydrolyzed in the digestive tract. In addition, it should not be dirQctly absorbed through the intestinal wall. While some t~pes of ~at substitutes may be non-digestible, they are not of su~ficiently high molecular weight to prevent them from being absorbed through tha intestinal wall. Tha thxeshold moleculax weight o~ non-ab~orbability for lipophilic molecules appears to be about 600.
In addition, the fat qubstitute mu3t it~el~ be non-toxic at high lev~ls o~ ing~stion. It mu~t contaln no toxic r~sidue or impuritie~. To th~ extent that a fat ~ubstitute may bQ partially hydrolyzed in the dige~tiv~ tract, any hydroly3is products must be non~toxic and/or ~etabolizable. I~ mQtabolizable, th6y should have very low caloric valu~ In g~naral, fat sub~titutes mu~t be without any seriou~ medical side a~ect~.
Th~ ~at ubstituts~ must al~o have good orga~oleptic gual$tie~ of mouth ~el and havs no taste. In addition, fat substitutes mu~t hav~ appropriate physical pro~Qrties ~or use in food composition~. That i~, thay should b~ liqutds or Yolids depen~ing on whether they ar~ ua~d a3 oil or ~hortening substitute~, and wher~ used for cooking, ~ust be thermally stabla. Whil~ certain pclysaccharide gums hav~ been used as thickening agents, bulking agsnts or fillers in low-calorie foods, they can give a pro~uct a "slimy" mouth ~e~l and are unsuita~la ~or cooking as they have no tharmal stability.
ACCQPtab1e synthatic fats would b~ add~d in large quantities (30 60~) to ~alad oil~, cooking oil~, ~argarine~, butter blends, ~ayonnaise, short~nings and the like to creata a new class o~
low-calorie product~. Whil~ "low caloria" mayonnaise and salad dressing~ are pr~s~ntly available, the reduction in calories is ~4-2 ~ ~
achieved by increasing the water content with a corr~sponding loss in the organolepkically '~rich" taste o~ such product~.
A currant review of the ~ield is found in a ~eature article entitled "Gett1a~ The Fat Out - Researcher~ Seek Substitutes For ~Yl~=Ea~ _Ea~" JAOCS, Vol. 63, No. 3, (March 1986) pp. 278-286, 2~8.
On~ prior ~rt proposed fat substitut~ i8 sucro~a polye~er (SPE), shown in UOS. patents 3,600,186 (Matson, et al. 1971), 3,521,827 and 3,963,699 (Rizzi, et al., 1976) of Proctor ~
Gamble. The SPEs are produced by kha reaction o~ a monosacch~ride, disaccharide or sugar alcohol having a minimum o~
~our hydroxyl groups with fatty acids ha~ing ~rom 8-22 carbon atoms. It was reported in "Chemical and Engineering News"
(July 26, 1982, page 32) that incorporating SPE aa a partial replacem~nt o~ tha fat~ in th~ diQt~ o~ ten obe~ patients dropped thQir caloric intake whils ~atis~ying thaix p~rceived need rOr ~ats. An additional ben~it was th~ lowering o~ serum chol2~tarol, low density lipo-prot~in and triglyceride~, all of which hav~ been imp].icated in artery hardening di~eases, 20 HOWQVer~ SPE has th~ s~rious di~advantag~ o~ cau~ing diarrhea, and pla~ma vlkamin A and vitamin ~ level~ ara d~rsa~ed.
The proces for production o~ SPE i~ ba~ically a m~thanoly~i.
~ollowQd by sst~ri~icakio~ and extraation. Th~ SPE proc~s require3 long rQactlon tim~ with alternating additions of fresh 2S tran5estQri~ication catalygt and ~xcss~ methyl ~oybean ~atty acid est2r (RCo2MQ)- Temparatura control is critical because sucrose will char at itR melting point of 185C. Further, in order t~ solubiliz~ sucros0 in ~he esterification solu~ion, it must be add~d 810wly as a micron-sized powder (produced by r~duction o~ ~ucros~ crystals in a hammermill) to a solution o~
RCO2Me containing hal~ as muGh alkali metal soap as sucrose.
A~t~r ~he ~ucrose is partially est2rified, exces~ RC02~e is added and th~ mixtur~ h~atad at 145C for ~-12 hours. The fatty e~ter starking mat~rial, RCO2M2, is ~ot mads in ~ continous process. Rather, it i~ made in a batch proc~ss and mu~t be washed with watox to recover all the glyc~rol. ~ommarcial cane ,, .
sugar must be reduced to a consist~ncy of fine talcum powder, on ths order of 50 microns or below i~ order to promote its disolution in the reaction solution. Two stage addition of RC02Me is necessary to prevant disproportionation to sucrose, which will char, and sucrose higher est:er3. For each pound of SPE made, one pound of RC02Me must b~ c:leaned up and recycled.
Because a large excess of RCO2~e is use~d, the isolation of SPE
is a complex process nea~ssitating liquid-liquid e~tractions at OC with methanol or ethanol to remov~ unreacted RCO2Me. A
lo ~inal extraction with hexane and clay bleaching is neceæsary to produce a li~ht colored p~oduct. The major yield loss occurs during the puriflcation process.
Patent 3,521,827 di~clo~as a preparation of SPE by means of a solvent~fre~ interest~rificatlon using phenyl est~rs. However, phenol is liberated during the reaction. Since phanol is extr~ly toxlc and cau~tic, lt contaminate the product and is vary di~ficult to separate. Accordingly, thi~ proces~ did not prove satis~actory ~or synthe~is o~ S~E~ ~or the ~ood industry.
Patent 3,963,699 call~ ~or ~olvent-fr~e transe terification involving heating a ~ixturQ o~ the polyol containing four hydroxyls, ~atty acid lower alkyl estQr, and alkali m~tal fatty acid ~oap in presenco o~ a ba~ic cataly~t to gorm a homogenous m~lt, and subse ~ en~ly adding to the r~ac~ion product o~ that heated mixture exc~s~ fatty acid lower alkyl ester~ to obtain the S~E.
U.S. patent 4,034,083 also to Proctor and Ga~blo discloses fortification o~ ~ha SPEs with fat-~oluble vita~in~ ~o form phar~a~utical ao~position~ ~or tx~ating or prQventing hyper-cole~t~role~ia in ani~al~, and Sor us~ in low calorie foods.
Thi~ mixtur~ i~ reguired because eatinq SPE causes vitamin depletion as noted above.
U.S. patent 3,818,089 indicates that the C12-~18 ether analogs o~ glyceride~, glycQrinQ al~yl ethers are not digestibl~
A~ shown ln C. U. Werl et al) Food ~osmet. Toxicol., 9 (1971) p. 479, ~onopropylen~ glycol (MPG) can be ingested with no .
s ~
harmful effects. It is metaboliz~d by thP same metabolic pathway~ us~d by carbohydrates. MPG is currently u ed a~ a humectant in shredd~d coconut and in moist cake mixes~ Ethylene oxide and propylen~ oxide-based food additives, such as propylene glycol mono-stearate, are recognize. ~ood additives, wikh allowable limit~ being prescribed by code.
Booth, A., and Gros, A., in a paper entitled Caloric Availability and_ Digestibility _of New-Tvpe Fats, Journal of the American Oil Che~ists Society, Vol. 40, October 1963, pp. 551-553, disclose that in rat ~e~ding studi~s amyloss palmitate,amylose stearate and amylose oleatQ are only 17 29~ digested. A
r~lated prior paper o~ Gros, A., and Feuga, R., entitled Propertie~ _of the FattY Acid Esters o~ Amylose, Journal of the ~merican Oil Che~ists Society, Vol. 39l January 1962, pp. 19-24 disclo~g that thas~ estars do not have sharp ~lting points and are extremely viscous when m~lted. The densiti3s wers so~ewhat greater than tho~e o~ corr~spondlng fr~e fatty acids and glycerides. While tha int~rQ~t was ~or us3 as dip-type coatings in both foods and non-~oods, no in~ormation app~ars to be available concerning the ability of the3~ compound~ to mimic sensory and ~unctional properki~q o~ triglyc~rido fat~ in foods.
~ angold and Paltau~ Qxt~nsiv~ly r~vlewed ethar lipid in th~ir book E~he~ p~ Acad~mic Pres~ 19~3. They report that trialkyl glycol having long alkyl chain~ ar~ not hydrolyzed or absorbed when ~ad to rats. The~e long chain trialkylat~d glycols ar~ reportedly non~toxic and do not int~r~ere with abs~rption of ~ f ats and f at ~olubl e vitamins . How~v0r, thsy ar~ oxidized much : ~ora oasily than normal ~ats having comparable acyl chains, so stability a~p~ars to b~ a problem. Furth~r, the e co~pounds are difficult and ~xp~n~iv~ to prapare.
Canadlan pa~nt 1,106,681 i3~u~d to Sw~t and Co~pany in 1981 relate~ to dialkyl glyc~rol e~hers wh$ch arQ ab~orbed only in s~all amount~ when ~d to rats. Blend~ ara said to exhibit the : phy~ical and organol~ptic propertias of conv~ntional ~at~.
U.S. Patent 2,962,419 di~closes ~sters of neopentyl type alcohol~ such as pentaerythritoltetracaprylate. Tha alcohols . . , contain from 1~8 hydroxyl radicals and include at lea~t one neopentyl nucleus while the fatty acids contain at least four carbon atom~. Thay were shown to b~ no~-hydrolyzable by pancreatic lipaseO Rat~ ~ed with the~e sstQrs had lower levels of lipids in there serum. HowQver, in demand ~eeding studies, rats which r~ceived these neopentyl alcohol e~tsrs ate more food than th~ control rats and thus there was no di~ferenc2 in weight gain a~ong tha two group Accordingly, it i~ possible khat ~at craving i~ ~timulated by these compound~ rather tha~ satis~ied.
Ratrofat~ are estera of fatty alsohols with tricarboxylic acid~. It is reported that they ar~ not hydrolyzed by pancreatic lipase and thus may have poten~ial as non-a~sorbable fat substitutes. However, increased stool bulX resulting ~rom ing~stion o~ tha non-absorbable retro~ats is reported to be a potential drawback.
Alkyl est~r~, such as dodecyl ester o~ 2,3-ditetradecyl-oxypropionic acld have been suggested as a fat substitute but were ~ound to b~ meta~olized and ab~orbed in in vivo rat ~tudy ~periments. The alkyl e~ter group was split o~f ~irst, followed by th~ alkyl ether groups.
A~ r~port d in JACS, Vol. 8 (1958) pp. 6338 f~ and JAOCS, Vol. 36 (1959) pp. 667 ff, th~ USDA ha~ synth~sized a number o~
d~glyceride e3ter5 0~ short chaln diba~ic acid~ ~or potential application in ~oods. Di~ arin glyc~ride esters of dicarboxcylic acid~ were found to b~ poorly dig~stad and utilized by rats. Disteari~ adipat~ was almo~t complet~ly non-digested while adipo~taarin wa~ only 58% digested in rat feeding trials.
In contrast, the ol~ost~arin and dolein estQr~ o~ dicar~oxylic acids w~re mor~ digestible and utilized. The symetrical diglyc~rlde e~ter~ of fumaric, succinic and adipic acid~ are more viscou~ th~ cottonsee~ oil and coconu~ oll. ~he~ may hav~ use a~ pan gr~ase~, slab drQs~ings or surfa~s coating~ ~or fosds.
U.SO Pat~nt 3,579,548 to Proct~r and Gamble in 1371 disclosas use5 0~ triglyceride ester~ o~ alpha-branch~d carboxylic acids as low calori~ ~a~s. The~e esters exhibit~d a coe~icient of absorbability ranging ~rom about 0-50 as compared to 90-100 for ; -8-ordinary triglyceride It is postulated that the alpha-branched carboxylate structure prevents the compounds ~rom being hydrolyzed by pancreatic enzyme~. Proposed use9 are as fat replacemQnt~ in salad oil, mayonnaise, margarine and dairy product~.
S PolyoxyethylQn~ stearate is an emul~i~y$ng agent with fat like properti~s that yield~ only 4.2 kcal/gra~ when ingest~d.
The molecule is hydrolyzed to stearic acid which is metabolizable, and to polyoxyethylenediol which i5 excreted unchanged. The use o~ fat-like ~mulsifying agents as low calorie ~at uhstitute has bQen suggested in the literature.
U.S. Patent 3,337,595, issued to Nalco Chemical in 1967, disclose a method o~ producing ~atty acid est~rs of polyoxypropylated glycerol o~ the ~ormula glycsrol (propylene ~ oxide~n(fatty acid~)m, which ~rom the molecular weisht values in the patent result ln n - 9 - 16 and m ~ l or 2. The~ esters ara disclosed to be useful ~or controlling, ~uppressing and/or preventing ~oaming o~ aqueous sy~tem3 having foa~ing tendencies in industrial proc~sse~. Illu3trative types o~ aqueous systems are cellulo~ic ~uspen~ion~ in~olved in the manu~actura o~ paper, s~wage disposal system~, detergent ~ontaining systems, saponin-containing systems, protaln containing ~y~te~3 and the like. 1,2-propyl~ne oxid~ is adducted on glycerol to produce a polyoxypropyla~ed glycerol (PO~) with a molecular weigh~ in the ranga of 600 l,000. Fatty acid est~r~ are pr~pared by stoichiomatric , e~tori~ication o~ the POG with saturated or unsatura~ed alphatic monocarboxlic acids having chain lengths o~
12-22 carbons. Th~ ~st0rification procQss occurs in ~ha range of 200-240C und~r a vacuuffl on the ord~r of 30-50 m~ mercury.
Sp~cific ~xamplQ~ ara dir~c~Qd ~o s~eariG acid dlesters of polyoxypropyl~tQd glyc~rol having a ~ol~cular w~i~ht o~ 700. An e~ulsi~ier i~ r~quired in tha an~ oa~ing formulations, the sp~cific ~xampla~ baing direct~d to polyo~yathylene glycol 400 : di-oleate. Th~ monocarboxylic acids u~ed to form tha diesters are those having Cl~_22 carbon~. There is no speci~ic disclosure o~ a triester or o~ completo etherification with _g _ . 9J ~ ~
propylene oxide. ThPre is also no disclosure o~ the use o~ the diester co~pounds as fat s~bstitutes in food products.
Gibson, U. H., and Quick, Q., in a paper entitled The Averaae olecular_ Structure of Base~3~_ed Low-Mole Adducts of S Pro~Ylene Oxide to _Glycerin, J. Applied Polymer Scl., Vol. 14 (1970) pp. 1059-1067 indicate that with a molar ratio of glycerin (G) to propylen~ oxlde (PO) of 1:3, 63% of the adduct product will have all three hydroxyls propo~ylated, with 1:4,92% are propoxylated, and with a ratio o~ 1:5 all the original hydroxyls will be propoxylated.
It is clear that there is a great need in the art for improved fat substitutes that are ea~y to synth~ize and do not have the disadvantages of tha prior art propos~d compounds.
The I~ventlon Obiects:
It is among the obiects of this invention to provide improved non-digestible fat substitute~ compri~iny e~erified epoxid~-sxtended polyol~ (EEEPs) whi~h may b~ used alone as cooking oils, ~ats or waxa~, or a. part o~ food compositions, as a partial or tot~l ~ub~titut~ ~or ~ats or oils.
It i a~other ob~ct oX this inv~ntion to provide a non-dige~tibls, non-ab30r~able, non-caloric fat substitut~ or fat mim~tic useful in ~ood compositions or for ~he prepaxation of food.
Anoth~r ob~ QCt 0~ this invention is to provide improved, sub ta~tially non-digestible ~at substitutes or partial substitut~, o~ ~ ~ epoxid~-extsnd~d polyols wherein tha epoxylation ind~x i~ su~cient to prev~nt a ~ubstantial degree : o~ hydroly~i~ by pancreatic lipas~:
~t i~ another ob;ac~ Or this invention i~ to provide improv~d, substan~ially non-digestibla fat 5ub~titute9 or partial substitute~, o~ esterified epoxide-extendad polyols o~ the J ~; Q) formula P (~) a I c (EPO) n (FE) b wherein ~he epos~ylation index, n, is above about 2, and preferably in he range of 2 - 8;
It is another obj ect of this invention to provide improved ~at ~ titutes which are peracylated epoxide-extended polyols in 5 which thQ polyol~ have 3 - 8 hydroxyl unit~;
It is another ob; QCt of this in~ention to provide improved fat substitutes compri~ing acylated epoxide-extended glycerols wherein the epoxide~ are C3-C6 epoxide~;
It ls another obj ect of thi~ invenltion to pxovi~e i~proved 10 fat substitute~ compri~ing acylated propylene oxide-extended glycerols wh~rein the propo~lation index, n, is above about 2, preferably in th~ range o~ 2 - 8;
It is another ob~ect o~ this invention to provide improved fat ~ubstitute~ comprising estQrifiad epoxide-axt~nded polyols, 15 and pre~erably acylated propyleno oxide exterld~d glyc~rols i which the acyl ~tex~ are CR-C24 compound~ and which have an in vitro pancraatic lipa e hydrolysis index r91ativ3 to olive oil o~ below about 10;
It i~ another ob~ ect o~ thi~ invention to provide acylated 2 0 epoxide-extended polyols in which the acyl groups are of sufficient size to prevent ab~orption through the walls of the digestlv2 ~y tem, the epox~lation index is suî~l~iently high to pr~v~t a subs~tantial desre~ o~ hydrolysi3, and which hav~ good organoleptic prop~rtie~ ~ and whicsh them~lves, and theix 25 hydroly~i~ product~, are non-toxic:;
Ik i~ anoth~r ob~ ~ct o~ thi~ invention to pxovid~ ~mproved fa~ substitute comprising triacylat~d polypropoxyla~ed glycarols in which ths propoxylation index i~ abov~ abcut 2 and prQferably about 5 or above and ~h6~ acyl group3 ars C8_24 compounds, 30 pre~erably C14~18~ and which have a lipase hydrolysl~ index of bQlow abs:~ut 10.
It i~ another ob~ ~ct af this in~Qntion to provide method~ of produc~ g the ~at ~ titut~ o~ this inventlon, and pr~i~erably which can u~ natu:rally availabla oils such a~ ~oyb~an oil as tha 35 sourc~ o~ th~ glycerol and fatty a~id moleties.
. .
It i~ another objPct of this invention to provide improved food composition and produ~ts employing the fat substitutes of this inventlon;
Still further and other ob~ ects will be evident ~rom the speci~ication and claims o~ thiq application.
Summarv:
~hi~ invention comprise3 est~ri~ied epoxide extended po}yol~
~EEEPs), method~ of preparation thereo~, and their use as non-digestlble ~at substitutes (fat mim~tics) having low-caloric ~ood value~, which have good organoleptic charact2ri~tics, are sub~tantially resistant to int2~tinal ab~orption, and do not appreciably hydrolyz~ in th~ digestive tract.
Tha structurQ o~ th~ non-digestibl~ ~at substltutes o~ this i~vention ~ay be generally charact~rized a~ P(~H)a+C
(EPO)n(RCOOH)b~ where: P(OH) is a polyol having a - 1 - 8 primary hydroxyl~ and c ~ O ~ 8 secondary plu~ tertiary hydroxyl~, with a ~ c bein~ in ~he rang~ o~ 3 - 8, EPO is a C3-C6 epoxidQ; ~ ig th~ minimu~ epoxylation index average nu~b~r having a valu~ genQrally equal to or great~r than a and is a n~ber ~u~icient that greater than 95% o~ the primary hydroxyl~ o~ th~ polyol arQ co~vort~d to ~condary or tartiary hydroxyls; and R OOH is a fatty acid acyl ~ai~ty in which R is an alkyl chain o~ 7 or mo~e carbon~, RCOO~ pr~erably b~ing C8_2~, and ~ i5 an av~ragQ nu~b~r ~n th~ rang~ o~ 2 < b ~ (a ~ c).
Suitable polyols include ~ugar~, glycQ~ides or sacaharides which ar~ raacted (eth~rift~d) with C3-C~ ~poxide~ such as propylen~ oxid~, butylene oxida, lsobutylene oxidQ, pentene oxid~ and ~he lik~ to produc~ ~oxid~-~xtended polyol~ (EEPsj h~ving an ~poxylatton index ~ini~um of 2, and gQn~rally in the rang~ 4~ 2 - 8. Sugar may b~ ~olect~d ~rom glucos~, mannose, galactose, arabino~a, xyl08e, ~orbitose, amylose, an~ the like.
-~12-? ~
We prefer ~he triol glycerol, with the resultant ~ormula bein~:
CH2 O-(CRlR2-Cg3~4-~)d~(CRs)X
S
CH-O-(C~lR2 CR3R4-O)9~(cO~s)y C~2-0--(CR1~2-CR3R~ OR~)z where d + e ~ ~ ~ n a~ da~ined abova, x + y ~ z = b as de~ined above, Rl ~ R2 ~ ~ R3 ~ ~ or alkyl, R4 - alkyl, and R5 - C7_23, preferablY C13-17. Where propylena oxide i5 employed a~ the epoxide Rl, R2 and R3 are ~, R4 i~ Me, and d + e ~ ~, the epoxylation (propo~ylation) index, is 2 ~, preferably about 3 - 5, based on in vitro pancreatic lipase acti~ity relativ2 to ol$v2 oilO
The epoxylation index i~ ~u~iclently high khat th~ resultant EEEP3 are resi~tant to digestive tract absorption and in vivo dige~tion by non-speci~ic diqestive or lingual lipa~es. There are ~wo fac~ors to be con~idersd. The ~irst i~ the apoxylation ~, index for non-digestability, th~ ~econd i~ acyl chain l~ngth for non absorption. ~hera n ~ 4 i~ ~ound to b~ the suitabla in vivo ~ thra~hold ~or non-dig~stability, then th~ cuto~f o~ th~ R5 acyl - chain l~ng~h ~or direct ab~orptio~ could be as low as C7 (the octanoatQ ester). Thi~ specia~ (using glycerol and propylene ~- oxid~) would have an average ~W Or 702, but since th~re is a MW
: di ribution in ~he mix~ure, spaci~a Or ~M o~ 586 and 644 would be pre~en~.
~he ~st~r~ o~ tertiary alcohol~ (R3 - ~4 alkyl) or secondary alcohols with bulky sub~tituont~ can provide good pro~ection fro~ lipasQ hydroly~ or example: 1,2-epoxybutane (R4 = ~k~, 2,3 epoxybutan~ (R2 ~ R4 a ~e) ~ both butylene oxid~; 1,2-epoxy-3-methylpr,opane (R3 - :R~ - Me), i~obutylene oxid~; l,2-epoxycyclohexana; and tha l$~, may be usQd.
;~ 35 It should bQ und~rstood that thQ apoxylation index encompas~es the mixtur~s produGed by the bas~ catalyzed reaction .
,,, ~ ,. . . .
, 2. ~i g of the polyol with the epoxide. Thus, where glycerol and propylena oxide are used with Cl6-Cl8 ~atty acids, we have found that a~ compared to olive oil as a representative substrate having a rate of in vitro lipase r~activity of 100, the propoxylation index of 2 or gr~ater has a hydrolysi~ rate value on the order o~ 20-30% of the olive oil. By nonrdigestability we mean a rate b~low about 20%, prQf2rably 10~. Thus, food products could be made or cooXed in a mixture o~ natural fats and the synthetic fat mimetics o~ thi~ invention blended in proportion to provide any predetermined amount o~ fat caloric value. Where n is 4-5, the relative lipasa rat~ is zero. Depending on the organoleptic qualitie~ desired, th~ amount of substitution would range ~rom a few percent, to giYe ~ractional redu~tion in caloric value, to entir~ sub~titituion ~or a non-Galoric product.
Conversely, wher~ th~ ~EE~ product has a relativs lipa~ rate clos~ to 20, di~erent amoun ~ ~ th~ EEEP ~t substitute of this invention could be us~d in the blend tG achieve a desired organolsptic quality or provid~ a paxticular cooking use, (e.g., oil v~. ~at).
zo For example, in ths case oS glycerol and propylene oxide where a - 2, c ~ l, n ~ 2 and b ~ 3, th~ resulting principal compound is triacyl-1,3-di-(2-hydroxypropyl) glycerol ~H3 fX-O-~OR
cH2-O-~2_fc~_o_co~
Conversely, wher~ n - a, e.g., n ~ 3 or ~ore ~or glycerol, the EEEP compound~ og this invention will includ8 polyepoxides in the expoxida-extsnded ink~rlinX between the polyol and th~ acyl ester moiQties. Thus, ~or propylen~ oxid~, ther~ will be present ~H-CH2-0~ and/or ~CH2~CH-O~ links, where ~ i~ 2 or C~3 C~3 more. ~h~ latter lin~a~es predomina~e. Whil~ we do not wish ~o be bound by theory, we b~liev~ that the non-digestibility of the ;3~
EEEPs of this invention is due to the alcohol ester linXage being se~ondaxy rather than primary.
Acylation with one or more C8_24 fatty acids produce an end product ester with physical properties ranging from a liquid oil, through fat~ and greases, and ultimately to wax@s. The resultant E~EP3 are useful in ~ood ~ormulations and for cooking as they hava good mouth feel and characterist:Lcs similar to vegetable oils and fats. Being relatively non-absorbable, non-digestible, and non-toxic they may be substituted :Eor natural or processed lo oils and fats, but have no caloric value.
Example of such fatty acid~ are c;~prylic, capric, lauric, myristic, ~yristoleic, ~t~aric, palmitlc, palmitoleic, rincinoleic, linoleic, linolenia, eleao~tearic, arachidic, behenic, erucic, oleic, and/or heptadecanoic acid. The fatty acids can b~ deri~ed from ~uitable naturally occ:urring or synthetio fatty acids a~d can be ~aturated or unsaturated, including positional and geometric isomers, d~pending on the desired physical propertlss, e.g., liquid or solid, of the fat compound.
Fatty acid~ por gQ or naturally occurring ~ats and oil3 can serve a~ the ~ource ~or the ~atty acid componQnt. For example, ~ rapeseed oil provid~ a good ~ource ~or C~2 ~atty acid.
:~ C16-C18 fatty acids can b~ provided by tallow, soybean oil, or co~ons~ed oil. Shorter chain ~at~y ac~d~ can be provided by coconut, palm kern~l oil, or baba~su oils~ Corn oil, fish oil, lard, olive oil, palm oll, peanut oil, saf~lower seed oil, sesame ; sesd oil, jo~oba oil and sun~lower ssed oil, ar~ example~ o~
other natural. oils which can serv~ a ths source of the fatty acid component. Among the fatty acids, ~hose that are preferred have from about 14 to about 18 carbon atom3~ and are most pre~erably selected ~rom the group con~i~ttng of myristic, pal~itic, stearic, oleic, and linoleic. Th~ pre~erred sourcPs ~or the ~atty acid compon~nt~ ara natural ~ats and oils which ha~e a high contant o~ thas~ fatty acids, a.g., ~oybaan oil, olive oil, cot~nse~d oil, corn oil, tallow and lard.
Best mode examples of the invention include acylated propoxylated glycerol compound mixture~ (APGs) of the ~ormula ~G(PO)n(FE)b], where G is glycerol (i.Q. a ~ 2 and c = 1 in the P(OH)a + c formula above), PO is Propylene Oxid~, FE is a S fatty acid ester moiety, the average propoxylatlon number n is in tha range of 2 - 5, and b i5 an average number between above 2 and 3. SuitablQ fatty acid~ ~nclud~ mixture~ o~ palmitlc acid or heptadecanoic acid with oleic acid. The~3e APGs are resistant to hydrolysi~ by porcine pancreatic lipasel the dominant enzyme in.
~at digestion, in vitro.
E~en where the fatty acid moietie~ are hydrolyzed of~ the EEEPs and APG3 o~ this invention, no outward slgn of toxicity of the resulting EEP wa~ observed in our study. I~deed, even propylene glycol which would be released on cleavag~ of the EEP
ether linkag~ i~ given GR~S (G2nerally Recognized as Sa~e) status by th~ FDA. Propylen~ glycol and its derivatlves are used at low levels in the ~ood industry, 3 .g. a~ ~olvents ~or ~lavors and pharmaceuticals, and in bak~d good~, salad drQ sings and ~auces.
ThQ proc~3~ o~ thi~ invention involves a base (pre~Qrably alkali metal) catalyzed reaction o~ th~ polyol with th~ epoxide.
As noted in the Gibson and Quick paper, supra, the base catalysis opens the oxiran~ ring of the propyl~n~ oxide in thQ addition : reaction to provid~ a predomi~ance of secondary hydrsxyl groups, on th~ order oP 98% sQcondary to 2% primary. We pref~r, in the case o~ gly~erol, to start with a ~at such as soybean oil, split it to form glycerol and RCO2H, and ~eparate th~ glycerol from the fatty acid. Thi~ provides the glyc~rol for th~ base catalyzed pr-~poxyla~ion addition r~action. The resultant G(PO~n~ pxe~erably n ~ ~ ~ 5, is th~n raacted rapidly at high 30 temperature, betw~Qn about 100 to 200~C, in the pre~ence of paratoluQn~ sulphonic acid (PTSA) with a stoichiomstric amount of th~ soybean oil ~atty acid to produc~ the r~sultant APGs mixture ; product. Tha APG~ product can b~ re~in~d a~d bleached in a conventional ~anner, ~.g. with alkali and clay, to pr~vide a cl~an product o~ low color and low acid valu~.
-16~
2 ~ ~
_tailed Description of the Best Mode The following detailed description is by way of example, not by way o~ limitation, of the principle~ of the invention to illustrate the be~t modQ of carrying out the invention.
In this example, the epoxida (EP0~ i~ represented by propylene oxide (PO), the polyol P(OH)a~C by glycerol (G), and the esteri~ied fatty acid acyl moiety (FE) by a mixture o~ either palmitic or heptadecanoir acids with ol~ic acid, to produce a food oil/fat sub3titute/~i~Qtic of the formula ~(PO)~(YE)b~, where n - 2 - 5 and b 3 3. Wlth the addition o~ 5 PO units, all the original polyol (in thi3 example a triol) hydroxyls will ha~e boen etheri~ied (in this exampl~ propoxylated)~
EX~P~ 1 I. Pro~o~ ed Gly~e~ nt~e~is A. Catalyst P~a~a~lon A catalyst solutlon ~or th~ propoxylation reaction is prepared to provide .25 wt % K+ in 6000 gm~ final propoxylat~d product. To prepar0 tha catalyst, 27.59 gram~ powdar~d potassium hydroxide a~d 300 gra~ glyc~rol, G, are charged to a 1000 cc rotary evaporation ~lask and heatsd undar nitrog~n at 75-80C with stirriny ~or about on~ hour. Th0 catalyst goe~ into ~olution leaving a clou~ product which is ~txipped on a rotary evaporator at 60-70C/5m~ ~g ~or one hour to remove water. Th~ theoretical wa~ar los~ i~ l2.38 gram~. The ca~alyst solution (314.62 gms) is added to a dry, nitrog~n ~lu hed 2-gallon stainle3s ~tael stirred reactor.
B. ProPox~l~tl~n Reaction, 1:3_G:pO
To prspare propoxylated glyaarol with thre~ oxypropylene units th~ initial glycorol charge i~ 2073.32 gms (i~a., 1773.32 gms charg~d as free glycerol, and 300 gms add~d with the c~talyst '.
,~ ., , charge). The remaining 1773~32 gm~ glycerol (~W = 92.1 gm/mole) was ~dded to the reactor under a continuou~ purge with dry nitrogen. The reactor was heated to 70-75C and nitrogen pressure was adjusted to 20 psig. An initial charge of 500 grams propylene oxide, P0, (MW 3 58.08 gm/mole) wa~ added to thP
reactor, and the reaction exotherm wa allowed ~o carry the temperature up to soc. A~ter th~ reaction was initiated, the temperature was adjusted to 90-95C and the remaining dry propylene oxide was added on a pressure demand basis over an 18 lo hour period. A pres~ure dema~d control valYa system was used to control the addition rate. A re~erence pressure was s~t at p~ig. If the reactor pressure dropped below this pre sure the control valve opened and more propyl~ne oxide wa~ charged to the reactor. When the pressure in~reased to ~reater than 60 psig, the valv~ clos~d. The propylene oxide wa~ contained in a yoke that wa~ suspended on a weight load cell, thareby permitt~ng the charging of the correct amount o~ propylene oxid~. To prepare propoxylated glycerol with three oxypropylene units the total propylene oxide charge i9 3926.68 gram3. Since th~ yoke had a psig nitrogen pre~ ur~ head, the overall reactor pressure increas~d to 80 psig when all the propylen~ oxide wa~ pu~hed out of th~ load cell yoko into the reactor. A~tQr all the propylene oxid~ had been added, the rQaction mixtur~ wa~ allow2d to cook out for an additional 4-6 hour~ to insure complQt~ reaction.
When th~ reaction wa~ c4mpl~ta, th~ product was removad hot from th~ reactor ~nd wa~ tr~ated with Magn~solR (4 grams per 2S0 ~rams product) ~or two hours at 100-llOC in order to remove the K+ catalyst. The r~sulting product was vacuum filtered through a C~lliteR (purified diatomacaou~ silica) bed at 60-~OC
to provide t~a pure olig~meric polyol. Hydroxyl Nu~ber, VPo molecular w~ight, G~l Per~ation Chromatography (GPC) analysis, and 13CNMR w~r~ used to charact rizs the hydroxy propoxylated glycerols mixture, HPGs. For thQ HPGs with thrbe oxypropylen~
unlts, polydispersity by GPC analy~i3 1~ 1.19 and the molac~lar weight calculat~d ~rom the Hydroxyl Numb~r is 266 gms/mola.
~18-II. Svnthesis_of APGs (Tri acylated HPGs).
In a typical ynthesis, a solution of 0.035 moles of redistilled acyl chlorides (a mlxture of a 1:5 molar ratio of either palmitoyl or heptadecanoyl chloride to oleeyl chloride) in dry chloro~orm (20 ml) is add~d dropwise to 2 stirred solution o~
O.01 mole of the HPGs in.dry chloroform (20 ml) and dry pyridine (6 ml). The addition is made at room temperature, under an atmosphere o~ dry nitrogen, and stirring is continu~d for a furth~r 24 hours. A phase separation occurs in the reaction vessel. At he end o~ the reaction, the mixture is added o water (500 ml) and extracted several times with pstroleum ether ~3 X 500 ml~. Tha comb$ned organic phase is than washed with water (2 X 500 ml), dilute aqueou~ HCl (2 X 500 ~l)~ water (2 X 500 ml~, a~ueous potassiu~ bicarbonatQ (2 X 500 ml), and then water (~ X 500 ml~, and dried ovQr anhydrous sodiu~ sulphate be~ore ~vaporation o~ th~ solv~nt. Prior to column chromatography, any free fatty acid~ still prQsent are methylat~d with ethereal diazomethane. Th~ crude acylat~d propoxylated glycerol mixtur~s (APGs) produc~ is puri~ied by passag~ down a silicic acid colu~n, eluting with a gradi~nt of di~thylether (O to lO0~ in petrol~u~ eth~r. Overall yield~ ~or th~ ~PGs s~nthe3i~ fall in ~ha rang~ o~ 5g-75%~ Puri~y and 3tructure of th2 APG ~roduat are confirmed by IR and lH N~R spectroscopy, and by Thin Layer Chro~atography (TLC~o The r~su}tant APG products are all oils at room temparature and generally vsry acceptable pal~ y~llow color, hut which can be easily bleachsd.or clari~ied by passing through char~oal. The APG~ exhibited raverse visco3ity, with tha n a 1 and n 3 2.2 productg (sea ~xa~pl~ 2 b~low) being slightly mor~ vi~cous than oliva oil, and th~ n ~ 5 and n ~ 8 products slightly l~s ~iscous than olive oil. Similarly the n 8 5 and n - 8 did not solidify at 5C wh~le th~ n ~ 1 and n ~ 2.2 exhibited partial crystallization at 5C. The molecular weight ranges are determined as ~ollows: n ~ 1, 884-1000, n ~ 2.2, 942-1116:
n - 5, 1058~1~90; and n - 8, lQ58-13~8 assuming th~ ~rioleoyl --19~
?~
derivatives and including 95% o~ the total mass of the polymeric mixtur~. All Exhibited organoleptically acceptable propQrties, having a bland oily mouth ~eel without belng slimy.
III~
Pancreatic Lipase EXAMPLE_2 Following the above procedur~ in Exa~ple 1, a number o~ APG
products o~ the EEEPs of this in~ention we.re prepar~d in which n was varied in the range of ~rom 1-8 by control o~ th~ amount of PO in th~ reaction. 100 mg of the APG Pat or oil o~ the in~ention to b2 tested is add~d to 10 ml o~ bu~fer containing 1 mM NaCl, 1 2M CaCl~, 3 ~ daoxycholate, 2 mM trl~, and 10 g/l o~ gum arabicO The mixtura is vigorou~ly shakan in a capped t2st-tube, and th~ e~ulsion is transf~rred to th~ pH stat r~action Ve~8~1. The pH i~ titratad to 8.0 using a Radiomater pH
stat (comprising a TTA80 titration assembly, a TTT80 titrator, and ABU80 autoburett~ and a pHM82 pH meter). Porcin~ pancreatic lipa~ (0.1 ml, equivalent ~o 1000 unit9 0~ QnZy~Q, at p~ 8.0) is added, th~ p~ rap~dly ra-~uilibrat~d to 8.0, and then the reaction ~ollow~d OVQr a 20'~inut~ period by autotitratio~ with m~ aqusou~ NaOH. m a initi21, linear rat~ i~ reported a~
2S micro ~ole3 Og NaO~ p~r hour requlred to ka~p ~h~ pH constant by neu~ralising th~ ~ree fat~y acid~ r~l~a.ad by th~ action o~
pancr~atic l~pa~e.
Tha r~ult ar~ givsn b~low in Tabla I, expras3ad as an average o~ 4 deter~inations, r~lati~a to oliv~ oil a~ a control 30 (100~3, wher~ the EPO i~ PO and thQ FE i9 as in Examp}2 I, part II.
, , .
2 ~ ~
Table I Di~stibility_(Lipase Activitv) ~y~ 3~~elative Rate*
Control: Olive Oil 100 Invention APG~ G(EPO)n(~E)b n - 0 76.2 ~ - 1 46.2 n = 2.2 1809 n = 5 0 n ~ 8 * Average o~ ~our determinations.
Bas~d on the above Tabl~ I data, at n - 3 th~ lipa e hydrolysis rate is about 10%, and at n 3 4 it is about 5%. W~ pre~r the lipase hydroly~$s rat~ to b~ below a~out 10~.
The corr~sponding ac~tat~ adducts of th~ te~ted ~PG~3 0~ Table I (n ~ 1, 2.2, S and R) w~ro assayed by Ga3 Liquid Chro~atography ~packQd column) to show th~ di tribution o~ polypropy:Len~ oxide units ln each. ~hQ re~ult~ are ~hown in Table II:
% Area by G~C (P2cX~d Colu~n) . ~, _ - G:F0 Adduct PG G I:l 1:2 1:3 1:4 1:5 1:6 1:7 1:8 1:9 l:lC
G(P0)1 ND 31.l 46.~ 19.9 2.7 _ _ _ _ _ .
__ __ _ _ _ . _ G(PO)a,~ ND 2.1 22.7 40.5 28.0 5.9 0.7 _ _ 30 GtP0)5 t ND ND 1.4 16.I 34.5 28.5 13.6 5.1 0.8 . _ _ _ _ _ _ G(PO)g t ND ND ND 4 9 13 3 22 3 25 8 22.6 8.3 2.7 ND
ND - Not detectabl~ t ~ tracQ P5 - propyleneglycol G = glycol Th~ above compon~n~s r~prese~t 90~ o~ ~he ~as~ ~rac~
in~egral, except for G(P0)8 where the valu~ was 67.8% du~ to ~ .. .. . .
~ ~ 2 ~ ~
presence of unknown additional components, (NOT triacetin). The area % not corrected to give mass or mole % (FID response factors unknown).
Where the APGs product averag~ molecular weight is too low, below about 600-900, it is not useful a~ a no~-digestible ~at substitute because it will be directly absorbed in the gut. We believe the non digestibility o~ ~h~ APG~ product o~ this invention is due primarily to t~e presence of secondary alcohol ester linkages.
IV. IN VIVO Testin.
EXAMPhE 3 FEEDING ST~DIES
Spra~u~ Dowley weanling rats (male) were ~ed a laboratory chow di~ containing 2.5% by weight o~ two di~ferent test com~ound~: ~ikhor th~ n ~ 2.2 conposition or th3 n - 5 compo~ltion o~ ~xample 2, each containing 18~ o~ heptadecanoic acid a~ a mark~r, the balance of the fatty acid ~acyl) ~oiaty in th~ EEEP t~t compound being oleic acid. Total dietary lipid ws kept at 10% (by wQight) with 2.75% added corn oil, the labo~atory chow alr2ady containing 4.5% lipid. Also, a known ncn dige~tibla mark~r compound, 1,2 didod~cyl-3-hexadecyl glycQrol, was add~d to tha diat~ at 0.25% (by w~ight) lav~l.
The ~eeding trial continuad ~or ~hree weeks, during which tim~ rat body wQight gain increas~d at a rata equal to that of control anlmal~. No outward 3igns o~ toxicity w2r~ obs~rved.
F~ce~ w~re collec~d and analys d for lipid cont~nt, u~ing a GLC
method basAd on heptadecanoic acid and 30 1,2-didod2cy1 3-h~xad~oylglycerol ~ark~r~. The data show the following percqntag~ recovQries o~ heptad~canoic acid (HDA) in the ~ces:
-~2-3 2, TAl~LE III Non-Digestability %HDA as Total Free Fatty%HDA Still Fecal Test Compound~ Acid Estsrified HDA%
n = 2.2 12 6 18 ~ - 5 13 31 4~
The percen~ages listed under %HDA a~ Free Fatty Acid3 xepre~ents tha percentage o~ the test compound that was not ab~orbed, but the HDA moiaty of which wa~ hydrolyzed in the ~ut or in th~
~eces by digestive enzymo3 or microbial action. ~h~ parcentages listed undar %HDA Still Esterified indicat~ th~ percentage 5till in original ~orm, not hydrolyzed in gut or ~ce~. ThQ last column shows the total o~ the two pr~ceeding columns, being the p~rcentage not absorbed or digested.
The data show that thæ t~st co~pounds, particularly the n - 5 compound~ (pentahydroxypropylglyc~rol), ar~ suitably resistant to overall digestion, which include~ hydrolysis and absorption in th~ upper intastine o~ the rat, and some hydrolysi~ and utilizatio~ by th~ microbial population o~ th cecum, colon, and fec~.
Th~ sy~th~ is above involvlng propyl~ne oxid~ can be employ~d ~or apoxylation with bu~yl~n~ oxid~ and isobutylene oxide~ to produco the corrosponding epoxld2 ext~ndad polyols which are then acylat~d, pra~erably p~racyla~ed as ab~ve~describe~.
It should be under~tood tha~ var~oll3 modifications within the ~cope o~ this inv~ntion can b~ mado by one of ordinary skill in the art ~i~hou~ d~parting ~ro~ ~he ~pirlt ~her~or. We there~or~ wi~h our invention to ba d~ined by the scope o~ the ap~ended clai~ as broadly as thQ prior art wlll per~it, and in view o~ thls ~pecification i~ n~ed b~.
~23--
Claims (50)
1. A reduced calorie food composition comprising fat-type ingredients and non-fat ingredients, wherein from about 10 to 100%
of the total fat-type ingredients comprises a mixture of epoxide-extended polyol esters obtainable by the reaction of (A) the product of reacting n moles of a C3-6 epoxide per mole of a polyol having the formula P(OH) a+c where a is the number of primary hydroxyl groups in the polyol and is in the range 1 to 8, c is the total number of secondary and tertiary hydroxyl groups in the polyol and is in the range of 0 to 7, the total of a+c being in the range 3 to 8; n is equal to or greater than a, and greater than 95% of the primary hydroxyl groups in the polyol are replaced in said product by secondary or tertiary hydroxyl groups with (B) b moles, per mole of said product of a fatty acid having the formula RCOOH where R has 7 to 23 carbon atoms and b is greater than 2 but not greater than a+c.
of the total fat-type ingredients comprises a mixture of epoxide-extended polyol esters obtainable by the reaction of (A) the product of reacting n moles of a C3-6 epoxide per mole of a polyol having the formula P(OH) a+c where a is the number of primary hydroxyl groups in the polyol and is in the range 1 to 8, c is the total number of secondary and tertiary hydroxyl groups in the polyol and is in the range of 0 to 7, the total of a+c being in the range 3 to 8; n is equal to or greater than a, and greater than 95% of the primary hydroxyl groups in the polyol are replaced in said product by secondary or tertiary hydroxyl groups with (B) b moles, per mole of said product of a fatty acid having the formula RCOOH where R has 7 to 23 carbon atoms and b is greater than 2 but not greater than a+c.
2. A reduced calorie food composition as claimed in claim 1 wherein n is sufficient to impart a pancreatic lipase hydrolysis rate of below about 10% compared to olive oil.
3. A reduced calorie food composition as claimed in claim 1 wherein n has an average value in the range 2 to 8.
4. A reduced calorie food composition as claimed in claim 2 wherein n has an average value in the range 2 to 8.
5. A reduced calorie food composition as claimed in claim 1, 2, 3 or 4 wherein R is of sufficient length that the epoxide-extended polyol esters are substantially resistant to digestive tract absorption.
6. A reduced calorie food composition as claimed in claim 1, 2, 3 or 4 wherein R is selected from C13-17 chains and mixtures thereof.
7. A reduced calorie food composition as claimed in claim 1, 2, 3 or 4 wherein the epoxide is selected from propylene oxide, pentene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxy-2-methylpropane, 1,2-epoxy-cyclohexane, and mixtures thereof.
8. A reduced calorie food composition as claimed in claim 5 wherein the epoxide is selected from propylene oxide, pentene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxy-2-methylpro-pane, 1,2-epoxy-cyclohexane, and mixtures thereof.
9. A reduced calorie food composition as claimed in claim 6 wherein the epoxide is selected from propylene oxide, pentene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxy-2-methylpro-pane, 1,2-epoxy-cyclohexane, and mixtures thereof.
10. A reduced calorie food composition as claimed in claim 1, 2, 3 or 4 wherein the polyol is selected from sugars, glycerol, saccharides and mixtures thereof.
11. A reduced calorie food composition as claimed in claim 5 wherein the polyol is selected from sugars, glycerol, saccha-rides and mixtures thereof.
12. A reduced calorie food composition as claimed in claim 6 wherein the polyol is selected from sugars, glycerol, saccha-rides and mixtures thereof.
13. A reduced calorie food composition as claimed in claim 7 wherein the polyol is selected from sugars, glycerol, saccha-rides and mixtures thereof.
14. A reduced calorie food composition as claimed in claim 8 wherein the polyol is selected from sugars, glycerol, saccha-rides and mixtures thereof.
15. A reduced calorie food composition as claimed in claim 9 wherein the polyol is selected from sugars, glycerol, saccha-rides and mixtures thereof.
16. A reduced calorie food composition as claimed in claim 10 wherein the sugar is selected from glucose, mannose, galactose, arabinose, xylose, sorbinose, amylose and mixtures thereof.
17. A reduced calorie food composition as claimed in claim 11, 12, 13, 14 or 15 wherein the sugar is selected from glucose, mannose, galactose, arabinose, xylose, sorbinose, amylose and mix-tures thereof.
18. A reduced calorie food composition as claimed in claim 1, 2, 3 or 4 wherein P(OH) a+c is glycerol, a is 2, c is 1, the epoxide is selected from propylene oxide butylene oxide and isobu-tylene oxide, n has an average value between of from 2 to 8, and b has an average value which is greater than 2 but not greater than 3.
19. A reduced calorie food composition as claimed in claim 5 wherein P(OH)a+c is glycerol, a is 2, c is 1, the epoxide is selected from propylene oxide, butylene oxide and isobutylene oxide, n has an average value between of from 2 to 8, and b has an average value which is greater than 2 but not greater than 3.
20. A reduced calorie food composition as claimed in claim 6 wherein P(OH)a+c is glycerol, a is 2, c is 1, the epoxide is selected from propylene oxide, butylene oxide and isobutylene oxide, n has an average value between of from 2 to 8, and b has an average value which is greater than 2 but not greater than 3.
21. A reduced calorie food composition as claimed in claim 7 wherein P(OH) aic is glycerol, a is 2, C is 1, the epoxide is pro-pylene oxide, n has an average value between of from 2 to 8, and b has an average value which is greater than 2 but not greater than 3.
22. A reduced calorie food composition as claimed in claim 8 or 9 wherein P(OH) a+c is glycerol, a is 2, c is 1, the epoxide is propylene oxide, n has an average value between of from 2 to 8, and b has an average value which is greater than 2 but not greater than 3.
23. A reduced calorie food composition as claimed in claim 10 wherein P(OH) a+c is glycerol, a is 2, c is 1, the epoxide is selected from propylene oxide, butylene oxide and isobutylene oxide, n has an average value between of from 2 to 8, and b has an average value which is greater than 2 but not greater than 3.
24. A reduced calorie food composition as claimed in claim 11, 12, 13, 14 or is wherein P(OH) a+c is glycerol, a is 2, c is 1, the epoxide is selected from propylene oxide, butylene oxide and isobutylene oxide, n has an average value between of from 2 to 8, and b has an average value which is greater than 2 but not greater than 3.
25. A reduced calorie food composition as claimed in claim 18 wherein n is in the range of 2 to 5 and b is 3.
26. A reduced calorie food composition as claimed in claim 19, 20, 21 or 23 wherein n is in the range of 2 to 5 and b is 3.
27. A reduced calorie food composition as claimed in claim 22 wherein n is in the range of 2 to 5 and b is 3.
28. A reduced calorie food composition as claimed in claim 24 wherein n is in the range of 2 to 5 and b is 3.
29. A reduced calorie food composition as claimed in claim 18 wherein n is in the range of 3 to 5 and b is 3.
30. A reduced calorie food composition as claimed in claim 19, 20, 21 or 23 wherein n is in the range of 3 to 5 and b is 3.
31. A reduced calorie food composition as claimed in claim 22 wherein n is in the range of 3 to 5 and b is 3.
32. A reduced calorie food composition as claimed in claim 24 wherein n is in the range of 3 to 5 and b is 3.
33. A method of preparing a mixture of epoxide-extended polyol esters for use as a fat-type ingredient in a reduced calorie food composition as claimed in claim 1, said method comprising the steps of:
(a) reacting said polyol of the formula P(OH) a+C in the pres-ence of a base catalyst with said C3-C6 epoxide, for a period of time sufficient to provide a polyepoxide-extended polyol having a minimum epoxylation index average number n which is not less than a and wherein greater than 95% of the primary hydroxyls of said polyol are converted to secondary or tertiary hydroxyls; and (b) reacting said epoxide-extended polyol with at least one fatty acid, RCOOH, to produce said mixture of epoxide-extended polyol esters.
(a) reacting said polyol of the formula P(OH) a+C in the pres-ence of a base catalyst with said C3-C6 epoxide, for a period of time sufficient to provide a polyepoxide-extended polyol having a minimum epoxylation index average number n which is not less than a and wherein greater than 95% of the primary hydroxyls of said polyol are converted to secondary or tertiary hydroxyls; and (b) reacting said epoxide-extended polyol with at least one fatty acid, RCOOH, to produce said mixture of epoxide-extended polyol esters.
34. A method as claimed in claim 33 which includes the steps of:
(a) splitting a natural fat or oil selected from soybean oil, rapeseed oil, tallow, cottonseed oil, coconut oil, palm oil, babassu oil, corn oil, lard, fish oil, olive oil, peanut oil, safflower seed oil, sesame seed oil, jojoba oil and sunflower seed oil and mixtures thereof to form glycerol and one or more fatty acids RCOOH
where R is a C7-C23 group;
(b) separating the glycerol from said fatty acid; and (c) employing said glycerol in said base catalyzed addition reaction.
(a) splitting a natural fat or oil selected from soybean oil, rapeseed oil, tallow, cottonseed oil, coconut oil, palm oil, babassu oil, corn oil, lard, fish oil, olive oil, peanut oil, safflower seed oil, sesame seed oil, jojoba oil and sunflower seed oil and mixtures thereof to form glycerol and one or more fatty acids RCOOH
where R is a C7-C23 group;
(b) separating the glycerol from said fatty acid; and (c) employing said glycerol in said base catalyzed addition reaction.
35. A method as claimed in claim 33 wherein P(OH)a+c is glycerol, a is 2, c is 1, the epoxide is propylene oxide, n has an average value above 2.2, and b has an average value between above 2 to 3.
36. A reduced calorie food composition as claimed in claim 1 wherein the fatty acid is released from caprylic acid, capric acid, lauric acid, myristic acid, myristoleic acid, stearic acid, palmitic acid, palmitoleic acid, rincinoleic acid, linoleic acid, linolenic acid, eleaostearic acid, arachidic acid, behenic acid, erucic acid, oleic acid, and heptadecanoic acid.
37. A reduced calorie food composition as claimed in claim 1 wherein n is at least 5.
38. A fat-type ingredient suitable for use in preparing reduced calorie food compositions comprising a blend of an edible oil or fat and a mixture of epoxide-extended polyol esters ob-tainable by the reaction of (A) the product of reacting n moles of a C3-6 epoxide per mole of a polyol having the formula P(OH) a+c where a is the number of primary hydroxyl groups in the polyol and is in the range 1 to 8, c is the total number of secondary and tertiary hydroxyl groups in the polyol and is in the range 0 to 7, the total of a+c being in the range 3 to 8; n is equal to or greater than a, and greater than 95% of the primary hydroxyl groups in the polyol are replaced in said product by secondary or tertiary hydroxyl groups with (B) b moles, per mole of said product of a fatty acid having the formula RCOOH where R has 7 to 23 carbon atoms and b is greater than 2 but not greater than a+c.
39. The fat-type ingredient as claimed in claim 38 wherein the C3-C6 epoxide is propylene oxide.
40. The fat-type ingredient as claimed in claim 38 wherein n has an average value in the range 2 to 8.
41. The fat-type ingredient as claimed in claim 38 wherein the polyol is glycerol.
42. The fat-type ingredient as claimed in claim 38 wherein n is at least 5.
43. The fat-type ingredient as claimed in claim 38 wherein the fatty acid is selected from caprylic acid, capric acid, lauric acid, myristic acid, myristoleic acid, stearic acid, palmitic acid, palmitoleic acid, rincinoleic acid, linoleic acid, linlenic acid, eleaostearic acid, arachidic acid, behenic acid, erucic acid, oleic acid and heptadecanoic acid.
44. The use, as a reduced calorific value substitute for an edible oil or fat, of a mixture of epoxide-extended polyol esters obtainable by the reaction of (A) the product of reacting n moles of a C3-6 epoxide per mole of a polyol having the formula P(OH) a+c where a is the number of primary hydroxyl groups in the polyol and is in the range 1 to 8, c is the total number of secondary and ter-tiary hydroxyl groups in the polyol and is in the range 0 to 7, the total of a+c being in the range 3 to 8; n is equal to or greater than a, and greater than 95% of the primary hydroxyl groups in the polyol are replaced in said product by secondary or tertiary hydroxyl groups, with (B) b moles, per mole of said product, of a fatty acid having the formula RCOOH where R has 7 to 23 carbon atoms and b is greater than 2 but not greater than a+c.
45. The use as claimed in claim 44 wherein n is sufficient to impart a pancreatic lipase hydrolysis rate of below about 10%
compared to olive oil.
compared to olive oil.
46. The use as claimed in claim 44 wherein n has an average value in the range 2 to 8.
47. The use as claimed in claim 44 wherein n is at least 5.
48. The use as claimed in claim 44 wherein the epoxide is selected from propylene oxide, pentene oxide, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxy-2-methylpropane, 1,2-epoxy-cyclohexane, and mixtures thereof.
49. The use as claimed in claim 44 wherein the polyol is selected from sugars, glycerol, saccharides and mixtures thereof.
50. The use as claimed in claim 44 wherein P(OH)a+c is glycerol, a is 2, c is 1, the epoxide is propylene oxide, n has an average value of from 2 to 8, and b has an average value which is greater than 2 but not greater than 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US889,552 | 1986-07-25 | ||
| US06/889,552 US4861613A (en) | 1986-07-25 | 1986-07-25 | Non-digestible fat substitutes of low-caloric value |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1311238C true CA1311238C (en) | 1992-12-08 |
Family
ID=25395342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000536602A Expired - Lifetime CA1311238C (en) | 1986-07-25 | 1987-05-07 | Non-digestible fat substitutes of low-caloric value |
Country Status (10)
| Country | Link |
|---|---|
| US (3) | US4861613A (en) |
| EP (1) | EP0254547B1 (en) |
| JP (1) | JP2518649B2 (en) |
| KR (1) | KR960004625B1 (en) |
| CA (1) | CA1311238C (en) |
| DD (1) | DD287484A5 (en) |
| DE (1) | DE3784195T2 (en) |
| ES (1) | ES2044935T3 (en) |
| GR (1) | GR3007102T3 (en) |
| IN (1) | IN167650B (en) |
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-
1987
- 1987-05-07 CA CA000536602A patent/CA1311238C/en not_active Expired - Lifetime
- 1987-06-19 JP JP62151583A patent/JP2518649B2/en not_active Expired - Lifetime
- 1987-07-22 DE DE8787306468T patent/DE3784195T2/en not_active Expired - Fee Related
- 1987-07-22 EP EP87306468A patent/EP0254547B1/en not_active Expired - Lifetime
- 1987-07-22 ES ES87306468T patent/ES2044935T3/en not_active Expired - Lifetime
- 1987-07-24 KR KR1019870008123A patent/KR960004625B1/en not_active IP Right Cessation
-
1988
- 1988-01-21 IN IN53/CAL/88A patent/IN167650B/en unknown
- 1988-01-22 DD DD88312391A patent/DD287484A5/en unknown
-
1993
- 1993-02-18 GR GR920402745T patent/GR3007102T3/el unknown
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1995
- 1995-06-07 US US08/476,816 patent/US5641534A/en not_active Expired - Fee Related
- 1995-06-07 US US08/476,815 patent/US5603978A/en not_active Expired - Fee Related
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| EP0254547A3 (en) | 1989-05-24 |
| AU606348B2 (en) | 1991-02-07 |
| IN167650B (en) | 1990-12-01 |
| US4861613A (en) | 1989-08-29 |
| DE3784195T2 (en) | 1993-06-03 |
| EP0254547B1 (en) | 1993-02-17 |
| DE3784195D1 (en) | 1993-03-25 |
| JPS6335568A (en) | 1988-02-16 |
| DD287484A5 (en) | 1991-02-28 |
| ES2044935T3 (en) | 1994-01-16 |
| JP2518649B2 (en) | 1996-07-24 |
| KR880001717A (en) | 1988-04-26 |
| AU7600587A (en) | 1988-01-28 |
| KR960004625B1 (en) | 1996-04-09 |
| GR3007102T3 (en) | 1993-07-30 |
| EP0254547A2 (en) | 1988-01-27 |
| US5641534A (en) | 1997-06-24 |
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