CA1268280C - Star-branched polyamides - Google Patents
Star-branched polyamidesInfo
- Publication number
- CA1268280C CA1268280C CA 494117 CA494117A CA1268280C CA 1268280 C CA1268280 C CA 1268280C CA 494117 CA494117 CA 494117 CA 494117 A CA494117 A CA 494117A CA 1268280 C CA1268280 C CA 1268280C
- Authority
- CA
- Canada
- Prior art keywords
- star
- branched
- oxazoline
- core
- whole number
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
-
- 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
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/16—Dendrimers and dendritic polymers
Abstract
ABSTRACT
A star-branched polyamine represented by the formula Z-[-NH-C(R2)2(CH2)xC(R2)2)?R
wherein Z is the residue of the core compound, each R2 is independently hydrogen, or hydrocarbyl, R is a chain-terminating group, m is a whole number from 2 to 100, x is 0 or 1 and n is a whole number from 3 to 100.
The polyamines are useful as viscosity enhancing agents in such applications as paints, mobility control agents and hydraulic fluids.
A star-branched polyamine represented by the formula Z-[-NH-C(R2)2(CH2)xC(R2)2)?R
wherein Z is the residue of the core compound, each R2 is independently hydrogen, or hydrocarbyl, R is a chain-terminating group, m is a whole number from 2 to 100, x is 0 or 1 and n is a whole number from 3 to 100.
The polyamines are useful as viscosity enhancing agents in such applications as paints, mobility control agents and hydraulic fluids.
Description
~Z~3~
1 6~693-3699D
This application is a divisional application of patent application number 494,117 filed on October 29th, 1985. The invention of this application relates to a star-branched polyamine represented by the formula z - [(NH-c(R )2(CH2)xc(R )2)m~ R
wherein Z is the residue of the core compound, each R2 is independently hydrogen, or hydrocarbyl, R is a chain-terminatiny group, m is a whole number from 2 to 1000, x is O or 1 and n is a whole number from 3 to 100.
The invention in the parent application xelates to a star-branched polyamide having at least 3 branches emanating from the residue of a core compound wherein each brand has a plurality of amide moieties in which each such amide moiety has its amide nitrogen in the chain of the branch and each such amide nitrogen bears a pendant carbonyl moiety, said amide moieties being hydrolysable to form amine moieties without cleaning the chain of the branch.
Water-soluble polyamines and polyamides are known to be effective thickeners or viscosity modifiers for aqueous media.
For example, acrylamide polymers and polyalkylenepolyamines such as polyethyleneimine have been employed extensively as thickeners for aqueous hydraulic fluids and fluid mobility control agents in secondary oil recovery. Hydrocarbon-soluble polyamides and polyamines have been used as viscosity modifiers and dispersants in lubricants. Unfortunately, however, such polymers often deyrade when solutions of the polymers are subjected to a high ....
- ~z~i~z~
1 6~693-3699D
This application is a divisional application of patent application number 494,117 filed on October 29th, 1985. The invention of this application relates to a star-branched polyamine represented by the formula z - [(NH-c(R )2(CH2)xc(R )2)m~ R
wherein Z is the residue of the core compound, each R2 is independently hydrogen, or hydrocarbyl, R is a chain-terminatiny group, m is a whole number from 2 to 1000, x is O or 1 and n is a whole number from 3 to 100.
The invention in the parent application xelates to a star-branched polyamide having at least 3 branches emanating from the residue of a core compound wherein each brand has a plurality of amide moieties in which each such amide moiety has its amide nitrogen in the chain of the branch and each such amide nitrogen bears a pendant carbonyl moiety, said amide moieties being hydrolysable to form amine moieties without cleaning the chain of the branch.
Water-soluble polyamines and polyamides are known to be effective thickeners or viscosity modifiers for aqueous media.
For example, acrylamide polymers and polyalkylenepolyamines such as polyethyleneimine have been employed extensively as thickeners for aqueous hydraulic fluids and fluid mobility control agents in secondary oil recovery. Hydrocarbon-soluble polyamides and polyamines have been used as viscosity modifiers and dispersants in lubricants. Unfortunately, however, such polymers often deyrade when solutions of the polymers are subjected to a high ....
- ~z~i~z~
2 6~693-3699D
degree of shear as is of-ten the case in many applications for viscous aqueous fluids and hydrocarbon lubricants.
Therefore, it would be highly desirable to provide a polyamide and a polyamine derivative thereof which acts as a viscosity enhancer in aqueous and hydrocarbon fluids and which resists degradation upon exposure to high degrees of shear.
The invention of the parent application relates to a polymer comprising a star-branched polyamide which polyamide has a plurality of branches emanating from a core with each branch having a plurality of amide moieties in the branch wherein each amide nitrogen is in the backbone or chain of the branch and bears a pendant carbonyl moiety and which amide moiety can be hydrolyzed to form an amine moiety without cleavage of the backbone of the branch. Such star-branched polymers are soluble in aqueous and/or hydrocarbon liquids and have sufficient molecular weight to measurably increase the viscosity of the liquid when dissolved therein. For the purposes of this invention, a star-branched polymer is one having at least three branches emanating from a single core as in classical star-branched polymers.
The invention of this application concerns star-branched amine derivatives of the aforementioned star-branched polyamide.
The invention of the parent application also concerns a process for making a water-soluble star-branched polyamide comprising contacting a core compound or a linear polymer having a plurality of electrophilic moieties with a 2-substituted-2-oxazoline or a substituted-2-oxazine in an amount and under conditions sufficient to cause the oxazoline or oxazine moiety to 3 G4693-36~9D
react with a plurality of the electrophilic moieties of the core compound thereby causing ring-opening polymerization of the oxa~oline or oxazine moieties to form the desired water-soluble star-branched polyamide. Generally the moles of oxazoline or oxazine moiety is at least nine times the moles of core compound or linear polymer and -the reaction is conducted at a temperature range of from 50C to 150C.
The star-branched polyamides and polyamines of the present invention are readily employed as viscosity enhancing agents in such applications as paint thickeners, hydraulic fluids, mobility control agents and fracturing fluids in oil recovery applications, and lubricants.
The star-branched polyamides and polyamines are polymers having at least 3 core branches emanating from a core or polymer.
The core branches are of sufficient length and contain sufficient amide or amine moieties to make the star-branched sufficient amide or amine moieties to make the star-branched polymer water-soluble and to enable it to perform as a viscosity increasing agent when added to an aqueous medium.
Preferred star-branched polyamides are represented by the formula.
Z[tN-c(R )2)CH2)xC(R )2)m]nR
C=O
Rl wherein Z is the residue of the core compound or polymer backbone; R1 is hydrocarbyl such as aryl, alkyl or arylalkyl; each R2 is individually hydrogen or hydrocarbyl; m is a number from 2 ~., ~2~i~2~
degree of shear as is of-ten the case in many applications for viscous aqueous fluids and hydrocarbon lubricants.
Therefore, it would be highly desirable to provide a polyamide and a polyamine derivative thereof which acts as a viscosity enhancer in aqueous and hydrocarbon fluids and which resists degradation upon exposure to high degrees of shear.
The invention of the parent application relates to a polymer comprising a star-branched polyamide which polyamide has a plurality of branches emanating from a core with each branch having a plurality of amide moieties in the branch wherein each amide nitrogen is in the backbone or chain of the branch and bears a pendant carbonyl moiety and which amide moiety can be hydrolyzed to form an amine moiety without cleavage of the backbone of the branch. Such star-branched polymers are soluble in aqueous and/or hydrocarbon liquids and have sufficient molecular weight to measurably increase the viscosity of the liquid when dissolved therein. For the purposes of this invention, a star-branched polymer is one having at least three branches emanating from a single core as in classical star-branched polymers.
The invention of this application concerns star-branched amine derivatives of the aforementioned star-branched polyamide.
The invention of the parent application also concerns a process for making a water-soluble star-branched polyamide comprising contacting a core compound or a linear polymer having a plurality of electrophilic moieties with a 2-substituted-2-oxazoline or a substituted-2-oxazine in an amount and under conditions sufficient to cause the oxazoline or oxazine moiety to 3 G4693-36~9D
react with a plurality of the electrophilic moieties of the core compound thereby causing ring-opening polymerization of the oxa~oline or oxazine moieties to form the desired water-soluble star-branched polyamide. Generally the moles of oxazoline or oxazine moiety is at least nine times the moles of core compound or linear polymer and -the reaction is conducted at a temperature range of from 50C to 150C.
The star-branched polyamides and polyamines of the present invention are readily employed as viscosity enhancing agents in such applications as paint thickeners, hydraulic fluids, mobility control agents and fracturing fluids in oil recovery applications, and lubricants.
The star-branched polyamides and polyamines are polymers having at least 3 core branches emanating from a core or polymer.
The core branches are of sufficient length and contain sufficient amide or amine moieties to make the star-branched sufficient amide or amine moieties to make the star-branched polymer water-soluble and to enable it to perform as a viscosity increasing agent when added to an aqueous medium.
Preferred star-branched polyamides are represented by the formula.
Z[tN-c(R )2)CH2)xC(R )2)m]nR
C=O
Rl wherein Z is the residue of the core compound or polymer backbone; R1 is hydrocarbyl such as aryl, alkyl or arylalkyl; each R2 is individually hydrogen or hydrocarbyl; m is a number from 2 ~., ~2~i~2~
to 1000 each R is a chain-terminating group; x is Q or 1; and n is a whole numher from 3 to 100. In preferred star-branched polyamides and polyamines, ~ is an n-valent hydrocarbon radlcal such as CH2 ~,~l CH2 ) n -H2 C -C -CH2 - ~
each R is alXyl, c,]kylaryl or aryl having from 1 to 20 carbons;
and ea~oh R2 is hv~drc)aen, x is 0 and n is a whole number in the range of 3 to 'V. Preferably n is from 3 to 6 and R is hydrogen Ol alkyl. In star:--hranched polymers, R1 and R2 are as defined before and Z in an n-valent polymer backbone such as ~30~CH2CHo ~ CH2CHO~nR
R C~-Ho~cH2cHotnR
C~2 -wherein R3 is the residue of a polyether polyol initiator, R4 is hycl.ro~len or C1-C3 alkyl, R is as defined hereinbefore, ancl x is a whole number from 3 to 100. Preferably, n is a whole number from 3 to ~0 and m is a whole number from 2 to 1000. The star-branched o]yamines are represented by the formula -5- ~G~ ) 64693- 3699D
Z~(NH-c~R )~(C~2)xc( R ) 2 ~nR
wherein Z, R2, R, m, x and n are as defined herein-before.
The star-branc~ed polymers of this .. 5 invention are readily prepared by reacting a compound capable of generating a polyvalent core or polymer backbone, e.g., ZXn wherein X is halo, sulfonyl halide, s~lfonate ester or triflate ester, and Z and n are as defined hereinbefore t with a compound having an oxazo-line or oxazine moiety, e.g., ~ C' ~ ~ R2 Rl Rl oxazoline oxazine wherein Rl and R2 are as defined hereinbefore, under conditions sufficient to cause the oxazoline or oxazine ring to undergo a ring-opening reaction to form Z~N-C(R )2(CH2~XC(R )2)m3~~
C=O
Rl Advantageously, the degree of polymerization of this polymer, which is equivalent to m, is controlled by the molar ratio of the oxazoline or oxazine compound to ~he 31, 963-F -5-r ~Z6~
core-generating compound. For example, when m is 3 and n is 3, then the molar ratio of the oxazoline or oxa-zine compound to the core-generating compound employed is at least from 9:1 to 14:1. If, however, it is desirable to provide a compound having a degree of polymerization where m equals 6 and n is equal to 3, then the molar ratio of the o~sazoline or oxazine compound to the core- or backbone-generating compound is at ~ least from 18:1- to 27:1. In general, the molar ratio of the oxazoline or oxazine compound to the core- or backbone-generating compound is preferably at least 1.5 (m x n) most preferably at least 2 (m x n). That is the moles of said oxazoline or oxazine moiety is preferably at least nine times the moles of the core- or backbone--generating compound because "n" is at least three and "m" is at least two as defined hereinabove.
Representative preferred core- and backbone--generating compounds include polyhalohydrocarbons hav-ing a number of reactive halo groups corresponding to n which halo groups are available for reaction with an oxazoline moiety. Examples of such polyhalohydro-carbons include tetra(halomethyl)methane, tetra(bromo-methyl)methane, hydroxymethyltri(bromomethyl)methane, 1,2,3,4,5,6-hexa(bromomethyl)benzene, 1,3,5-tri(bromo-methyl)-2,4,6-trimethyl benzene, polyallyl halides such as polyallyl bromide, polyallyl chloride and copolymers of.allyl bromide and ethylene. Other preferred core-and backbone-generating compounds include polytosyl-hydrocarbons and polytrifylhydrocarbons having a number of tosyl or triflate groups corresponding to n which tosyl or triflate groups are available for reaction in an oxazoline moiety. Examples of such polytosyl- and polytrifylhydro-carbons include tetra(tosylmethyl)me-thane, 31,963-F -6-...
, . . .
126~3ZI~
tetratetra(trifylmethyl)methane, polyglycidol per-tosylates, polyglycidol copolymer pertosylates, poly-vinyl alcohol pertosylates and pertriflates. In general, multifunctional core- or backbone-generating compounds having three or more (n>3) moieties which are able to undergo nucleophilic replacement by the oxazo-~ line nitrogen to generate oxazolinium cations or initi-ator sites are employed. It is preferred that the chemical bond resulting from this oxazoline replacement reaction be stable to (i.e., resist) acid or alkaline hydrolysis. Of the foregoing core- and backbone-generating compounds, the halides such as bromides and iodides are more preferred, with the tosylates and the triflate esters being the most preferred.
Representative oxazoline co~pounds that may be suitably employed in the practice of this invention include 2-alkyloxazolines such as 2-methyloxazoline, 2-ethyloxazoline and 2-propyloxazollne; other alkylox-azolines such as 2,4-dimethyloxazoline, 2,5-dimethyl-oxazoline, 2,4,5-trimethyloxazoline and the like;
hydroxyalkyloxazolines such as 2-hydroxymethylethyl-oxazoline; haloalkyloxazolines such as 2-(chlorometh-yl)oxazoline and 2-(1,1-dichloroethyl~oxazoline; and aryloxazolines such as 2-phenyloxazoline and 2-(p-tolyl)oxazoline. Of the foregoing oxazolines, the2-methyl-, 2-ethyl-, 2-phenyl- and 2-hydroxymethyl-ethyloxazolines are preferred, with the 2-ethyloxazo-line being the most preferred. Representative oxazine compounds are those which correspond in all other respects to the aforementioned oxazoline compounds. Of the oxazine compounds, the 2-methyl-, 2-ethyl-, 2-phenyl-and 2-hydroxymethylethyloxazines are preferred, with the 2-ethyloxazines being the most preferred.
31,963-F -7-- -. -8- ~2~
The reaction to prepare the desired star-branched polyamide is carried out by contacting the core- or backbone-generating compound with the oxazoline or oxazine compound in the presence of potassium iodide or other similar catalysts. Pre-ferably, the reaction is carr:ied out at temperatures in the range from 50C to 150C, and may be effected under neat conditions or in a solvent such as dimethylform-amide or another nonreactive, but polar solvent. The resulting polyamide can be readily recovered by conven-tional means as illustrated in the examples set for'h hereinafter. When Rl is Cl-C3 alkyl or hydroxyalkyl, the resulting polyamide is a watersoluble polymer exhibiting use as a viscosity enhancer when dissolved in aqueous media. When Rl is a C4 or higher alkyl or aryl, the polymer is generally soluble in organic liquids such as hydrocarbons. However, upon hydrolysis to amines, the lipophilic polyamides are converted to water-solu~le polyamines.
The polyamide is readily converted to poly-amine by contacting the polyamide with strong acid such as hydrochloric or sulfuric acid under conditions suf-ficient to hydrolyze the amide groups, thereby forming the amine. The conditions employed for this hydrolysis are those well-known in the art for the hydrolysis of amines to amides such as described by K. M. Kem, J. Polym. Sci., 17, 1977-1990 (1979). Preferably, however, the hydrolysis is carried out using a-strong acid such as hydrochloric acid or sulfuric acid in concentrations from 6N (normal) to 12N and at tempera-tures in the range from 50C to 125~C. When total hydrolysis is desired, the total acid employed is preferably from 1.1 to 1.5 equivalents of acid per 31,963-F -8-~9~ ~68Z~
equivalent of amide moiety in the polymer. It is further understood that partial hydrolysis of the amide can be achieved by employing less acid on a mole basis than is required to hydrolyze all of the amide moieties, for example, about 1.3X equivalents of acid per equiva-lent of amide wherein X is equal to the mole percent of hydrolysis desired. The resulting polyamines are also very water-soluble and are useful as viscosity enhan-cers for aqueous compositions such as paints, lubri-cants and liguids used in secondary oil recovery cppli-cations. More importantly, such polyamines are espe-cially useful as core-generating compounds in the preparation of dendritic polymers.
The following examples are given to illustrate the inventions of the parent and this divisional appli-cation and should not be construed as limiting their scope.
All parts and percentages in the following examples are by weight unless otherwise indicated.
Example 1 - Preparation of Star-Branched PolYamide An 85-g (0.86 mole) portion of 2-ethyl-~
oxazoline was combined with 9.6 g (0.029 mole) of tri-bromoneopentyl alcohol ~hydroxymethyltribromometl~yl-methane~ and 1.4 g of potassium iodide in a 3-necked flask equipped with a reflux condenser, stirrer and heating mantle. The reaction mixture was heated with stirring at 90C while protecting the mixture from moisture with a calcium chloride drying tube. The reaction mixture was heated at 90C to 100C for a period of 50 hours to produce an orange amber glassy mass wllich flows at 125C and whicll was very water-soluble. This glassy, brittle polymer was ground into a 31,963-F -9-~3~
~a~,, - -10- ~ z~
tan colored powder and dissolved in methylene chloride at a ratio of 4.5 g of polymer in 30 ml of methylene chloride. This solution was slowly poured into 80 ml of diethyl ether while stirring with a magnetic stirrer.
Initially, a light tan solid precipitated which became a syrupy gum after the entire methylene chlo-ride solution was added. The cloudy supernatant was decanted leaving a syrupy residue which was then ~ redissolved in 25 ml of methylene chloride. Half of.
this solution was added dropwise while stir ing to 80 ml of diethyl ether. A light colored solid precipitated and was filtered and washed with two 10-ml portions of diethyl ether. This polymer has a softening point of 83C to 91C. Analysis of this sample by nuclear magnetic resonance and infrared spectroscopy indicated a star-shaped structure having polyamide moieties in the branches. Si7e exclusion chromatography indicated that this polymer is quite polydispersed which is probably due to the presence of star branched polymers having branches with a wide range of degree of polymeri-zation. A monodispersed component is noted at longer elution times which is believed to be a small amount of homopolymer.
Example 2 - Preparation of Star-Branched PolYamide An 8.76-y (0.0217 mole) portion of 1,3,5-tribromomethylme$itylene was dissolved in 203.77 g (2.79 mole) of dimethylformamide and charged to a l-liter, 3-necked round-bottom flask equipped with a reflux condenser and a stirrer. To this solution WdS added 83-.198 g (0.98 mole) of 2-methyloxa~oline. The ratio of initiator, i.e., 1,3,5-tribromomesitylene, -to the methyloxazoline was 1 mole of initiator per 45 moles of 31,963-F -10--11- 126~?;~
methyloxazoline. The reaction mixture was then heated from ambient temperature to 45C and maintained at this temperature while monitoring the progress of the reac-tion with size exclusion chromatography. Within a few minutes after all reactants were mixed, a white precipi-tate was observed to form. Within 2.5 hours, the reac-tion was clear and samples of the resulting yellowish solution were withdrawn and analyzed. After approxi-mately 7 hours, the reaction was nearing gO percent completion and was terminated. Termination of the reaction was accomplished by vacuum distilling all volatiles away from the polymeric residue. Distil-lation was performed at a maximum temperature of 65C
and a maximum vacuum of 2 mm of mercury. The resulting polymer was analyzed by size exclusion chromatography and determined to contain a significant quantity of trapped dimethylformamide. To remove this residual dimethylformamide, the residue was dissolved in methyl-ene chloride at a ratio of 1 g of residue in 6 ml of methylene chloride and precipitated by slowly dropping this solution into 200-300 ml of diethyl ether. The polymer im~ediately precipitates from solution and was filtered and dried overnight in a vacuum oven. The resulting crystalline polymer was analyzed by scanning electron chromatography and for carbon 13 structure confirmation using nuclear magnetic resonance. These analyses indicated a star-branched polyamide having a degree of polymerization such that m equa~s ~ to 15.
Example 3 - Preparatlon of a Star-Branched Polyamine The star-branched polyamide of Example 2 was hydrolyzed to a star-branched polyamine by the follow-ing procedure. A 5.8-g (1.37 x 10 3 mole) portion of 31,963-F -11--12- ~2682~0 the polyamide of Example 2 was combined with 10.5 g of 36 percent hydrochloric acid in water. A mild exotherm was noted upon combination and the reaction mixture was heated at reflux for 3 hours after which time a white solid product was observed. After a total reflux time of 5 hours, the reaction product was dissolved in 20 ml of deionized water. Sufficient hydroxide form of an ion-exchange resin was added to the reaction mixture to increase the pH of the mixture to about 8. The recov-ered amber colored syrup weighs 3.89 g wherein theore-tical weight for total hydrolysis is 3.16 g. Therefore, it is assumed that the star-branched polyamide ls approximately 72 percent hydrolyzed to the polyamine.
Nuclear maynetic resonance analysis of the resulting mixture indicated a somewhat higher degree of hydroly-sis and nuclear magnetic resonance and infrared spec-troscopy as well as size exclusion chromatography confirm the star-branched character of the polyamine.
Example 4 - Preparation of a Comb-Branched Polyamide A butanol-initiated copolymer of propylene oxide and glycidol represented by the formula:
n-c4H9o~cH2cHo]l6[cH2,cHO~9 was prepared by reacting 16 moles of propylene oxide with 9 moles of tbutylglycidyl ether in the presence of 1 mole of butanol at 50C. The copolymer has a mole-cular weight of 1594 as determined by fast atom bombard-ment mass spectroscopy and an equivalent weight of 177.
31,963-F -12--13- ~,26~~
A ~.43-g portion (25 milliequivalents (meg)) was dissolved in 25 ml of dry methylene chlo-ride and cooled to 0C. To this solution was added 9.54 g (50.0 meq) of tosyl chloride and 8.0 g (100 meq) of pyridine in 25 ml of methylene chloride which had been pre-cooled to 0C. I~he resulting slightly orange homogeneous solution was stirred for one hour while cooling in an ice bath. The reaction vessel containing the solution was tightly stoppered and stored at 4C for 7 day~. After the storage period, a 1.97-g portion of pyridine hydrochloride crystals were removed from the solution by filtration. The filtrate was then poured into 50 ml of an ice bath, stirred and then transferred to a separatory funnel.
The organic layer was washed with two 25-ml portions of 50 percent hydrochloric acid (25C) and then with a 25-ml portion of water (25C). The washed organic layer was dried over anhydrous Na2SO4 and sol-vent is removed via rotary evaporator (<50C) to pro-vide 10.02 g of a viscous brown oil which was shownby infrared analysis to be a tosylate of the copoly-mer. The tosylate copolymer was further purified by dissolving it in diethyl ether (30 ml) and then extracting it with two 50-ml portions of a saturated solution of NaHC03. The organic layer was separated, dried over anhydrous Na2S04 for 2 hours, filtered and devolatilized to provide 8.56 g of a clear orange--brown viscous liguid which was determined by infrared analysis to be a to~ally tosylated form of the copoly-mer (pertosylated copolymer).
The pertosylated copolymer was divided intoseveral portions and each was reacted with an amount of 2-ethyl-2-oxazoline (dried over molecular sieves to 31,963-F -13--14- ~26~Z~
16 ~g H20/ml) as indicated in Table I. The following procedure was used to carry out the reaction. The entire reaction apparatus was dried at 125C for at least 15 minutes and then cooled in a dry nitrogen stream. A 0.30-ml portion o~ a solution of pertosyl-ated copolymer in dry methylene chloride (0.1 g/ml) was-injected into a capped 20--ml- serum vial. For each sample, an appropriate volume of the solution was transferred to a dry 20-ml ampoule`and the methyl-ene chloride was removed using a stream of dry nitro-gen to leave the pertosylated copolymer in the ampoule which was then capped with a serum cap. A 2-ml portion of dry, purified oxazoline was added through the serum cap to each ampoule. The ampoules were cooled in meth-ylene chloride/dry ice bath evacuated to <25 Torr,back-flushed with nitrogen and flame sealed. The ampoules were placed in an oil bath heated to 150C
and maintained there for 40 hours.
TABLE I
Monomer:Ini-Sample tiator Oxazoline, Initiator, No. Mole Ratio g (moles) g (moles) 1 500 2 0.12 (2.02 x 10 3) (4.04 x 10 5) 2 1000 2 0.06 (2.02 x 10 3) (2.02 x 10 5) 3 2000 2 0.03 (2.02 x 10 3) (1.01 x 10 5) 4 4000 2 0.015 (2.0~ x 10 3) (5.05 x 10 6) 5000 2 0.0075 (2.02 x 10 3) (2.52 x 10 6) 31,963-F -14-12~
The ampoules were opened by cooling in dry ice, thus causing the polymer product to contract from the glass walls of the ampoules and to break the ampoules in some cases. The polymer product was separated from the glass, placed in aluminum trays, heated at 160C
and 8 Torr for 15 minutes and then reweighed. Based on weight loss determinations, the~polymerizations are found to be complete to form comb-branched poly-amides. ~ ~~
Solutions were prepared of each of the poly-mers (0.25 percent of the polymer in water containing potassium phosphate monobasic buffer (pH = 7)). Using size exclusion chromatography, the molecular weights of the comb-branched polyamides were as follows:
TABLE II
Sample No. Mw (x 10 4) Mn (x 10 4) 1 2.53 1.89 2 4.15 2.68 3 1.40 51.12 20 4 2.73 87.0 3.62 102.0 The comb-branched polyamides of Sample Nos. 4 and 5 were dissolved in water at concentrations ranging from 2.6 percen-t to 10 percent and subjected to shear rates ranging from 192 to 2693 sec 1 using 31,963-F -15--16- ~6~2~
a Haake Viscometer, Model RV-21 operating at 25C.
Under such sh~aring conditions, the solutions exhibi-ted a loss of viscosity of less than 10 percent of origi-nal non-sheared viscosity. The shear thinning at high shear rates that was observed was not permanent, but returned to original viscosity at lower shear ràtes.
31,963-F -16-
each R is alXyl, c,]kylaryl or aryl having from 1 to 20 carbons;
and ea~oh R2 is hv~drc)aen, x is 0 and n is a whole number in the range of 3 to 'V. Preferably n is from 3 to 6 and R is hydrogen Ol alkyl. In star:--hranched polymers, R1 and R2 are as defined before and Z in an n-valent polymer backbone such as ~30~CH2CHo ~ CH2CHO~nR
R C~-Ho~cH2cHotnR
C~2 -wherein R3 is the residue of a polyether polyol initiator, R4 is hycl.ro~len or C1-C3 alkyl, R is as defined hereinbefore, ancl x is a whole number from 3 to 100. Preferably, n is a whole number from 3 to ~0 and m is a whole number from 2 to 1000. The star-branched o]yamines are represented by the formula -5- ~G~ ) 64693- 3699D
Z~(NH-c~R )~(C~2)xc( R ) 2 ~nR
wherein Z, R2, R, m, x and n are as defined herein-before.
The star-branc~ed polymers of this .. 5 invention are readily prepared by reacting a compound capable of generating a polyvalent core or polymer backbone, e.g., ZXn wherein X is halo, sulfonyl halide, s~lfonate ester or triflate ester, and Z and n are as defined hereinbefore t with a compound having an oxazo-line or oxazine moiety, e.g., ~ C' ~ ~ R2 Rl Rl oxazoline oxazine wherein Rl and R2 are as defined hereinbefore, under conditions sufficient to cause the oxazoline or oxazine ring to undergo a ring-opening reaction to form Z~N-C(R )2(CH2~XC(R )2)m3~~
C=O
Rl Advantageously, the degree of polymerization of this polymer, which is equivalent to m, is controlled by the molar ratio of the oxazoline or oxazine compound to ~he 31, 963-F -5-r ~Z6~
core-generating compound. For example, when m is 3 and n is 3, then the molar ratio of the oxazoline or oxa-zine compound to the core-generating compound employed is at least from 9:1 to 14:1. If, however, it is desirable to provide a compound having a degree of polymerization where m equals 6 and n is equal to 3, then the molar ratio of the o~sazoline or oxazine compound to the core- or backbone-generating compound is at ~ least from 18:1- to 27:1. In general, the molar ratio of the oxazoline or oxazine compound to the core- or backbone-generating compound is preferably at least 1.5 (m x n) most preferably at least 2 (m x n). That is the moles of said oxazoline or oxazine moiety is preferably at least nine times the moles of the core- or backbone--generating compound because "n" is at least three and "m" is at least two as defined hereinabove.
Representative preferred core- and backbone--generating compounds include polyhalohydrocarbons hav-ing a number of reactive halo groups corresponding to n which halo groups are available for reaction with an oxazoline moiety. Examples of such polyhalohydro-carbons include tetra(halomethyl)methane, tetra(bromo-methyl)methane, hydroxymethyltri(bromomethyl)methane, 1,2,3,4,5,6-hexa(bromomethyl)benzene, 1,3,5-tri(bromo-methyl)-2,4,6-trimethyl benzene, polyallyl halides such as polyallyl bromide, polyallyl chloride and copolymers of.allyl bromide and ethylene. Other preferred core-and backbone-generating compounds include polytosyl-hydrocarbons and polytrifylhydrocarbons having a number of tosyl or triflate groups corresponding to n which tosyl or triflate groups are available for reaction in an oxazoline moiety. Examples of such polytosyl- and polytrifylhydro-carbons include tetra(tosylmethyl)me-thane, 31,963-F -6-...
, . . .
126~3ZI~
tetratetra(trifylmethyl)methane, polyglycidol per-tosylates, polyglycidol copolymer pertosylates, poly-vinyl alcohol pertosylates and pertriflates. In general, multifunctional core- or backbone-generating compounds having three or more (n>3) moieties which are able to undergo nucleophilic replacement by the oxazo-~ line nitrogen to generate oxazolinium cations or initi-ator sites are employed. It is preferred that the chemical bond resulting from this oxazoline replacement reaction be stable to (i.e., resist) acid or alkaline hydrolysis. Of the foregoing core- and backbone-generating compounds, the halides such as bromides and iodides are more preferred, with the tosylates and the triflate esters being the most preferred.
Representative oxazoline co~pounds that may be suitably employed in the practice of this invention include 2-alkyloxazolines such as 2-methyloxazoline, 2-ethyloxazoline and 2-propyloxazollne; other alkylox-azolines such as 2,4-dimethyloxazoline, 2,5-dimethyl-oxazoline, 2,4,5-trimethyloxazoline and the like;
hydroxyalkyloxazolines such as 2-hydroxymethylethyl-oxazoline; haloalkyloxazolines such as 2-(chlorometh-yl)oxazoline and 2-(1,1-dichloroethyl~oxazoline; and aryloxazolines such as 2-phenyloxazoline and 2-(p-tolyl)oxazoline. Of the foregoing oxazolines, the2-methyl-, 2-ethyl-, 2-phenyl- and 2-hydroxymethyl-ethyloxazolines are preferred, with the 2-ethyloxazo-line being the most preferred. Representative oxazine compounds are those which correspond in all other respects to the aforementioned oxazoline compounds. Of the oxazine compounds, the 2-methyl-, 2-ethyl-, 2-phenyl-and 2-hydroxymethylethyloxazines are preferred, with the 2-ethyloxazines being the most preferred.
31,963-F -7-- -. -8- ~2~
The reaction to prepare the desired star-branched polyamide is carried out by contacting the core- or backbone-generating compound with the oxazoline or oxazine compound in the presence of potassium iodide or other similar catalysts. Pre-ferably, the reaction is carr:ied out at temperatures in the range from 50C to 150C, and may be effected under neat conditions or in a solvent such as dimethylform-amide or another nonreactive, but polar solvent. The resulting polyamide can be readily recovered by conven-tional means as illustrated in the examples set for'h hereinafter. When Rl is Cl-C3 alkyl or hydroxyalkyl, the resulting polyamide is a watersoluble polymer exhibiting use as a viscosity enhancer when dissolved in aqueous media. When Rl is a C4 or higher alkyl or aryl, the polymer is generally soluble in organic liquids such as hydrocarbons. However, upon hydrolysis to amines, the lipophilic polyamides are converted to water-solu~le polyamines.
The polyamide is readily converted to poly-amine by contacting the polyamide with strong acid such as hydrochloric or sulfuric acid under conditions suf-ficient to hydrolyze the amide groups, thereby forming the amine. The conditions employed for this hydrolysis are those well-known in the art for the hydrolysis of amines to amides such as described by K. M. Kem, J. Polym. Sci., 17, 1977-1990 (1979). Preferably, however, the hydrolysis is carried out using a-strong acid such as hydrochloric acid or sulfuric acid in concentrations from 6N (normal) to 12N and at tempera-tures in the range from 50C to 125~C. When total hydrolysis is desired, the total acid employed is preferably from 1.1 to 1.5 equivalents of acid per 31,963-F -8-~9~ ~68Z~
equivalent of amide moiety in the polymer. It is further understood that partial hydrolysis of the amide can be achieved by employing less acid on a mole basis than is required to hydrolyze all of the amide moieties, for example, about 1.3X equivalents of acid per equiva-lent of amide wherein X is equal to the mole percent of hydrolysis desired. The resulting polyamines are also very water-soluble and are useful as viscosity enhan-cers for aqueous compositions such as paints, lubri-cants and liguids used in secondary oil recovery cppli-cations. More importantly, such polyamines are espe-cially useful as core-generating compounds in the preparation of dendritic polymers.
The following examples are given to illustrate the inventions of the parent and this divisional appli-cation and should not be construed as limiting their scope.
All parts and percentages in the following examples are by weight unless otherwise indicated.
Example 1 - Preparation of Star-Branched PolYamide An 85-g (0.86 mole) portion of 2-ethyl-~
oxazoline was combined with 9.6 g (0.029 mole) of tri-bromoneopentyl alcohol ~hydroxymethyltribromometl~yl-methane~ and 1.4 g of potassium iodide in a 3-necked flask equipped with a reflux condenser, stirrer and heating mantle. The reaction mixture was heated with stirring at 90C while protecting the mixture from moisture with a calcium chloride drying tube. The reaction mixture was heated at 90C to 100C for a period of 50 hours to produce an orange amber glassy mass wllich flows at 125C and whicll was very water-soluble. This glassy, brittle polymer was ground into a 31,963-F -9-~3~
~a~,, - -10- ~ z~
tan colored powder and dissolved in methylene chloride at a ratio of 4.5 g of polymer in 30 ml of methylene chloride. This solution was slowly poured into 80 ml of diethyl ether while stirring with a magnetic stirrer.
Initially, a light tan solid precipitated which became a syrupy gum after the entire methylene chlo-ride solution was added. The cloudy supernatant was decanted leaving a syrupy residue which was then ~ redissolved in 25 ml of methylene chloride. Half of.
this solution was added dropwise while stir ing to 80 ml of diethyl ether. A light colored solid precipitated and was filtered and washed with two 10-ml portions of diethyl ether. This polymer has a softening point of 83C to 91C. Analysis of this sample by nuclear magnetic resonance and infrared spectroscopy indicated a star-shaped structure having polyamide moieties in the branches. Si7e exclusion chromatography indicated that this polymer is quite polydispersed which is probably due to the presence of star branched polymers having branches with a wide range of degree of polymeri-zation. A monodispersed component is noted at longer elution times which is believed to be a small amount of homopolymer.
Example 2 - Preparation of Star-Branched PolYamide An 8.76-y (0.0217 mole) portion of 1,3,5-tribromomethylme$itylene was dissolved in 203.77 g (2.79 mole) of dimethylformamide and charged to a l-liter, 3-necked round-bottom flask equipped with a reflux condenser and a stirrer. To this solution WdS added 83-.198 g (0.98 mole) of 2-methyloxa~oline. The ratio of initiator, i.e., 1,3,5-tribromomesitylene, -to the methyloxazoline was 1 mole of initiator per 45 moles of 31,963-F -10--11- 126~?;~
methyloxazoline. The reaction mixture was then heated from ambient temperature to 45C and maintained at this temperature while monitoring the progress of the reac-tion with size exclusion chromatography. Within a few minutes after all reactants were mixed, a white precipi-tate was observed to form. Within 2.5 hours, the reac-tion was clear and samples of the resulting yellowish solution were withdrawn and analyzed. After approxi-mately 7 hours, the reaction was nearing gO percent completion and was terminated. Termination of the reaction was accomplished by vacuum distilling all volatiles away from the polymeric residue. Distil-lation was performed at a maximum temperature of 65C
and a maximum vacuum of 2 mm of mercury. The resulting polymer was analyzed by size exclusion chromatography and determined to contain a significant quantity of trapped dimethylformamide. To remove this residual dimethylformamide, the residue was dissolved in methyl-ene chloride at a ratio of 1 g of residue in 6 ml of methylene chloride and precipitated by slowly dropping this solution into 200-300 ml of diethyl ether. The polymer im~ediately precipitates from solution and was filtered and dried overnight in a vacuum oven. The resulting crystalline polymer was analyzed by scanning electron chromatography and for carbon 13 structure confirmation using nuclear magnetic resonance. These analyses indicated a star-branched polyamide having a degree of polymerization such that m equa~s ~ to 15.
Example 3 - Preparatlon of a Star-Branched Polyamine The star-branched polyamide of Example 2 was hydrolyzed to a star-branched polyamine by the follow-ing procedure. A 5.8-g (1.37 x 10 3 mole) portion of 31,963-F -11--12- ~2682~0 the polyamide of Example 2 was combined with 10.5 g of 36 percent hydrochloric acid in water. A mild exotherm was noted upon combination and the reaction mixture was heated at reflux for 3 hours after which time a white solid product was observed. After a total reflux time of 5 hours, the reaction product was dissolved in 20 ml of deionized water. Sufficient hydroxide form of an ion-exchange resin was added to the reaction mixture to increase the pH of the mixture to about 8. The recov-ered amber colored syrup weighs 3.89 g wherein theore-tical weight for total hydrolysis is 3.16 g. Therefore, it is assumed that the star-branched polyamide ls approximately 72 percent hydrolyzed to the polyamine.
Nuclear maynetic resonance analysis of the resulting mixture indicated a somewhat higher degree of hydroly-sis and nuclear magnetic resonance and infrared spec-troscopy as well as size exclusion chromatography confirm the star-branched character of the polyamine.
Example 4 - Preparation of a Comb-Branched Polyamide A butanol-initiated copolymer of propylene oxide and glycidol represented by the formula:
n-c4H9o~cH2cHo]l6[cH2,cHO~9 was prepared by reacting 16 moles of propylene oxide with 9 moles of tbutylglycidyl ether in the presence of 1 mole of butanol at 50C. The copolymer has a mole-cular weight of 1594 as determined by fast atom bombard-ment mass spectroscopy and an equivalent weight of 177.
31,963-F -12--13- ~,26~~
A ~.43-g portion (25 milliequivalents (meg)) was dissolved in 25 ml of dry methylene chlo-ride and cooled to 0C. To this solution was added 9.54 g (50.0 meq) of tosyl chloride and 8.0 g (100 meq) of pyridine in 25 ml of methylene chloride which had been pre-cooled to 0C. I~he resulting slightly orange homogeneous solution was stirred for one hour while cooling in an ice bath. The reaction vessel containing the solution was tightly stoppered and stored at 4C for 7 day~. After the storage period, a 1.97-g portion of pyridine hydrochloride crystals were removed from the solution by filtration. The filtrate was then poured into 50 ml of an ice bath, stirred and then transferred to a separatory funnel.
The organic layer was washed with two 25-ml portions of 50 percent hydrochloric acid (25C) and then with a 25-ml portion of water (25C). The washed organic layer was dried over anhydrous Na2SO4 and sol-vent is removed via rotary evaporator (<50C) to pro-vide 10.02 g of a viscous brown oil which was shownby infrared analysis to be a tosylate of the copoly-mer. The tosylate copolymer was further purified by dissolving it in diethyl ether (30 ml) and then extracting it with two 50-ml portions of a saturated solution of NaHC03. The organic layer was separated, dried over anhydrous Na2S04 for 2 hours, filtered and devolatilized to provide 8.56 g of a clear orange--brown viscous liguid which was determined by infrared analysis to be a to~ally tosylated form of the copoly-mer (pertosylated copolymer).
The pertosylated copolymer was divided intoseveral portions and each was reacted with an amount of 2-ethyl-2-oxazoline (dried over molecular sieves to 31,963-F -13--14- ~26~Z~
16 ~g H20/ml) as indicated in Table I. The following procedure was used to carry out the reaction. The entire reaction apparatus was dried at 125C for at least 15 minutes and then cooled in a dry nitrogen stream. A 0.30-ml portion o~ a solution of pertosyl-ated copolymer in dry methylene chloride (0.1 g/ml) was-injected into a capped 20--ml- serum vial. For each sample, an appropriate volume of the solution was transferred to a dry 20-ml ampoule`and the methyl-ene chloride was removed using a stream of dry nitro-gen to leave the pertosylated copolymer in the ampoule which was then capped with a serum cap. A 2-ml portion of dry, purified oxazoline was added through the serum cap to each ampoule. The ampoules were cooled in meth-ylene chloride/dry ice bath evacuated to <25 Torr,back-flushed with nitrogen and flame sealed. The ampoules were placed in an oil bath heated to 150C
and maintained there for 40 hours.
TABLE I
Monomer:Ini-Sample tiator Oxazoline, Initiator, No. Mole Ratio g (moles) g (moles) 1 500 2 0.12 (2.02 x 10 3) (4.04 x 10 5) 2 1000 2 0.06 (2.02 x 10 3) (2.02 x 10 5) 3 2000 2 0.03 (2.02 x 10 3) (1.01 x 10 5) 4 4000 2 0.015 (2.0~ x 10 3) (5.05 x 10 6) 5000 2 0.0075 (2.02 x 10 3) (2.52 x 10 6) 31,963-F -14-12~
The ampoules were opened by cooling in dry ice, thus causing the polymer product to contract from the glass walls of the ampoules and to break the ampoules in some cases. The polymer product was separated from the glass, placed in aluminum trays, heated at 160C
and 8 Torr for 15 minutes and then reweighed. Based on weight loss determinations, the~polymerizations are found to be complete to form comb-branched poly-amides. ~ ~~
Solutions were prepared of each of the poly-mers (0.25 percent of the polymer in water containing potassium phosphate monobasic buffer (pH = 7)). Using size exclusion chromatography, the molecular weights of the comb-branched polyamides were as follows:
TABLE II
Sample No. Mw (x 10 4) Mn (x 10 4) 1 2.53 1.89 2 4.15 2.68 3 1.40 51.12 20 4 2.73 87.0 3.62 102.0 The comb-branched polyamides of Sample Nos. 4 and 5 were dissolved in water at concentrations ranging from 2.6 percen-t to 10 percent and subjected to shear rates ranging from 192 to 2693 sec 1 using 31,963-F -15--16- ~6~2~
a Haake Viscometer, Model RV-21 operating at 25C.
Under such sh~aring conditions, the solutions exhibi-ted a loss of viscosity of less than 10 percent of origi-nal non-sheared viscosity. The shear thinning at high shear rates that was observed was not permanent, but returned to original viscosity at lower shear ràtes.
31,963-F -16-
Claims (4)
1. A star-branched polyamine represented by the formula Z -{(-NH-C(R2)2(CH2)xC(R2)2)m?nR
wherein Z is the residue of the core compound, each R2 is independently hydrogen, or hydrocarbyl, R is a chain-terminating group, m is a whole number from 2 to 1000, x is 0 or 1 and n is a whole number from 3 to 100.
wherein Z is the residue of the core compound, each R2 is independently hydrogen, or hydrocarbyl, R is a chain-terminating group, m is a whole number from 2 to 1000, x is 0 or 1 and n is a whole number from 3 to 100.
2. The star-branched polyamine of Claim 1 wherein Z is an n-valent hydrocarbon radical, each R2 is hydrogen, x is 0 and n is a whole number in the range from 3 to 20.
3. The star-branched polyamine of Claim 1 wherein Z is 31,963A-F -17- C(CH2-)4 or wherein n is from 3 to 6 and R is hydrogen or alkyl.
4. The star-branched polyamine of Claim 1 wherein Z is or wherein R3 is the residue of a polyether polyol initiator, R4 is hydrogen or C1-C3 alkyl, R is a chain-terminating group, n is a whole number from 3 to 20 and y is a whole number from 3 to 100.
31,963A-F -18-
31,963A-F -18-
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000609060A CA1268280A (en) | 1984-12-18 | 1989-08-22 | Star-branched polyamides |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US683,299 | 1984-12-18 | ||
| US06/683,299 US4599400A (en) | 1984-12-18 | 1984-12-18 | Star/comb-branched polyamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA1265641A1 CA1265641A1 (en) | 1990-02-06 |
| CA1268280C true CA1268280C (en) | 1990-04-24 |
Family
ID=24743422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 494117 Expired - Lifetime CA1268280C (en) | 1984-12-18 | 1985-10-29 | Star-branched polyamides |
Country Status (11)
| Country | Link |
|---|---|
| US (2) | US4599400A (en) |
| EP (1) | EP0195126B1 (en) |
| JP (1) | JPH0672127B2 (en) |
| KR (1) | KR920000698B1 (en) |
| AU (1) | AU576392B2 (en) |
| CA (1) | CA1268280C (en) |
| DE (1) | DE3587606T2 (en) |
| DK (1) | DK591485A (en) |
| FI (1) | FI85713C (en) |
| NO (1) | NO165445C (en) |
| NZ (1) | NZ214401A (en) |
Families Citing this family (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4599400A (en) * | 1984-12-18 | 1986-07-08 | The Dow Chemical Company | Star/comb-branched polyamide |
| US4694064A (en) * | 1986-02-28 | 1987-09-15 | The Dow Chemical Company | Rod-shaped dendrimer |
| US4713975A (en) * | 1986-05-30 | 1987-12-22 | The Dow Chemical Company | Dense star polymers for calibrating/characterizing sub-micron apertures |
| IL83567A (en) * | 1986-08-18 | 1992-02-16 | Dow Chemical Co | Starburst conjugates with a carried material,such as an agricultural or pharmaceutical material |
| US5773527A (en) * | 1990-08-27 | 1998-06-30 | Dendritech, Inc. | Non-crosslinked, polybranched polymers |
| US5631329A (en) * | 1990-08-27 | 1997-05-20 | Dendritech, Inc. | Process for producing hyper-comb-branched polymers |
| US5871713A (en) * | 1991-12-04 | 1999-02-16 | Guerbet S.A. | Macromolecular polyamine iodine-containing compound, process for its preparation and its use as a contrast agent |
| US5530092A (en) * | 1992-01-13 | 1996-06-25 | Dsm N.V. | Dendritic macromolecule and the preparation thereof |
| US5610268A (en) * | 1992-01-13 | 1997-03-11 | Dsm N.V. | Dendritic macromolecule and the preparation thereof |
| JP3355612B2 (en) * | 1992-04-14 | 2002-12-09 | 株式会社豊田中央研究所 | Star-shaped nylon and its production method, and tetrasubstituted carboxylic acid and its production method |
| TW320784B (en) * | 1994-05-13 | 1997-11-21 | Gould Electronics Inc | |
| AUPM623994A0 (en) * | 1994-06-15 | 1994-07-07 | Biomolecular Research Institute Limited | Antiviral dendrimers |
| US5449519C1 (en) | 1994-08-09 | 2001-05-01 | Revlon Consumer Prod Corp | Cosmetic compositions having keratolytic and anti-acne activity |
| EP0844891A4 (en) * | 1995-08-11 | 2004-05-06 | Dow Chemical Co | Hyper comb-branched polymer conjugates |
| DE19543161A1 (en) | 1995-11-18 | 1997-05-22 | Basf Ag | Process for the production of branched polyamides |
| US6051312A (en) * | 1996-06-06 | 2000-04-18 | Dsm Nv | Fibers of strongly branched polyamide |
| DE19743135A1 (en) * | 1997-09-30 | 1999-04-01 | Hoechst Marion Roussel De Gmbh | Biologically compatible low molecular weight polyethyleneimines |
| US6649138B2 (en) | 2000-10-13 | 2003-11-18 | Quantum Dot Corporation | Surface-modified semiconductive and metallic nanoparticles having enhanced dispersibility in aqueous media |
| FR2830255B1 (en) * | 2001-10-01 | 2004-10-22 | Rhodia Industrial Yarns Ag | COMPOSITE MATERIALS COMPRISING A REINFORCING MATERIAL AND AS A THERMOPLASTIC MATRIX, A STAR POLYAMIDE, PRECURSOR COMPOSED ARTICLE OF SUCH MATERIALS AND PRODUCTS OBTAINED FROM SUCH MATERIALS |
| JP3984541B2 (en) * | 2001-12-26 | 2007-10-03 | 財団法人川村理化学研究所 | Particles comprising star-shaped polyoxazoline and method for producing the same |
| CA2477675C (en) | 2002-03-05 | 2013-05-21 | Ramot At Tel-Aviv University Ltd. | Immunizing composition and method for inducing an immune response against the .beta.-secretase cleavage site of amyloid precursor protein |
| US20060160988A1 (en) * | 2003-02-03 | 2006-07-20 | Tomalia Donald A | Heterocycle functionalized dendritic polymers |
| WO2004096661A1 (en) * | 2003-05-02 | 2004-11-11 | Almar Packaging International Inc | Intermediate bulk container |
| US7459502B2 (en) * | 2003-11-03 | 2008-12-02 | Ilypsa, Inc. | Pharmaceutical compositions comprising crosslinked polyamine polymers |
| US7385012B2 (en) * | 2003-11-03 | 2008-06-10 | Ilypsa, Inc. | Polyamine polymers |
| US7449605B2 (en) * | 2003-11-03 | 2008-11-11 | Ilypsa, Inc. | Crosslinked amine polymers |
| US7335795B2 (en) * | 2004-03-22 | 2008-02-26 | Ilypsa, Inc. | Crosslinked amine polymers |
| US7767768B2 (en) * | 2003-11-03 | 2010-08-03 | Ilypsa, Inc. | Crosslinked amine polymers |
| US7608674B2 (en) * | 2003-11-03 | 2009-10-27 | Ilypsa, Inc. | Pharmaceutical compositions comprising cross-linked small molecule amine polymers |
| US7754500B2 (en) * | 2003-11-21 | 2010-07-13 | Anp Technologies, Inc. | Asymmetrically branched polymer conjugates and microarray assays |
| US20050171298A1 (en) * | 2004-01-29 | 2005-08-04 | Tomalia Donald A. | Pyrrolidone, piperidone and azetidinone terminated and functionalizes dendritic polymers |
| JP4510881B2 (en) | 2004-04-20 | 2010-07-28 | デンドリティック ナノテクノロジーズ，インコーポレイテッド | Dendritic polymers with enhanced expandability and internal functionality |
| WO2006102484A2 (en) * | 2005-03-21 | 2006-09-28 | Anp Technologies, Inc. | Symmetrically branched polymer conjugates and microarray assays |
| JP2008545621A (en) | 2005-04-20 | 2008-12-18 | デンドリティック ナノテクノロジーズ，インコーポレイテッド | Dendritic polymers with enhanced expandability and internal functionality |
| AU2006242303A1 (en) | 2005-05-02 | 2006-11-09 | Anp Technologies, Inc. | Polymer conjugate enhanced bioassays |
| US20080020043A1 (en) * | 2006-07-20 | 2008-01-24 | Marc Gingras | Dendrimer-Drug Conjugates |
| US20090001802A1 (en) * | 2007-05-21 | 2009-01-01 | Diallo Mamadou S | Extraction of Actinides From Mixtures and Ores Using Dendritic Macromolecules |
| US8715684B2 (en) | 2007-08-28 | 2014-05-06 | Ramot At Tel Aviv University Ltd. | Peptides inducing a CD4i conformation in HIV gp120 while retaining vacant CD4 binding site |
| DE102008043863A1 (en) | 2007-11-19 | 2009-05-20 | Basf Se | Use of branched homo- or copolymer obtained by polymerization of a monomer of e.g. 2-phenyl-4,5-dihydro-oxazole compound, to increase the glass transition temperature of thermoplastic partially aromatic polyamides |
| WO2009120875A2 (en) * | 2008-03-26 | 2009-10-01 | Shrieve Chemical Products, Inc. | Shale hydration inhibition agent(s) and method of use |
| US8450529B2 (en) * | 2008-10-02 | 2013-05-28 | Covidien Lp | Branched polyamines and formulations thereof for use in medical devices |
| US9815712B2 (en) | 2008-10-03 | 2017-11-14 | California Institute Of Technology | High capacity perchlorate-selective resins from hyperbranched macromolecules |
| WO2010040117A2 (en) * | 2008-10-03 | 2010-04-08 | California Institute Of Technology | Extraction of anions from solutions and mixtures using hyperbranched macromolecules |
| WO2011084719A2 (en) | 2009-12-17 | 2011-07-14 | California Institute Of Technology | Soluble anion exchangers from hyperbranched macromolecules |
| EP3257921B1 (en) * | 2016-06-14 | 2021-04-28 | Infineum International Limited | Lubricating oil additives |
| EP3492566B1 (en) * | 2017-11-29 | 2022-01-19 | Infineum International Limited | Lubricating oil additives |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3251852A (en) * | 1959-06-15 | 1966-05-17 | Petrolite Corp | Amino polymers |
| DE1720436A1 (en) * | 1968-02-01 | 1971-07-08 | Huels Chemische Werke Ag | Process for the production of polyamines |
| US3575890A (en) * | 1969-02-26 | 1971-04-20 | Allied Chem | Oxazine and oxazoline derived c-n backbone polymers |
| US4056510A (en) * | 1975-01-23 | 1977-11-01 | The Dow Chemical Company | Amine-modified polyethers |
| US4001147A (en) * | 1975-03-03 | 1977-01-04 | The Dow Chemical Company | Oxazoline and/or oxazine-modified polymers |
| US4143100A (en) * | 1977-05-16 | 1979-03-06 | The Firestone Tire & Rubber Company | Graft copolymers containing polyoxazoline and polyoxazine, and the preparation thereof |
| NO157821C (en) * | 1981-04-27 | 1988-05-25 | Dow Chemical Co | BRANCHED POLYAMIDOAMINE AND USE THEREOF FOR AA INCREASED WATER STRENGTH FOR PAPER. |
| US4435548A (en) * | 1981-04-27 | 1984-03-06 | The Dow Chemical Company | Branched polyamidoamines |
| US4507466A (en) * | 1983-01-07 | 1985-03-26 | The Dow Chemical Corporation | Dense star polymers having core, core branches, terminal groups |
| US4587329A (en) * | 1984-08-17 | 1986-05-06 | The Dow Chemical Company | Dense star polymers having two dimensional molecular diameter |
| US4599400A (en) * | 1984-12-18 | 1986-07-08 | The Dow Chemical Company | Star/comb-branched polyamide |
-
1984
- 1984-12-18 US US06/683,299 patent/US4599400A/en not_active Expired - Lifetime
-
1985
- 1985-10-25 AU AU49065/85A patent/AU576392B2/en not_active Ceased
- 1985-10-29 CA CA 494117 patent/CA1268280C/en not_active Expired - Lifetime
- 1985-11-18 FI FI854530A patent/FI85713C/en not_active IP Right Cessation
- 1985-12-02 NZ NZ214401A patent/NZ214401A/en unknown
- 1985-12-12 DE DE85115834T patent/DE3587606T2/en not_active Expired - Lifetime
- 1985-12-12 EP EP85115834A patent/EP0195126B1/en not_active Expired - Lifetime
- 1985-12-17 KR KR1019850009475A patent/KR920000698B1/en not_active IP Right Cessation
- 1985-12-17 JP JP60282124A patent/JPH0672127B2/en not_active Expired - Fee Related
- 1985-12-17 NO NO855075A patent/NO165445C/en unknown
- 1985-12-18 DK DK591485A patent/DK591485A/en not_active Application Discontinuation
-
1986
- 1986-03-07 US US06/837,126 patent/US4690985A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US4690985A (en) | 1987-09-01 |
| JPH0672127B2 (en) | 1994-09-14 |
| NZ214401A (en) | 1988-02-29 |
| KR860004949A (en) | 1986-07-16 |
| KR920000698B1 (en) | 1992-01-20 |
| DE3587606D1 (en) | 1993-11-04 |
| AU576392B2 (en) | 1988-08-25 |
| NO165445B (en) | 1990-11-05 |
| AU4906585A (en) | 1986-06-26 |
| FI854530A0 (en) | 1985-11-18 |
| EP0195126A3 (en) | 1988-08-24 |
| CA1265641A1 (en) | 1990-02-06 |
| FI854530A (en) | 1986-06-19 |
| NO165445C (en) | 1991-02-13 |
| DK591485D0 (en) | 1985-12-18 |
| DK591485A (en) | 1986-06-19 |
| DE3587606T2 (en) | 1994-03-03 |
| EP0195126A2 (en) | 1986-09-24 |
| FI85713C (en) | 1992-05-25 |
| NO855075L (en) | 1986-06-19 |
| JPS61151159A (en) | 1986-07-09 |
| US4599400A (en) | 1986-07-08 |
| EP0195126B1 (en) | 1993-09-29 |
| FI85713B (en) | 1992-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1268280C (en) | Star-branched polyamides | |
| EP0234408B1 (en) | Rod-shaped dendrimers | |
| US4631337A (en) | Hydrolytically-stable dense star polyamine | |
| Gnanou et al. | Synthesis of star‐shaped poly (ethylene oxide) | |
| Hobson et al. | Poly (amidoamine) hyperbranched systems: synthesis, structure and characterization | |
| EP0671429B1 (en) | Dense star polymers and a process for producing dense star polymers | |
| US4737550A (en) | Bridged dense star polymers | |
| Kopolow et al. | Cation Binding Properties of Poly (vinyl macrocyclic polyethers) | |
| US4587329A (en) | Dense star polymers having two dimensional molecular diameter | |
| US5631329A (en) | Process for producing hyper-comb-branched polymers | |
| EP0473088B1 (en) | Non-crosslinked, polybranched polymers | |
| CN108714398B (en) | Preparation method of polyquaternium surfactant | |
| Daccord et al. | α, ω-Difunctionalized poly (p-thiophenylene) oligomers: 1. Synthesis and properties | |
| Schulz et al. | Some new polyelectrolytes | |
| EP0610818B1 (en) | Method for preparation of a silicone resin | |
| US5679765A (en) | Polyether having heterofunctional groups at both ends, process for the preparation thereof and polymerization initiator therefor | |
| US4285851A (en) | Process for controlled gelation of polymeric solution (C-974) | |
| US3975347A (en) | Linear dimethylamine-epichlorohydrin copolymer | |
| US3640971A (en) | End-blocked copolymers of vinyl monomers with cyclic monomers and method for preparing the same | |
| Penczek | Cationic ring‐opening polymerization | |
| Kubota et al. | Preparation and properties of macromolecular complexes consisting of chitosan derivatives and potassium metaphosphate | |
| Cassidy et al. | Polyimidines: A new class of polymers. III. A comparison of isomers of polypyromellitimidines | |
| CN1387946A (en) | Bimetal cyanide catalyst and its prepn and application | |
| Schulz | Synthetic approaches to new polymers | |
| CA2049643C (en) | Non-crosslinked polybranched polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed | ||
| MKEC | Expiry (correction) |
Effective date: 20121205 |