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Publication numberUS3622604 A
Publication typeGrant
Publication dateNov 23, 1971
Filing dateApr 9, 1969
Priority dateOct 15, 1964
Publication numberUS 3622604 A, US 3622604A, US-A-3622604, US3622604 A, US3622604A
InventorsManfred Drawert, Eugen Griebsch
Original AssigneeSchering Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Synthetic polyamides of a dimeric fatty acid, a lower aliphatic carboxylic acid ethylene diamine, and a co-diamine
US 3622604 A
Abstract  available in
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Description  (OCR text may contain errors)

O Unlted States Patent 1 1 3,622,604

[72] Inventors Manfred Drawer! [50] Field of Search 260/4045 Werne a.d. Lippe; Eugen Griebsch, Unna, both of Germany [56] Re'erences (med [21] App1.No. 815,279 UNITED STATES PATENTS 1 1 d A r. 9, 1969 2,379,413 7/1945 Bradley 260/4045 5] Palgrmed Nov-23,1971 2,886,543 5/1959 Peerman et a1. 260/4045 Asslgnee Schema AG 3,037,871 6/1962 Floyd 61.3] 260/4045 Berlin, Germany 3,224,893 12/1965 Floyd et a1. 260/4045 Pnormes Oct-15,1964 3,268,461 8/1966 Jacobson 260/4045 Germany 3,297,730 1/1967 Fischer et a1. 260/4045 1] 591135965; 3,408,317 10/1968 Vertnik 260/4045 1965. GermannNm Sch 365671 3,412,115 11/1968 Floyd et a]. 260/4045 a y 36782 3,420,789 1/1969 Wilson 260/4045 ConunuImn-ln-pm 9! 81111118111011 3,499,853 3/1970 Griebsh et a1 260/4045 527,107, Feb. 14, 1966, now abandoned I and a continuatiomimpm 0 495.319, och Prunary Exam1r 1erJames 0. Thomas, Jr. 1 12, 1965 now abandoned This application AsslslanlExam171erG. Hollrah p 9, Ser. No. Attorney-Curtis, MOl'l'lS & Safford ACID A C folrmulatlon Of prmtlng Inks, fonmed bctween a dlmel:lC ETHYLENE DIAMINE, AND A Commm acld, an unsu0sututed 1owe1' ahphatlc monocartpxyhf: acld, 10 Claims, No Drawings ethylene d1an11ne and ce1'ta1n a roma11c, cycloahpha t1c, and other ahphauc dlammes, mcludmg allphatlc ether dlamlnes; [52] US. CL 260/4045, th ds f preparing such polyamides,

106/20, 106/27, 106/243 [51] Int. C091 7/00 SYNTHETIC POLYAMIDES OF A DIMERIC FATTY ACID, A LOWER ALIPHATIC CARBOXYLIC ACID ETHYLENE DIAMINE, AND A CO-DIAMINE This application is a continuation-in-part of application Ser. No. 527,107, filed Feb. 14, 1966 (now abandoned), and ofapplication Ser. No. 495,319, filed Oct. 12. 1965 (now abandoned).

This invention relates to synthetic polyamides comprising dimeric fatty acids and to methods for making the same. In particular, this invention relates to synthetic polyamides notable either for their good solubility in alcohols, particularly in ethanol, or for good solubility in solvent mixtures coupled with a high-softening point, and to methods of making such polyamides.

The polyamides of the invention are used to advantage as printing ink binders.

Polyamides comprising polymerized unsaturated fatty acids and ethylene diamine, and having a molecular weight range of from 3,000 to 5,000, are known in the art. However, only butanolic solutions of such products are stable at room temperature.

it has also been proposed in the prior art to increase the solubility of polyamides by the incorporation therein of branch-chain alkylol amines or branched dicarboxylic acids, or of branch-chain diamines having an amino group on a tertiary carbon atom.

Although certain progress has been made in the prior art toward increasing the solubility of polyamides, the disadvantages of prior'art polyamides include a strong tendency toward blocking in sheets printed with inks comprising the polyamides as binders, an insufficient resistance of solutions of the polyamides to gelation, and a lack or low degree of reversibility of gel formation in such solutions. A further disadvantage in those prior art polyamides having improved solubility is that their softening point is too low to permit them to be used as printing ink binders.

The present invention concerns new polyamides and their preparation by the thermal polycondensation of monocarboxylic acid, diamine, and dimerized fatty acid which may optionally contain smaller quantities of trimeric fatty acid and monomeric fatty acid. The monocarboxylic acid is a straightchain unsubstituted (i.e. hydrocarbon) aliphatic carboxylic acid having one to five carbon atoms, suitably a lower alkanoic monoacid such as acetic acid. As the diamine are used mixtures of ethylene diamine with either: (1) a branched or straight-chain unsubstituted (i.e. hydrocarbon) aliphatic codiamine having six to twelve carbon atoms, particularly a C -C alkylene diamine; or (2) certain aromatic and cycloaliphatic codiamines or (3) certain ether codiamines.

In particular, aromatic amines of the formulas and cycloaliphatic diamines of the formula R] R2 1 xH2x) can be employed,

wherein x is zero or a small integer and wherein R,-R are hydrogen or lower alkyl. Those cyclic amines in which at most two of the substituents R R are lower alkyl are of particular interest because of their current commercial availability.

As ether codiamines, materials having the formula can be used, wherein n is an integer from 3 to 5 inclusive, .r is an integer from 0 to 3 inclusive, and R is an alkylene radical having from one to 12 carbon atoms, which radical may optionally have one or two alkyl substituents having from lto 4 carbon atoms thereon.

According to the invention, suitable aromatic and cycloaliphatic codiamines include p-phenylene diamine, mtoluylene diamine; 4,4 -diamino diphenylmethane; 3,3"- dimethyl-4,4'-diamino diphenylmethane;4,4'-diamino diphenylpropane; 4,4'diamino dicyclohexylmethane; 3,3'-dimethyl- 4,4'-diamino dicyclohexyl-methane; xylylene diamine; bis-(B- aminoethyl) benzene; bis-(B'aminoethyl)-dirnethylbenzene; bis-(aminomethyl)-cyclohexane; 3-aminomethyl-3,5,5- trimethyl-cyclohexylamine; l-methyl-4( l-aminol -methylethyl )-cyclohexylamine; and 9,9-bis-( 3-aminopropyl fluorene.

Suitable ether codiamines include l,7-diamino-4-oxa-heptane; l,l l-diamino-6-oxa-undecane; l,7-diamino-3,5-dioxaheptane; l,lO-diamino-4,7-dioxa-decane; l,l0-diamino-4,7- dioxa- S-methyl-decane; l,l l-diamino-4,8-dioxa-undecane; l,l l-diamino- 4,8-dioxa-5-methylundecane; l l Z-diamino- 4,9-dioxa-dodecane', l,l 3-diamino-4,l O-dioXa-tridecane; l,l4-diamino-4,l l-dioxa-tetradecane; l,l l-diamino-4,8- dioxa-5,6-dimethyl-7-propionylundecane', l, l 4-diamino- 4,7, l O-trioxa-tetradecane; l l 3-diamino- 4,7, l 0-trioxa-5,8- dimethyl-tridecane; l ,l6diamino-4,7, l 0, l 3-tetra-oxa hexadecane; l,l l-diamino-4,8-dioxa-6,o-dimethyl-undecane; and

l ,20-diamino4. l 7-dioxa-eicosane.

Preferred embodiments of the invention include those in which the equivalence ratio between ethylene diamine and the codiamine is between 0.8202 and 0.5:0.5, especially at 0.7:0.3, and in which the equivalence ratio between the dimeric fatty acid and the monocarboxylic acid lies between 0.8102 and 0.7203, particularly at 0.75:0.25.

In the process of the invention, the greater the proportion of the aromatic, cycloaliphatic, long chain, or ether codiamine present, the better are the solubility properties of the resultant polyamide. The greater the proportion of ethylene diamine present, the higher is the softening point of the resultant polyamide.

show little tendency to block, in contrast with those printed with known ethanol-soluble printing ink resins. Also, ink resins according to the invention show outstanding adherence and good shine on conventional carriers, especially on pretreated polyethylene. The scratch resistance of printed Because of their low cost and relatively easy polymerizability, oleic acid and linoleic acid are preferred as starting materials for the preparation of polymeric fatty acids.

The usual approximate composition of the commercial sheets is excellent, particularly for those polyamides compris- 5 dimeric fatty acid product prepared from an unsaturated ing an ether codiamine. Resistance to cracking and scaling is uty d s: 5-15 percent by weight of Cir also at high levels. The mechanical properties of the resin y acid, 60-80 P y 8 of sr y acid, films, such as hardness and elasticity, as well as the properties and lor-35 P611361!t y Weight of sr' y acid and desirable in the coating arts, all meet the demands imposed on higher carboxylic acid Productsh 10 The mixtures obtained by polymerization can be fracp d i f h l id resins fth invention i l tionated by the usual distillation or solvent extraction reaction of the diamines, dimeric fatty acid, and monocarboxmethods. They can be hydrogenated before or after distillaylic acid at condensation temperatures between about 180 C. tion in order to decrease the degree of unsaturation using high and about 250 C., especially at about 230 C. Any remaining 1 5 pressure hydrogen in the presence of a hydrogenation catalyst. water of condensation is conveniently removed by applying a The preferred content of dimeric fatty acids in the fatty acid vacuum for one to two hours. in place of the free dimeric fatty Used in h Pr n n en i n i between 5 8nd 1 percent acids, their amide-forming derivatives can also be used, such y Weight The Content of mixtures of monomericdimflic, as their esters, in particular those which easily undergo and trimeric fatty acids can be determined either by gas chroaminolysis, such asthe methyl and ethyl esters. matography or according to the microdistillation method of For preparation of the polyarnides of the invention, those oil Chfin- XXX], 5 dimeric fatty acids are used which can be obtained by the free A bet er n er n ing of the present invention and of its radical, ionic, or thermal polymerization of fatty acids. The m ny advantages will be had y referring to h f l ing fatty acid can be a saturated or a monoor poly-ethylenically Specific eXamPIBS- given y y illustrationor acetylenically unsaturated natural or synthetic aliphatic monobasic acid, suitably having 8 to 24 carbon atoms. These Example 1 fatty acids can be polymerized by difierent means, but all give functionally similar products which can generally be charac- 400 grams of a commercially available dimerized fatty acid terized as polymeric fatty acids. The polymer products usually equivalent) P p from an unsamfllcd uracid o tai a ed i t amount f di i fatty id d and having a content of about 75 percent dimeric fatty acid, smaller amou ts of trimeri r hi her olyme i as ll a 15 percent trimeric fatty acid, and I0 percent monomeric monomeric, fatty acids. The term dimeric fatty acid" as used acid. grams of glacial acelic acid q in the specification and claims is to be understood to refer also 39.45 grams of ethylene diamin (0. q and to such mixtures containing small quantities of non-dimeric grams of hexamethylene diamine (0,3 equivalent) were mixed materials. 35 together and heated to 125 C. over a period of about 15 Polymerization of saturated fatty acids can be carried out at minutes under a nitrogen atmosphere with stirring. This temelevated temperatures with peroxide catalysts such as di-tperature was maintained for half an hour, then the mixture butyl-peroxide, for example. The straight chain and branchas raised to 225 C. over a period of two hours and held at chain acids such as caprylic, pelargonic, capric, lauric, this temperature for three additional hours. Finally. a vacuum myristic, palmitic, isopalmitic, stearic, arachidic, behinic, and of 15 mm. Hg. was applied for one more hour at a temperature lignoceric acids are suitable saturated fatty acids. However, of 225 C. this process is of little interest because of the small yield. The resulting product had an amine number of 2.64, an acid The polymerization of ethylenically unsaturated fatty acids number of 2.02, and a ring-and-ball softening point of l l3 C. is much more common. This can be done with or without The polyamide obtained was soluble in ethanol throughout catalysts, but uncatalyzed polymerization requires higher temthe entire concentration range up to percent. peratures. Suitable catalysts are acid or alkaline clays, di-t- Examples 2-i0 tabulated in tables I and ll below were butyl-peroxide, boron trifluoride and other Lewis acids, prepared in analogous fashion using other monocarboxylic anthroquinone, sulfur trioxide, and the like. The monomeric acids and aliphatic codiamines. The polyamide products are fatty acids commonly polymerized include the branchedhain 50 all soluble in ethanol, and their alcoholic solutions can be 1 and straight-chain, polyand/or mono-ethylenically unsatup epa ed ither c0ld 0r at the boiling point.

TABLE 1 Purity MOllOcllr- Dimeric (dimer boxyliv Ethylene Equivalence fatty acid content m-id Equivalence diamine (To-diamine rntio of 5 Example No. (gm.) in percent) (gm ratio oi ncids (gm.) (gm.)

200 Ca. 75 14.05 Ac 0. 75:11.25 19.12 22.78 NDA 200 011.75 14.05 A0 0. 75:0.25 22.55 15.18 NDA 200 (111.75 14.05115 0.75:0.25 16.90 30.38 NBA 200 Ca. 75 20.3110 0. 8010.20 25.03 15.217 NDA 200 Ca. 09 14.05111; 0. 7510.25 111. 72 22.78NDA 400 Ca. 75 21.05 Ac 0.80:0.20 42.24 27.75'1511) 200 011. 75 17,32 Pr 0. 7510.25 10.72 22.78 NDA 400 011.75 41.2511 0. 75:0.25 453.89 43.55 HDA 200 Cu. 75 25.51 Pr 0. 70:03!) 21.17 30.08 DDA N0'rE.-Ac=acetic acid. Pr=propionio acid. NI)'A=1,9-diami11o-nonanv. TMD=trinwthyl-lluxamothylemdiamine. HDA=hexumethylenediamlnm DDA=1,ILZ-diamino-dodecano.

rated acids such as 3-octene acid, ll-dodecene acid, linderic acid, lauroleic, oleic, elaidic, vaccenic, gadoleic, cetoleic, erucic, linoleic, linolenic, elaostearic, arachidic, clupanodonic, nisinic, and chaulmoogra oil acid.

The acetylenically unsaturated fatty acids, which-can be polymerized in the absence of catalysts because of their higher reactivity, seldom occur in nature and are expensive to synthesize. For this reason they are economically'less interesting. A number of acetylenically unsaturated fatty acids, either straight chain or branch chain, mono-unsaturated or polyunsaturat'ed, can be used for the preparation of polymeric fatty acids. For example, o-octadecyn, 9-octadecyn, l3-dokosyn and l7-octadecen-9,l l-diyn acids can be mentioned.

1 Dissolved in 24 hrs, in cold solvent, Dissolved in V hr. in worn) solvent,

Example 1 1 200 grams of dimeric fatty acid (0.75 equivalent), 14.05 grams of acetic acid (0.25 equivalent), 19.7 grams of ethylene Solutions of the polyamides according to the invention can be prepared in concentrations of at least 30 percent either at boiling temperatures or at room temperature.

For purposes of comparison, examples 1 and 20 of U5. Pat.

diamine (0.7 equivalent), and 17.15 grams of m-toluylene 5 diamine (0.3 equivalent) were mixed and heated to 125 C. 'ii f g iig i p P ff i ffg d over a period of 15 minutes. This temperature was maintained g o a pa en ls mso u e m 6 am) for 30 minutes percent solution 11'] isopropanol gels at room temperature. A Thereafter, the temperature was raised over a period of 2 em g z l f i ir a Kg: 3 hours to 225 C. and held at this temperature for a further 3 re i i i g f g 1 2:: 2 3: hours. Finally, a vacuum of about mm. Hg. was applied for p mbl g t l th I 1 l d afimher hour. glvens e percen so u ions in e a c0 0 5 men lone The polymer product had an amine number of 2,23, an acid E l 25 number of 3.69, and a softening point (ring and ball) of 1 12 C. 15 Four-hundred grams of dimerized fatty acid (0.75 Additi l l id were prepared according to the equivalent), 28.1 g. of acetic acid (0.25 equivalent), 45.08 g. vention in an analogous fashion. Tables 111 and 1V summarize of ethylene d'amme equwalem), and 25-12 8- 0f h results ff nh examples 12-24 diamino-4-oxahe tane (0.2 equivalent) were mixed with one TABLE 111 Equiv- Equiv- Dimcric Monoalence Ethylene alcnce tty carboxylic ratio of diamine ratlo of Example No. acid (gm.) acid (gm.) acids (gm.) Co'dmmine (gin) dlumincs 200 14.05 Ac 0.75:0.25 19.7 15.17 phcnylcnc diaminc.. 0720.3 200 14.05 Ac 0. 75:0. 25 19. 7 27.8 4,4 -diam1no diphenylmcthano 7:0. 3 200 14.05 Ac 0. 75:0. 25 19. 7 31.7 3,3-dimethy1-4,4-dlainino diphcny1mcthunc 0. .3 200 14.05 Ac 0. 75:0. 25 10.7 29.6 4,4-diamino-tlicyc1ohcxylmethane 0.7:0. 3 200 14.05 Ac 0. 75:0. 25 10. 7 33.45 3,3'-di111ethyl-4,4-diamino dicyclohcxylmcthunc. 0. 7:0. 3 200 14.05 Ac 0. 75:0. 25 15.89 31.01,4-bis-(amlnoethyD-bcnzcnc 0020.4 200 14.05 Ac 0. 75:0. 25 22.52 17.081,4-bis-(aminocthy1)-2,5-dimcthylbcnzcnc 0.810.! 400 14.05 Ac 0. 75:0. 25 39. 45 47.75 3-aminomethy1-3,5,5-trimcthyl cyelohcxylaminm. 0. 7:0. 3 400 37.7 Pr 0.75:0.25 39.45 ....(10 07:0.3 400 52.9 Bu 0. 7:0. 3 42. 25 51.30 3-arniuomethyl-3,5,fi-trimethyl cyclohvxylnmine 0. 7:0. 3 200 10.05 Ac 0. 8:0. 2 18. 50 21.60 l-methy1-4(1-amino-1-mcthyl-cthyl) cyclolu'xyluminc 07:11.3 200 14.05 Ac 0. 75:0. 25 10. 7 22.18 l-nicthyM(l-amino-Lmctltyl-cthyl) cyclohcxylamlnc 0. 7:0. 3 200 14.05 Ac 0.75:0. 25 10. 7 40.2 9,0-bis(uminopropyl)-fluorcnc 0. 7:0. 3

NOTE.A0=8C8tiO acid. Pr=propionic acid. Bu=butyric acid.

TABLE IV another and heated to 125 C. with stirring in an inert gas at- Sonenin mosphere. The temperature was held at 125 C. for one-hall Example No. Amine No. Acid No. point 0. hour, then raised to 225 C. over a period of two hours, and 58 so 115 left at the latter temperature for five hours. During the last two 2. 4 2:, 14.82 105 hours, a vacuum ofabout 15-20 mm./Hg. was applied. 5 :3? 1 The resulting polyamide resin had an amine number of 2.59, :12. 0:1; 13 an acid number of 2.64. and a ring and ball softening point of 120.5 C. The product could easily be dissolved in ethanol by 2. it; 2. 51 117 shaking, either at room temperature or at the boiling point. 3: :52 Additional polyamides were prepared according to the in- 100 vention in an analogous fashion. Tables V and V1 summarize g; g: 32 the results of further examples 26-35.

I TABLE v Dimeric Monocar- Equivalence Ethylene Equivalence boxylic ratio oi dlaminc ratio of acid (gm.) acids (gun) Co-diaminc (gnu) (hamhics 14.05 Ac 0. 75:0. 25 19.70 26.4 1,11-d1am1n0-6-oxaundecanc 0. 7:0. 3 28.10 Ac 0. 75:0. 25 30. 44 40.41,10-11lamina-4,7-d1oxa-dccanc 07:11.? 18.05 Ac 0. 70:0. 30 21. 13 28.72 1,IO-diamino-4,7-dioxa-5 mcthyl-decane 07:11.5 28.10 Ac 0. 75:0. 25 39. 44 53.65 1,11-diamino-4,8-dloxa-undccanc 07:11. 5 14.05 Ac 0. 75:0. 25 19. 70 28.60 1,ll-cllam1no-4,8-5-methy1-undccane 0. 7:0. .5 10.52 Ac 0. 80:0. 20 19. 70 22.50 1,12-d1amino-4,9-dloxa-dodccanc.. 0. 75:0. 25 14.05 Ac 0. 75:0. 25 22. 20.60 1,13-dlamin04,10-d1oxa-tr1dccane.. 0.15:0. 2 14.05 Ac 0. 75:0. 25 22. 50 20.6 1,13-d1um1no-4,7,IO-trloxa-trldccane. 0. 8:0. 2 17.35 Pr 0. 75:0. 25 19.70 24.72 1,10d1amino-4,7-d1oxa-decane 0. 7:0.? 20.6 B11 0. 75:0. 25 19. 70 .do 0. 7:0. 6

Nora-Ae acetic acid. Bu butyric acid. Pr propionic acid.

7 I What 1 claim:

1. A synthetic polyamide prepared by cocondensing, at a g ffi temperature between about 180 C. and about 250 C.. sub- Emmple No. Amine No. Acid No. C.) stantially equivalent amounts of an acid component consisting 26 Q96 3.63 112 essentially of (1) a dimeric fatty acid prepared by polymeriz- 27 2.23 2.12 113 ing a monobasic acid of an aliphatic hydrocarbon having 8-2 4 g IIII kg? 3:3; 5:? carbon atoms and (2) a monobasic straight chain alkanolc 30 1.53 2.61 111 acid having [-5 carbon atoms, and of an amine component 3% i'gg gag flag consisting essentially of ethylene diamine and a co-diamine 33::::::::::: 1:84 2:93 119 selected from the group consisting of 1) an alkylene diamine ggIIIIIIIII g:% kg? having 6 to 12 carbon atoms; (2) an aromatic diamine having one of the following formulas:

(3) a cycloaliphatic diamine having one of the following formulas:

wherein x in said formulas is zero or a small whole number from l to 3 inclusive, and wherein R -R are hydrogen and up to two of said radicals R R may be lower alkyl; and (4) an ether diamine of the fonnula wherein n is an integer from 3 to 5 inclusive, x is zero or an integer from I to 3 inclusive, and R is an unsubstituted alkylene radical having 1 to 12 carbon atoms or such a radical having one or two alkyl substituents thereon, said substituents having 1 to 4 7 carbon atoms, the equivalence ratio between said dimeric fatty acid and said monobasic acid being between 0.8:0.2 and 0.7:0.3. and the equivalence ratio between said ethylene diamine and said codiamine being between 0.8;0.2 and 0.5:0.5.

2. A polyamide as in claim 1 .wherein said monocarboxylic acid is acetic acid.

3. A polyamide as in claim I wherein a mixture of ethylene diamine and an alkylene diamine having six to 12 carbon atoms is employed.

4. A polyamide as in claim 3 wherein said alkylene diamine is l,6-diaminohexane, l,9-diaminononane. l. l Z-diaminododecane, or trimethyl-hexamethylene diamine.

5. A polyamide as in claim 1 wherein a mixture of ethylene diamine and an aromatic diamine is employed.

6. A polyamide as in claim 5 wherein said aromatic diamine is l,4-bis(aminoethyl)-benzene or 9.9-bis( aminopropyl)- fluorene.

7. A polyamide as in claim 1 wherein a mixture of ethylene diamine and a cycloaliphatic diamine are employed.

8. A polyamide as in claim 7 wherein said cycloaliphatic diamine is 3-aminomethyl-3,5,5-trimethyl-cyclohexylamine.

9. A polyamide as in claim 1 wherein a mixture of ethylene diamine and an ether diamine is employed.

10. A polyamide as in claim 9 wherein said ether diamine is l, l 0-diamino-4,7-dioxa-decane, l l 0-diarnino-4,7- dioxa-S- methybdecane, l,l3-diamino-4,7,loTrioxa-decane, and l,l2- diamino-4,9-dioxa-dodecane.

I! t i t i

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U.S. Classification524/599, 106/243, 528/339.3, 106/31.76
International ClassificationC09D11/10, C08G69/34
Cooperative ClassificationC09D11/102, C08G69/34
European ClassificationC09D11/102, C08G69/34