USH1043H - Bis-hydroxy diamides and methods therefor - Google Patents
Bis-hydroxy diamides and methods therefor Download PDFInfo
- Publication number
- USH1043H USH1043H US07/465,666 US46566690A USH1043H US H1043 H USH1043 H US H1043H US 46566690 A US46566690 A US 46566690A US H1043 H USH1043 H US H1043H
- Authority
- US
- United States
- Prior art keywords
- hydroxy
- diamides
- acid
- bis
- carbon atoms
- 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.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract 3
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 101150108015 STR6 gene Proteins 0.000 claims 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 24
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 abstract description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 12
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 12
- ASDQMECUMYIVBG-UHFFFAOYSA-N 2-[2-(2-aminoethoxy)ethoxy]ethanol Chemical compound NCCOCCOCCO ASDQMECUMYIVBG-UHFFFAOYSA-N 0.000 abstract description 11
- ANOJXMUSDYSKET-UHFFFAOYSA-N 2-[2-[2-(2-aminoethoxy)ethoxy]ethoxy]ethanol Chemical compound NCCOCCOCCOCCO ANOJXMUSDYSKET-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001361 adipic acid Substances 0.000 abstract description 11
- 235000011037 adipic acid Nutrition 0.000 abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 10
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001412 amines Chemical class 0.000 abstract description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- QPGBFKDHRXJSIK-UHFFFAOYSA-N 2-tert-butylbenzene-1,3-dicarboxylic acid Chemical compound CC(C)(C)C1=C(C(O)=O)C=CC=C1C(O)=O QPGBFKDHRXJSIK-UHFFFAOYSA-N 0.000 abstract description 2
- CDZMWAHBQLPCHD-UHFFFAOYSA-N 3-(4-carboxyphenyl)-1,1,3-trimethyl-2h-indene-5-carboxylic acid Chemical compound C12=CC(C(O)=O)=CC=C2C(C)(C)CC1(C)C1=CC=C(C(O)=O)C=C1 CDZMWAHBQLPCHD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 239000002816 fuel additive Substances 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 150000001470 diamides Chemical class 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- -1 tetraethylene glycol diamines Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 150000001408 amides Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 241000801593 Pida Species 0.000 description 4
- ZBIKORITPGTTGI-UHFFFAOYSA-N [acetyloxy(phenyl)-$l^{3}-iodanyl] acetate Chemical compound CC(=O)OI(OC(C)=O)C1=CC=CC=C1 ZBIKORITPGTTGI-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- 239000004831 Hot glue Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- AMEDKBHURXXSQO-UHFFFAOYSA-N azonous acid Chemical class ONO AMEDKBHURXXSQO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JJOJFIHJIRWASH-UHFFFAOYSA-N icosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 150000003077 polyols Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 description 1
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- XFEGRFIENDJTCK-UHFFFAOYSA-N 2-phenyl-2,3-dihydroindene-1,1-dicarboxylic acid Chemical compound C1C2=CC=CC=C2C(C(=O)O)(C(O)=O)C1C1=CC=CC=C1 XFEGRFIENDJTCK-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920006039 crystalline polyamide Polymers 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical group OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
Definitions
- the invention relates to by-products from the manufacture of polyoxyalkyleneamines, and, in one aspect, more particularly relates to bis-hydroxy amides prepared by the reaction of such by-products with carboxylic acids.
- Triethylene and tetraethylene glycol diamines may be continuously produced from glycols catalytically.
- the triethylene glycol diamine and tetraethylene glycol diamine products are known under the trade names JEFFAMINE® EDR-148 Amine and JEFFAMINE® EDR-192 Amine, respectively, as made by Texaco Chemical Co. These materials are useful as intermediates in the preparation of hydrophilic nylon resins, and as epoxy curing agents.
- JEFFAMINE® EDR-148 Amine and JEFFAMINE® EDR-192 Amine are useful as intermediates in the preparation of hydrophilic nylon resins, and as epoxy curing agents.
- a crystalline polyamide which has improved tensile strength and which has a heat deflection temperature in excess of 240° C. when filled is formed from dicarboxylic acid compounds comprising compounds of terephthalic acid and isophthalic acid in a molar ratio of at least 80:20 to about 99:1 and diamines comprising hexamethylene diamine and trimethylhexamethylene diamine in a molar ratio of about 98:2 to about 60:40, according to U.S. Pat. No. 4,617,342.
- Hot melt adhesives are also related to these kinds of materials.
- U.S. Pat. No. 4,656,242 describes that poly(ester-amide) polymers made from an acid component and a substantially equivalent amount of an amine and a diol component are suitable as hot melt adhesives for holding plastics.
- the acid component has 10-80 equivalent percent of a dimer acid having about 36 carbon atoms and 40-90 equivalent percent of a linear dicarboxylic acid.
- the amine and diol component has from 40-90 equivalent percent of an organic diamine and 10-60 equivalent percent of a diol.
- 4,611,051 which teaches poly(ester-amide) hot-melt adhesives prepared from condensation of a mixture of polymeric fatty acids and 1,18-octadecanedicarboxylic acid, and a substantially equivalent proportion of a mixture of a polyamine and a polyol.
- Suitable polyamines include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexamethylene-diamine, piperazine, and 4,4'-methylene-bis-(cyclohexylamine).
- Appropriate diols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexamethylenediol, cyclohexane-methanol, polyethylene glycol and polybutylene glycol.
- polyesteramides are prepared by condensing (A) dimerized fatty acids having 16 to 44 carbon atoms, (B) a diamine having a formula of NH 2 --R--NH 2 where R is an aliphatic hydrocarbyl having 3 to 36 carbon atoms and (C) aminoethoxy-ethanol and at least one dicarboxylic acid having the formula R"OOC--R'--COOR" where R' is a hydrocarbyl of 4 to 12 carbon atoms and R" is H or alkyl having 1 to 8 carbon atoms.
- R' is a hydrocarbyl of 4 to 12 carbon atoms and R" is H or alkyl having 1 to 8 carbon atoms.
- U.S. Pat. No. 4,397,991 describes similar products.
- the polyesteramides are used as adhesives which combine good elongation, quick setting times and good low temperature flexibility.
- Another object of the invention to provide a method for making these novel materials that is very simple.
- novel bis-hydroxy diamides having the formula: ##STR2## where R is an alkylene moiety having from 3 to 34 carbon atoms or an arylene moiety having from 6 to 34 carbon atoms and where x ranges from 3 to 6.
- polyethylene glycol monoamines that are produced as by-products in the production of JEFFAMINE® EDR amines, by-products such as triethylene glycol monoamine and tetra-ethylene glycol monoamine, as well as materials such as diethylene glycol monoamine, may be advantageously reacted with dicarboxylic acids to form novel bis-hydroxy diamides.
- novel bis-hydroxy diamides are useful to make mixed polyamide-esters and polyurethanes, as is seen in companion patent application Ser. No. 07/465,290, filed of even date, incorporated by reference herein.
- novel bis-hydroxy diamides of this invention may be made according to the reaction that may be schematically diagrammed as: ##STR3## where (I) are the polyethylene glycol monoamine by-products or other materials where x ranges from 2 to 6, preferably 2 to 5 and most preferably from 3 to 4. When x is 2, the compound is diethylene glycol monoamine. When x is 3 and 4, the compounds are triethylene glycol monoamine and tetraethylene glycol monoamine, respectively.
- Compound (II) is the dicarboxylic acid and R may be an alkylene moiety having from 3 to 34 carbon atoms in one embodiment, in one aspect from 4 to 20 carbon atoms, and in a further aspect from 4 to 9, or an alkylene moiety having from 6 to 34 carbon atoms.
- the dicarboxylic acid may be selected from the group consisting of adipic acid, terephthalic acid, isophthalic acid, t-butyl isophthalic acid, 1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl) indane also known as phenylindane dicarboxylic acid or PIDA and mixtures thereof.
- the dicarboxylic acid may be "dimer” acid which is mainly a C-36 dicarboxylic acid. This product is prepared by dimerizing unsaturated fatty acids. The esters of these acids may also be used.
- the novel bis-hydroxy diamides are represented as compound (III) where R and x have the meanings given above.
- the bis-hydroxy diamides may be made by contacting at least two moles of the polyethylene glycol monoamine for every mole of dicarboxylic acid in the presence of heat, from approximately 180° to about 250° C. as a narrower range, where a broad temperature range for this reaction is from about 160° to about 280° C.
- the molar ratio of monoamine to dibasic acid is about 2:1.
- No catalyst is required for this reaction, although one may be yet discovered that might prove beneficial.
- the reaction may also be conducted at atmospheric pressure. The reaction is quite selective yielding the bis-hydroxy diamides in nearly quantitative yield.
- the products are light-colored solids or liquids, depending on the starting materials. The products and methods of this invention will be described in more detail with reference to the following examples.
- the saponification number was 15.41 mg. KOH/g. which was determined by refluxing with alcoholic sodium hydroxide. This indicates only 5.4% of the product reacted with potassium hydroxide--or from another point of view this amide is hard to hydrolyze--in fact, all of the hydrolysis took place at an ester linkage, since NMR showed an ester to hydroxyl linkage ratio of about 1.1 to 32.3. Thus, the reaction was not 100% amide, but was selective in the order of 95%. There was no unreacted amine.
- the weight average molecular weight was 407 and the number average molecular weight was 407 by Gel Permeation Chromatography (GPC); the theoretical molecular weight was 408. These results prove the selectivity involved.
- Table I illustrates that the product properties depend on the starting materials.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
Description
TABLE I __________________________________________________________________________ Diols with Amide Linkages Properties Hydroxy- Hydroxyl No. Ex. Carboxylic Acid amine meq/g. (Theory) __________________________________________________________________________ 2 Adipic acid DGA 5.9 (6.0) Solid, creamy, light brown, opaque 3 Terephthalic acid DGA 2.5 (5.5) Solid, brown, hard, transparent 4 Isophthalic acid DGA 3.6 (5.5) Solid, soft, brown, t-Butyl IPA transparent 5 PIDA DGA 3.4 (4.0) Solid, glass-like, transparent, brown, brittle 6 NDC DGA -- -- Solid, hard, black 7 Adipic acid TEGMA 4.9 (4.9) -- 8 Terephthalic acid TEGMA 4.5 (4.7) Solid, creamy white Isophthalic acid t-Butyl IPA 9 PIDA TEGMA 2.8 (3.4) Solid, hard, NDC transparent, brown Trimesic acid 10 Adipic acid T4EGMA -- -- Solid, creamy, white 11 Terephthalic acid T4EGMA 3.70 (3.88) Liquid, brown, transparent 12 Isophthalic acid T4EGMA 3.55 (3.75) Liquid, brown, transparent 13 t-Butyl IPA T4EGMA 3.30 (3.47) Liquid, brown, transparent 14 PIDA T4EGMA 2.84 (2.94) Semisolid, brown, NDC elastomeric __________________________________________________________________________
______________________________________ GLOSSARY ______________________________________ DGA Diethylene glycol monoamine (DEGMA) or Diglycolamine ® Agent made by Texaco Chemical Company. IPA Isophthalic acid. NDC Naphthalene dicarboxylic acid - esters of this acid are preferred because of their relatively higher purity. TEGMA Triethylene glycol monoamine. T.sub.4 EGMA Tetraethylene glycol monoamine. T.sub.5 EGMA Pentaethylene glycol monoamine. ______________________________________
Claims (3)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/465,666 USH1043H (en) | 1990-01-16 | 1990-01-16 | Bis-hydroxy diamides and methods therefor |
EP19900314427 EP0437981B1 (en) | 1990-01-16 | 1990-12-28 | Polyamide-esters, processes for the manufacture thereof and intermediates therefor |
DE69014582T DE69014582D1 (en) | 1990-01-16 | 1990-12-28 | Polyamide esters, processes for their preparation and interconnections therefor. |
CA002033584A CA2033584A1 (en) | 1990-01-16 | 1991-01-03 | Bis-hydroxy diamides and methods therefor |
JP1499091A JPH05105750A (en) | 1990-01-16 | 1991-01-16 | Polyamideester, process for manufacturing same and its intermediate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/465,666 USH1043H (en) | 1990-01-16 | 1990-01-16 | Bis-hydroxy diamides and methods therefor |
Publications (1)
Publication Number | Publication Date |
---|---|
USH1043H true USH1043H (en) | 1992-04-07 |
Family
ID=23848687
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/465,666 Abandoned USH1043H (en) | 1990-01-16 | 1990-01-16 | Bis-hydroxy diamides and methods therefor |
Country Status (2)
Country | Link |
---|---|
US (1) | USH1043H (en) |
CA (1) | CA2033584A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040231556A1 (en) * | 2002-12-26 | 2004-11-25 | Canon Kabushiki Kaisha | Anticurling agent, ink jet ink, method for ink jet recording and method for reducing curling |
CN113201319A (en) * | 2015-11-20 | 2021-08-03 | 瀚森公司 | Chemical product for surface protection |
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-
1990
- 1990-01-16 US US07/465,666 patent/USH1043H/en not_active Abandoned
-
1991
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040231556A1 (en) * | 2002-12-26 | 2004-11-25 | Canon Kabushiki Kaisha | Anticurling agent, ink jet ink, method for ink jet recording and method for reducing curling |
US6966944B2 (en) * | 2002-12-26 | 2005-11-22 | Canon Kabushiki Kaisha | Anticurling agent, ink jet ink, method for ink jet recording and method for reducing curling |
CN113201319A (en) * | 2015-11-20 | 2021-08-03 | 瀚森公司 | Chemical product for surface protection |
Also Published As
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