CN114874414B - Asparagus resin and synthesis method thereof - Google Patents
Asparagus resin and synthesis method thereof Download PDFInfo
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- CN114874414B CN114874414B CN202110640348.7A CN202110640348A CN114874414B CN 114874414 B CN114874414 B CN 114874414B CN 202110640348 A CN202110640348 A CN 202110640348A CN 114874414 B CN114874414 B CN 114874414B
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- epoxy compound
- primary amine
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- epoxy
- resin
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- 229920005989 resin Polymers 0.000 title claims description 17
- 239000011347 resin Substances 0.000 title claims description 17
- 241000234427 Asparagus Species 0.000 title abstract description 7
- 235000005340 Asparagus officinalis Nutrition 0.000 title abstract description 7
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000004593 Epoxy Substances 0.000 claims abstract description 23
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 14
- -1 dibasic ester primary amine Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims description 7
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 5
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 3
- VQMQXWYQIIUJIT-UHFFFAOYSA-N 2-[[4-(oxiran-2-ylmethoxymethyl)cyclohexyl]methoxymethyl]oxirane Chemical compound C1OC1COCC(CC1)CCC1COCC1CO1 VQMQXWYQIIUJIT-UHFFFAOYSA-N 0.000 claims description 3
- UMILHIMHKXVDGH-UHFFFAOYSA-N Triethylene glycol diglycidyl ether Chemical compound C1OC1COCCOCCOCCOCC1CO1 UMILHIMHKXVDGH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 229960005237 etoglucid Drugs 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 2
- VTPXYFSCMLIIFK-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propan-1-ol Chemical compound C1OC1COCC(COCC1OC1)(CO)COCC1CO1 VTPXYFSCMLIIFK-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 5
- 238000006243 chemical reaction Methods 0.000 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229920006395 saturated elastomer Polymers 0.000 description 16
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 13
- 125000003342 alkenyl group Chemical group 0.000 description 13
- 150000003141 primary amines Chemical class 0.000 description 11
- 239000000499 gel Substances 0.000 description 10
- HMNXRLQSCJJMBT-LURJTMIESA-N diethyl (2s)-2-aminobutanedioate Chemical compound CCOC(=O)C[C@H](N)C(=O)OCC HMNXRLQSCJJMBT-LURJTMIESA-N 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000012154 double-distilled water Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229920000805 Polyaspartic acid Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 108010064470 polyaspartate Proteins 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NZSVGVCYSJJQBS-UHFFFAOYSA-N C.C1(=CC=CC=C1)C1(C(COCC2(C(O2)(C2=CC=CC=C2)C2=CC=CC=C2)C2=CC=CC=C2)(O1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C.C1(=CC=CC=C1)C1(C(COCC2(C(O2)(C2=CC=CC=C2)C2=CC=CC=C2)C2=CC=CC=C2)(O1)C1=CC=CC=C1)C1=CC=CC=C1 NZSVGVCYSJJQBS-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000608 Polyaspartic Polymers 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005406 washing Methods 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
Abstract
The invention relates to the field of synthesis of asparaguses, in particular to asparaguses and a synthesis method thereof. More particularly, the invention relates to an asparaben prepared from primary amine of dibasic esters and an epoxy compound, and provides an asparaben which can be obtained in high yield by using the epoxy compound containing dibasic esters and primary amine to attack polyepoxy groups, so that the residue of primary amine can be effectively reduced, the subsequent curing can be promoted to be smoothly carried out, and the curing time and the construction rate can be adjusted. In addition, the inventors found that the yield of asparaguson is not only related to the structure of primary amine but also to the structure of epoxy compound, especially when using a polyepoxy compound, when the chain or ring structure of epoxy compound to which the epoxy group is linked is improper in the epoxy compound, not only is the yield unfavorable, but also the residual primary amine is more difficult to remove, resulting in the generation of gel during the subsequent curing.
Description
Technical Field
The invention relates to the field of synthesis of asparaguses, in particular to asparaguses and a synthesis method thereof.
Background
As a special type of steric hindrance secondary amine, the polyaspartic acid ester (Polyaspartic Ester, PAE) has better construction performance compared with the traditional polyurea material, and because of the imine structure, the curing speed can be effectively regulated, and the rigidity and toughness after curing are improved.
At present, polyaspartic acid ester is mainly prepared from primary amine and maleic acid ester, but the reaction is often incomplete, the conversion rate of more than 90% is difficult to obtain, and the residual primary amine is easy to excessively congeal in the subsequent and isocyanate curing processes, so that the appearance and mechanical properties of the coating are affected.
In order to promote the reaction of primary amine, the main two modes at present are respectively adding special catalysts such as nitrogen-containing aromatic heterocyclic catalysts, triazole or tetrazole, or metal catalysts such as organic tin salts, and the other mode is to further add reactants such as maleate or acrylic ester at the later stage of the reaction to promote the reaction, but the two modes easily cause the increase of cost, and the catalysts or reactants with different structures can be introduced to influence the subsequent removal and even the curing.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides an asparaguson resin, which is prepared from primary dibasic ester and epoxy compound, wherein the structural formula of the primary dibasic ester is shown as the formula (1):
r is C1-C10 alkyl.
As a preferred embodiment of the present invention, the epoxy compound includes an epoxy resin and/or a glycidyl ether.
As a preferable technical scheme of the invention, the number of epoxy groups of the glycidyl ether is 2-5.
As a preferable technical scheme of the invention, the glycidyl ether is chain glycidyl ether and/or cyclic glycidyl ether.
As a preferable technical scheme of the invention, when the number of epoxy groups of the glycidyl ether is 2, the structural formula of the chain glycidyl ether is shown as the formula (2) or the formula (3):
m is 2-30;
n is 1 to 30, X is a C1 to C10 alkyl group.
As a preferable technical scheme of the invention, when the number of epoxy groups of the glycidyl ether is 3 or 4, the structural formula of the chain glycidyl ether is shown as the formula (4):
when p is 3, R 1 Is H or alkyl, when p is 4, R 1 Is H;
y is selected from one or more of C1-C30 alkyl, C1-C30 alkenyl, C1-C30 alkyl derivative and C1-C30 alkenyl derivative.
As a preferable technical scheme of the invention, the structural formula of the cyclic glycidyl ether is shown as a formula (5) or a formula (6):
q is 2-5, Z is selected from one or more of C1-C30 alkyl, C1-C30 alkenyl, C1-C30 alkyl derivative and C1-C30 alkenyl derivative;
R 2 h, C1 is a C1-C6 cyclic alkyl group or a C1-C6 chain alkyl group.
As a preferable embodiment of the present invention, the C1-C30 alkyl derivative is a C1-C30 alkyl derivative in which a methylene group is substituted with O, S, NH, C =o or c=oo, and the C1-C30 alkenyl derivative is a C1-C30 alkenyl derivative in which a methylene group is substituted with O, S, NH, C =o or c=oo.
As a preferable technical scheme of the invention, the molar ratio of the amine group of the dibasic ester primary amine to the epoxy group of the epoxy compound is 1: (0.9-1.1).
The second aspect of the present invention provides a method for synthesizing the asparaguson, comprising: and (3) reacting the dibasic ester primary amine with an epoxy compound at 60-100 ℃ to obtain the asparaguste.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides an asparaben, which can obtain asparaben with high yield by using a primary amine containing dibasic ester to attack epoxy compound with multiple epoxy groups, effectively reduce the residue of primary amine, promote the successful proceeding of subsequent curing, and adjust the curing time and the construction rate.
(2) In addition, the inventors found that the yield of asparaguson is not only related to the structure of primary amine but also to the structure of epoxy compound, especially when using a polyepoxy compound, when the chain or ring structure of epoxy compound to which the epoxy group is linked is improper in the epoxy compound, not only is the yield unfavorable, but also the residual primary amine is more difficult to remove, resulting in the generation of gel during the subsequent curing.
(3) And the inventors have unexpectedly found that, as the number of epoxy groups increases, such as 3 or 4 epoxy groups, the chain length of X or Y or R between the epoxy groups 1 The isosubstituted groups have an important influence on the attack of primary amines, the yield increases and decreases with increasing chain length of X or Y, and R 1 The structure of the substituents is not too large, which would otherwise affect the subsequent yields, and the residual primary amine, even during the reaction, to give gels.
Detailed Description
The contents of the present invention can be more easily understood by referring to the following detailed description of preferred embodiments of the present invention and examples included. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
The singular forms include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or event may or may not occur, and that the description includes both cases where the event occurs and cases where the event does not.
Approximating language, in the specification and claims, may be applied to modify an amount that would not limit the invention to the specific amount, but would include an acceptable portion that would be close to the amount without resulting in a change in the basic function involved. Accordingly, the modification of a numerical value with "about", "about" or the like means that the present invention is not limited to the precise numerical value. In some examples, the approximating language may correspond to the precision of an instrument for measuring the value. In the present specification and claims, the range limitations may be combined and/or interchanged, such ranges including all the sub-ranges contained therein if not expressly stated.
Furthermore, the indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirements of the number of elements or components (i.e. the number of occurrences). Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component also includes the plural reference unless the amount is obvious to the singular reference.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
In a first aspect, the present invention provides an asparagus resin prepared from a primary dibasic ester and an epoxy compound.
Dibasic ester primary amine
In one embodiment, the structural formula of the dibasic ester primary amine is shown as a formula (1):
r is a C1-C10 alkyl group, and examples thereof include methyl, ethyl, isopropyl, butyl, hexyl, octyl, etc., and is preferably a C1-C5 alkyl group.
The primary dibasic ester of the invention can firstly obtain the structure of the dibasic acid according to the reaction of RO 126760AO maleic acid and ammonia waterAnd then the dibasic acid and alcohol are prepared under the catalysis of catalysts such as sulfuric acid and the like according to CN 108440494A.
Epoxy compound
In one embodiment, the epoxy compounds of the present invention include an epoxy resin and/or a glycidyl ether.
Examples of the epoxy resin include, but are not limited to, bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydrogenated bisphenol a epoxy resin, hydrogenated bisphenol F epoxy resin, and glycidyl type epoxy resin.
Preferably, the glycidyl ethers of the invention have a number of epoxide groups of from 2 to 5, preferably from 2 to 4.
More preferably, the glycidyl ether of the present invention is a chain glycidyl ether and/or a cyclic glycidyl ether.
Further preferably, when the number of epoxy groups of the glycidyl ether is 2, the structural formula of the chain glycidyl ether is shown as formula (2) or formula (3):
m is 2 to 30, and examples thereof include 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, and 30;
n is 1 to 30, examples of which include 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28 and 30, X is a C1 to C10 alkyl group, examples of which include methyl, ethyl, isopropyl, butyl, hexyl and octyl, and examples of which are preferably C1 to C6 alkyl groups.
Still more preferably, when the number of epoxy groups of the glycidyl ether is 3 or 4, the structural formula of the chain glycidyl ether is shown as formula (4):
when p is 3, R 1 Is H or alkyl, preferably R 1 Is H or C1-C3 alkyl, when p is 4, R 1 Is H;
y is selected from one or more of C1-C30 alkyl, C1-C30 alkenyl, C1-C30 alkyl derivative and C1-C30 alkenyl derivative, preferably one or more of C1-C20 alkyl, C1-C20 alkenyl, C1-C20 alkyl derivative and C1-C20 alkenyl derivative, and methyl, ethyl, butyl, octyl, dodecyl, tridecyl, octadecyl, docosyl, vinyl, butenyl, octenyl, dodecenyl, tridecenyl, octadecenyl and docosanyl are exemplified.
In a preferred embodiment, the structural formula of the cyclic glycidyl ether of the present invention is represented by formula (5) or formula (6):
q is 2 to 5, preferably 2 to 4,Z, and is one or more selected from C1-C30 alkyl, C1-C30 alkenyl, C1-C30 alkyl derivatives and C1-C30 alkenyl derivatives, preferably one or more selected from C1-C20 alkyl, C1-C20 alkenyl, C1-C20 alkyl derivatives and C1-C20 alkenyl derivatives, and examples thereof include methyl, ethyl, butyl, octyl, dodecyl, tridecyl, octadecyl, docosyl, vinyl, butenyl, octenyl, dodecenyl, tridecenyl, octadecenyl and docosanyl;
R 2 h, C1 is a C1-C6 cyclic alkyl group or a C1-C6 chain alkyl group.
Aryl or cycloalkyl, preferably phenyl, naphthyl, cyclohexyl, cyclopentyl.
In a more preferred embodiment, the C1-C30 alkyl derivative of the present invention is a C1-C30 alkyl wherein the methylene group is replaced with O, S, NH, C =o or c=oo, and a C1-C30 alkenyl derivative is a C1-C30 alkenyl wherein the methylene group is replaced with O, S, NH, C =o or c=oo. The number of carbon atoms substituted in the C1-C30 alkyl derivative and the C1-C30 alkenyl derivative according to the present invention may be one or more, and is not particularly limited.
Examples of glycidyl ethers include, but are not limited to, triphenylglycidyl ether methane, trimethylol triglycidyl ether, tetraglycidyl xylene diamine, ethylene glycol diglycidyl ether, glycerol triglycidyl ether, castor oil triglycidyl ether, pentaerythritol tetraglycidyl ether, 1, 4-bis [ (glycidyloxy) methyl ] cyclohexane, tetraphenyl glycidyl ether ethane, triethylene glycol diglycidyl ether, resorcinol diglycidyl ether.
In one embodiment, the molar ratio of amine groups of the dibasic ester primary amine of the present invention to epoxy groups of the epoxy compound is 1: (0.9 to 1.1), for example, 1:0.9, 1:0.95, 1:1. 1:1.05, 1:1.1.
in a second aspect, the present invention provides a method for synthesizing asparaguse as described above, comprising: and (3) reacting the dibasic ester primary amine with an epoxy compound at 60-100 ℃ to obtain the asparaguste. The end point of the reaction of the present invention can be monitored by TLC,
in one embodiment, after the reaction of the present invention, an organic solvent is added and mixed, and after washing with alkali solution and water, the asparaguson is obtained by reduced pressure distillation and drying.
In one embodiment, the organic solvent is selected from one or more of esters, ethers and ketones, such as ethyl acetate, butyl acetate, diethyl ether, acetone and methyl ethyl ketone.
In one embodiment, the alkali solution of the present invention may be a common alkali solution, such as saturated sodium bicarbonate aqueous solution, saturated sodium chloride aqueous solution, saturated ammonium chloride solution, etc., without specific limitation.
Examples
The present invention will be specifically described below by way of examples. It is necessary to point out that the following examples are given for further illustration of the invention and are not to be construed as limitingIn order to limit the scope of the present invention, those skilled in the art may make various modifications and adjustments, which are not essential, according to the above-described aspects of the present invention, while still falling within the scope of the present invention. The structure of diethyl aspartate in examples 1-8 isR is ethyl.
Example 1
The present example provides an asparaguse resin and a method of preparing the same, comprising: under the protection of nitrogen, 87 g of ethylene glycol diglycidyl ether is added dropwise into a four-neck flask filled with 189 g of diethyl aspartate, the temperature is slowly increased to 60 ℃, the reaction is continued at the temperature after the dropwise addition, and TLC monitors the end of the reaction. After the reaction, ethyl acetate was added, and the mixture was washed with a saturated aqueous sodium hydrogencarbonate solution, a saturated aqueous sodium chloride solution and double distilled water, and after the solvent was distilled off under reduced pressure, anhydrous sodium sulfate was added to dry the mixture. 260 g of a pale yellow oily liquid was obtained in 94.2% yield without gel.
Example 2
The present example provides an asparaguse resin and a method of preparing the same, comprising: under the protection of nitrogen, 101 g of butanediol diglycidyl ether is added dropwise into a four-neck flask filled with 189 g of diethyl aspartate, the temperature is slowly increased to 60 ℃, the reaction is continued at the temperature after the dropwise addition, and TLC monitors the end of the reaction. After the reaction, ethyl acetate was added, and the mixture was washed with a saturated aqueous sodium hydrogencarbonate solution, a saturated aqueous sodium chloride solution and double distilled water, and after the solvent was distilled off under reduced pressure, anhydrous sodium sulfate was added to dry the mixture. 280 g of pale yellow oily liquid are obtained in 96.6% yield without gel.
Example 3
The present example provides an asparaguse resin and a method of preparing the same, comprising: under the protection of nitrogen, 151 g of trimethylolpropane triglycidyl ether is added dropwise into a four-neck flask filled with 284 g of diethyl aspartate, the temperature is slowly raised to 60 ℃, the reaction is continued at the temperature after the dropwise addition, and TLC monitors the end point of the reaction. After the reaction, ethyl acetate was added, and the mixture was washed with a saturated aqueous sodium hydrogencarbonate solution, a saturated aqueous sodium chloride solution and double distilled water, and after the solvent was distilled off under reduced pressure, anhydrous sodium sulfate was added to dry the mixture. 400 g of yellow oily liquid is obtained, the yield is 92.0%, and no gel exists.
Example 4
The present example provides an asparaguse resin and a method of preparing the same, comprising: 180 g of pentaerythritol glycidyl ether is added dropwise into a four-neck flask containing 378 g of diethyl aspartate under the protection of nitrogen, the temperature is slowly raised to 60 ℃, the reaction is continued at the temperature after the dropwise addition, and TLC monitors the end of the reaction. After the reaction, ethyl acetate was added, and the mixture was washed with a saturated aqueous sodium hydrogencarbonate solution, a saturated aqueous sodium chloride solution and double distilled water, and after the solvent was distilled off under reduced pressure, anhydrous sodium sulfate was added to dry the mixture. 510 g of brown oily liquid are obtained in a yield of 91.3% without gel.
Example 5
The present example provides an asparaguse resin and a method of preparing the same, comprising: under the protection of nitrogen, 184.6 g of glycerol triglycidyl ether is added dropwise into a four-neck flask containing 567 g of diethyl aspartate, the temperature is slowly raised to 60 ℃, the reaction is continued at the temperature after the dropwise addition, and TLC monitors the end of the reaction. After the reaction, ethyl acetate was added, and the mixture was washed with a saturated aqueous sodium hydrogencarbonate solution, a saturated aqueous sodium chloride solution and double distilled water, and after the solvent was distilled off under reduced pressure, anhydrous sodium sulfate was added to dry the mixture. 700 g of a yellow oily liquid was obtained in 93.1% yield without gel.
Example 6
Under the protection of nitrogen, 131 g of triethylene glycol diglycidyl ether is added dropwise into a four-neck flask filled with 189 g of diethyl aspartate, the temperature is slowly increased to 60 ℃, the reaction is continued at the temperature after the dropwise addition, and TLC monitors the end of the reaction. After the reaction, ethyl acetate was added, and the mixture was washed with a saturated aqueous sodium hydrogencarbonate solution, a saturated aqueous sodium chloride solution and double distilled water, and after the solvent was distilled off under reduced pressure, anhydrous sodium sulfate was added to dry the mixture. 400 g of a pale yellow oily liquid are obtained in 96.5% yield without gel.
Example 7
The present example provides an asparaguse resin and a method of preparing the same, comprising: under the protection of nitrogen, 128 g of 1, 4-bis [ (glycidoxy) methyl ] cyclohexane is added dropwise into a four-neck flask filled with 189 g of diethyl aspartate, the temperature is slowly increased to 60 ℃, the reaction is continued at the temperature after the dropwise addition, and TLC monitors the end point of the reaction. After the reaction, ethyl acetate was added, and the mixture was washed with a saturated aqueous sodium hydrogencarbonate solution, a saturated aqueous sodium chloride solution and double distilled water, and after the solvent was distilled off under reduced pressure, anhydrous sodium sulfate was added to dry the mixture. 388 g of a pale yellow oily liquid were obtained in 94.2% yield without gel.
Example 8
The present example provides an asparaguse resin and a method of preparing the same, comprising: under the protection of nitrogen, 551 g of castor oil triglycidyl ether is added dropwise into a four-neck flask filled with 284 g of diethyl aspartate, the temperature is slowly increased to 80 ℃, the reaction is continued at the temperature after the dropwise addition, and TLC monitors the end point of the reaction. After the reaction, ethyl acetate was added, and the mixture was washed with a saturated aqueous sodium hydrogencarbonate solution, a saturated aqueous sodium chloride solution and double distilled water, and after the solvent was distilled off under reduced pressure, anhydrous sodium sulfate was added to dry the mixture. 780 g of a pale brown oily liquid is obtained in 93.4% yield.
As shown by the test results, the invention can obtain the asparaguse resin with high yield by controlling the structures of the dibasic primary amine and the epoxy compound, thereby reducing the production cost and reducing the residue of the primary amine in the asparaguse resin. The inventor discovers that gel and the like are not generated in the curing process of the asparaguse resin and isocyanate, such as HDI trimer and the like, which are beneficial to subsequent construction.
The foregoing examples are illustrative only and serve to explain some features of the method of the invention. The appended claims are intended to claim the broadest possible scope and the embodiments presented herein are merely illustrative of selected implementations based on combinations of all possible embodiments. It is, therefore, not the intention of the applicant that the appended claims be limited by the choice of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within which variations in these ranges should also be construed as being covered by the appended claims where possible.
Claims (2)
1. The asparaguson resin is characterized in that the asparaguson resin is prepared from primary dibasic ester and an epoxy compound, and the structural formula of the primary dibasic ester is shown as a formula (1):（1）；
r is C1-C10 alkyl;
the epoxy compound is at least one of ethylene glycol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, glycerol triglycidyl ether, triethylene glycol diglycidyl ether, 1, 4-bis [ (glycidoxy) methyl ] cyclohexane and castor oil triglycidyl ether;
the molar ratio of the amine group of the dibasic ester primary amine to the epoxy group of the epoxy compound is 1: (0.9-1.1).
2. A method of synthesizing an asparaguse resin according to claim 1, comprising: and (3) reacting the dibasic ester primary amine with an epoxy compound at 60-100 ℃ to obtain the asparaguste.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4284755A (en) * | 1979-05-08 | 1981-08-18 | Ciba-Geigy Corporation | N-Substituted aspartic acid derivatives as curing agents for epoxide resins |
| CN1865229A (en) * | 2004-07-14 | 2006-11-22 | 拜尔材料科学有限公司 | Aspartic ester functional compounds |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4284755A (en) * | 1979-05-08 | 1981-08-18 | Ciba-Geigy Corporation | N-Substituted aspartic acid derivatives as curing agents for epoxide resins |
| CN1865229A (en) * | 2004-07-14 | 2006-11-22 | 拜尔材料科学有限公司 | Aspartic ester functional compounds |
Non-Patent Citations (1)
| Title |
|---|
| Non Lewis acid catalysed epoxide ring opening with amino acid esters;Christine Philippe et al.;《Org. Biomol. Chem》;第7卷;第2026–2028页、SP第1-33页 * |
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