WO2023025282A1 - 一种奇数碳聚酰胺弹性体及其制备方法 - Google Patents
一种奇数碳聚酰胺弹性体及其制备方法 Download PDFInfo
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- WO2023025282A1 WO2023025282A1 PCT/CN2022/115125 CN2022115125W WO2023025282A1 WO 2023025282 A1 WO2023025282 A1 WO 2023025282A1 CN 2022115125 W CN2022115125 W CN 2022115125W WO 2023025282 A1 WO2023025282 A1 WO 2023025282A1
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- Prior art keywords
- odd
- polyamide elastomer
- general formula
- carbon polyamide
- numbered carbon
- Prior art date
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 99
- 229920002647 polyamide Polymers 0.000 title claims abstract description 99
- 229920001971 elastomer Polymers 0.000 title claims abstract description 84
- 239000000806 elastomer Substances 0.000 title claims abstract description 84
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 59
- 239000003054 catalyst Substances 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000012266 salt solution Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 21
- 229920000570 polyether Polymers 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 12
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 12
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 3
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 9
- 238000010170 biological method Methods 0.000 abstract description 5
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 92
- 229910052757 nitrogen Inorganic materials 0.000 description 46
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 239000000654 additive Substances 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920006345 thermoplastic polyamide Polymers 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011359 shock absorbing material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 2
- 229920002614 Polyether block amide Polymers 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- -1 olefin diols Chemical class 0.000 description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920002397 thermoplastic olefin Polymers 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QUMAGNHFBJNTAZ-UHFFFAOYSA-N C(CCCCCCCCCCC)NC(C(=O)O)CCCCCCCCCC Chemical compound C(CCCCCCCCCCC)NC(C(=O)O)CCCCCCCCCC QUMAGNHFBJNTAZ-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical group [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006130 high-performance polyamide Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- 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
- C08G69/40—Polyamides containing oxygen in the form of ether 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
- 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 an odd-numbered carbon polyamide elastomer and a preparation method thereof.
- Thermoplastic elastomers are marketed as various resin compositions such as polyurethanes, polystyrenes, polyolefins, polyesters, and polyamides.
- Polyamide thermoplastic elastomer (TPAE) is a member of the thermoplastic elastomer family. Compared with widely used thermoplastic polyurethane elastomer (TPU), thermoplastic polyolefin elastomer (TPO), styrene thermoplastic elastomer (SBC), Thermoplastic polyvinyl chloride elastomer (TPVC) and thermoplastic polyether ester elastomer (TPEE), etc., the preparation and application of TPAE started relatively late. Due to its high elasticity, low specific gravity, high flexibility, and good low-temperature performance, polyamide elastomers are widely used in automobiles, sports equipment, medical appliances, seals, and mechanical parts.
- Polyamide thermoplastic elastomer is mainly a copolymer composed of polyamide hard segment and polyether or polyester soft segment, among which polyamide as hard segment mainly includes PA6, PA66, PA11, PA12, etc., the hard segment part It mainly determines the density, hardness, melting point, tensile strength, and resistance to various organic chemicals of polyamide thermoplastic elastomers; as the soft segment, there are mainly polycaprolactone (PCL), polyethylene glycol (PEG) , polypropylene oxide ether (PPG), polytetrahydrofuran (PTMEG), etc., the soft segment mainly determines the low temperature properties, hygroscopicity, antistatic properties, dyeability and stability to certain chemicals of polyamide thermoplastic elastomers characteristics such as sex.
- PCL polycaprolactone
- PEG polyethylene glycol
- PPG polypropylene oxide ether
- PTMEG polytetrahydrofuran
- PA12 is the most common commercialized polyamide elastomer, such as the XPA series products of Ubeko Corporation in Japan, the PEBAX series products of Arkema Corporation in France, and the VESTAMIDE E series products of Evonik Corporation in Germany.
- the hard segment of PA12 is generally made from dodecylaminododecanoic acid or laurolactam obtained by petrochemical methods. The cost is relatively high, and it is monopolized by a few companies.
- the monomer caprolactam of PA6-based elastomers has a shorter carbon chain, and the comprehensive performance of elastomers with the same hardness is not as good as that of long-chain nylon-based elastomers.
- the invention provides an odd-numbered carbon (i.e., tridecane) polyamide elastomer prepared by a biological method prepared from pentamethylenediamine, tridecanedioic acid, and polyether and a preparation method thereof.
- the elastomer has properties Excellent, the source of polymerized monomers is stable, it solves the problem of high cost of polyamide elastomers, broadens the application scenarios of elastomers, and has high commercial value.
- the invention provides an odd-numbered carbon polyamide elastomer, which contains several structural units of general formula C and general formula D, and the structural units are formed by connecting ester groups;
- the general formula C is several general formula A and general formula
- the structural units of formula B are connected by amide bonds;
- R is a C 1 -C 5 alkylene group, or the C 1 -C 5 alkylene group is substituted by a C 1 -C 5 alkylene group.
- odd carbons means thirteen carbons.
- the R is selected from any one or more of methyl, ethyl, propyl, n-butyl, n-pentyl, and their isomers.
- the mass content of the general formula C and the general formula D in the odd-numbered carbon polyamide elastomer is more than 95%, preferably more than 97%.
- the relative viscosity of the odd-numbered carbon polyamide elastomer is 1.0-2.0, more preferably 1.25-1.59.
- the number average molecular weight of the odd-numbered carbon polyamide elastomer is 9,000-70,000, and further 10,000-50,000.
- the mass percentage of the general formula A is 10-35%; the mass percentage of the general formula B is 30-70%, for example, 35-70% %; the mass percentage of the general formula D is 10-60%, such as 20-50%.
- the mass percentage of the general formula A is 13-25%; the mass percentage of the general formula B is 40-65%; the general formula The mass percentage of D is 12-47%.
- the raw materials of the odd-numbered carbon polyamide elastomer include pentamethylenediamine, tridecanedioic acid and polyether.
- the molar ratio of tridecanedioic acid to pentamethylenediamine is 0.9-1.8:1, more preferably 1.08-1.4:1.
- the polyether includes one or a mixture of polyoxygenated C2-C5 olefin diols.
- the polyether includes one of polyethylene glycol (PEG), polypropylene oxide ether (PPG), polytetrahydrofuran (PTMEG), or a mixture thereof.
- PEG polyethylene glycol
- PPG polypropylene oxide ether
- PTMEG polytetrahydrofuran
- the number average molecular weight of the polyether is 400-5000, or 400-2000.
- the polyether includes PTMEG1000 (1000 represents the number average molecular weight of PTMEG, the same below), PTMEG2000, PEG400 or PPG1000.
- the odd-numbered carbon polyamide elastomer is prepared by the following method: first polymerize pentamethylenediamine and tridecanedioic acid to obtain a prepolymer, and then polymerize the prepolymer and polyether to obtain an odd-numbered carbon polyamide elastomer. Carbon polyamide elastomer.
- the number average molecular weight of the prepolymer is 500-10000, further 900-5000.
- the mass ratio of the prepolymer to the polyether is 0.1-10:1, further 0.6-7:1, and further 0.7-6.7:1.
- pentamethylenediamine i.e. 1,5-pentamethylenediamine
- pentamethylenediamine is a nitrogenous base with biological activity widely existing in living organisms, which can be obtained through a series of reactions of glutaronitrile by chemical methods, and can also be obtained by lysine Acid decarboxylase acting on lysine biological method.
- the present invention preferably uses biologically derived pentamethylenediamine.
- one or both of pentamethylenediamine and tridecanedioic acid as raw materials are preferably produced by biological methods.
- the raw material of the odd-numbered carbon polyamide elastomer further includes additives, and the additives include lubricants, nucleating agents, antioxidants, and the like.
- the lubricant includes aliphatic amide, aliphatic alcohol, aliphatic bisamide, polyethylene wax and the like.
- the nucleating agent includes silicon dioxide, talcum powder, kaolin, clay and the like.
- the antioxidants include hindered phenol compounds, hydroquinone compounds, hydroquinone compounds, phosphite compounds and their substitutes, iodides, copper salts and the like.
- the mass content of the additive in the odd-numbered carbon polyamide elastomer is 5% or less, more preferably 3% or less.
- the odd-numbered carbon polyamide elastomer has a density of 1.00-1.30 g/mL, and further 1.01-1.07 g/mL.
- the Shore hardness of the odd-numbered carbon polyamide elastomer is 20D-75D, such as 27D, 33D, 35D, 45D, 40D, 50D, 55D, 60D, 65D or 70D.
- the elongation at break of the odd-numbered carbon polyamide elastomer is above 200%, preferably 200-1200%, for example 346%, 392%, 428%, 693%.
- the tensile strength of the odd-numbered carbon polyamide elastomer is 20-60 MPa.
- the notched impact strength of the odd-numbered carbon polyamide elastomer is above 10 kJ/m 2 , more preferably NB (Non-impact).
- the present invention also provides a kind of preparation method of odd-numbered carbon polyamide elastomer as described above, it comprises the steps:
- step S2 Preparation of elastomer: Polymerize the prepolymer and polyether obtained in step S1 in the presence of a second catalyst to obtain an odd-numbered carbon polyamide elastomer; the mass ratio of the prepolymer to polyether is 0.1- 10:1, then 0.7 to 7:1, and then 1 to 6.7:1.
- the molar ratio of tridecanedioic acid to pentamethylenediamine is 0.9-1.8:1, more preferably 1.08-1.4:1.
- the first catalyst is selected from phosphoric acid, phosphorous acid, trimethyl phosphite, triphenyl phosphite, trimethyl phosphate, triphenyl phosphate, sodium hypophosphite, zinc hypophosphite, One or more of calcium hypophosphite and potassium hypophosphite.
- the second catalyst is selected from one or more of titanium-based catalysts, zirconium-based catalysts, antimony-based catalysts and germanium-based catalysts.
- the titanium-based catalyst is preferably one or more of tetrabutyl titanate, tetraethyl titanate and tetrapropyl titanate.
- the zirconium-based catalyst is preferably tetrabutyl zirconate and/or tetrapropyl zirconate.
- the antimony-based catalyst is preferably antimony glycol.
- the germanium-based catalyst is preferably GeO 2 .
- the mass of the first catalyst accounts for 0.01 to 5 wt% (mass percentage) of the total amount of the pentamethylenediamine, tridecanedioic acid and the first catalyst, such as 0.15% .
- the aforementioned additives are also added to the polyamide salt solution.
- the additive accounts for 0.01-5 wt% (mass percentage) of the total amount of the pentamethylenediamine, the tridecanedioic acid and the additive.
- step S1 and step S2 are carried out under vacuum, nitrogen or inert gas conditions.
- the inert gas generally refers to one or more of neon, argon, krypton, xenon and radon.
- the mass percent concentration of the polyamide salt solution is 30%-70%, such as 60%.
- step S1 is carried out in a salt-forming kettle, and the heating is carried out in a polymerization kettle; step S2 is carried out in a polyester kettle.
- the mass of the second catalyst accounts for 0.01-5wt% of the total amount of the prepolymer, the polyether and the second catalyst, and is further 0.1-1wt% (mass percentage), for example, 0.4wt%, 0.2wt%.
- step S2 the prepolymer and the polyether are firstly mixed at 220-260° C., such as 240° C., for 10-120 minutes, such as 90 minutes, and then the second catalyst is added.
- the polymerization reaction described in step S2 includes: under the condition of vacuum degree of -0.01 ⁇ -0.09MPa, such as -0.06MPa, stirring reaction for 1-5h, such as 2h, 2.5h, and then at 0.5 Reduce the absolute pressure to below 500 Pa within ⁇ 2h (so that the reactants are placed in a high vacuum), and continue the reaction for 1-5h, such as 2h, 3h.
- the polymerization reaction in step S2 further includes charging nitrogen to a positive pressure before discharging.
- the present invention also provides an odd-numbered-carbon polyamide elastomer prepared by the above-mentioned odd-numbered-carbon polyamide elastomer preparation method.
- the present invention also provides a method for forming the odd-numbered carbon polyamide elastomer, which can be formed into a desired shape by injection molding, blow molding, film molding and other molding methods.
- the present invention also provides an application of the aforementioned odd-numbered carbon polyamide elastomer in shoe soles, conduit materials, micro-transmission mechanical parts, shock-absorbing materials or damping and sound-insulating materials.
- the sole may be a sports shoe sole.
- the catheter material may be a medical catheter material.
- the shock-absorbing material may be a sports equipment shock-absorbing material.
- the reagents and raw materials used in the present invention are all commercially available.
- the positive and progressive effect of the present invention lies in: the present invention uses the renewable material bio-based pentamethylenediamine and odd-numbered carbon long-chain dibasic acid as monomers to prepare polyamide elastomers, and its performance is comparable to that of Arkema's pebax series elastomers. Well, it has high hardness and a certain degree of transparency; at the same time, the price has a great advantage, which has a huge role in promoting the industrialization of high-performance polyamide elastomers, especially in the application of transparent catheters and other fields.
- the preparation method of the polyamide elastomer of the invention has low cost and reproducible raw materials.
- the Shore D hardness is carried out according to the international standard ISO7619.
- Tensile tests (including elongation at break and tensile strength) were performed according to international standard ISO527.
- the notched impact strength is carried out according to the test standard ISO 180.
- the relative viscosity test adopts Ubbelohde viscometer, and the mobile phase adopts 96% concentrated sulfuric acid. Density tests are carried out according to the international standard ISO 1183.
- pentamethylenediamine and tridecanedioic acid were purchased from Kaisai (Jinxiang) Biomaterials Co., Ltd., both of which were produced through biological fermentation; polytetrahydrofuran (PTMEG) was purchased from Changlian Chemical ( Changchun); others not specified are commercially available.
- PTMEG polytetrahydrofuran
- Changchun Changlian Chemical
- the polymer finally obtained includes several structural units of general formula C and general formula D, and the structural units are formed by connecting ester groups; The structural units are connected by amide bonds;
- R is ethyl, propyl or n-butyl.
- the weight after drying is 5066g, the yield is 65%, and the number average molecular weight It is 37109; R is n-butyl, the mass percent of general formula A is 18%, the mass percent of general formula B is 48%, and the mass percent of general formula D is 34%.
- the performance test is shown in Table 2.
- the weight after drying is 4378g, the yield is 63%, and the number average molecular weight It is 23877;
- R is n-butyl, the mass percentage of general formula A is 21%, the mass percentage of general formula B is 53%, and the mass percentage of general formula D is 26%.
- the performance test is shown in Table 2.
- the weight after drying is 4875g, the yield is 63%, and the number average molecular weight It is 40191; R is n-butyl, the mass percentage of general formula A is 19%, the mass percentage of general formula B is 47%, and the mass percentage of general formula D is 34%.
- the performance test is shown in Table 2.
- the weight after drying is 3738g, the yield is 65%, and the number average molecular weight is 28169; R is ethyl, the mass percentage of general formula A is 25%, the mass percentage of general formula B is 63%, and the mass percentage of general formula D is 12%.
- the performance test is shown in Table 2.
- the present invention uses pentamethylenediamine and tridecanedioic acid as monomers, and the polyamide elastomer prepared has better performance than the polymer obtained by using hexamethylenediamine as a monomer raw material.
- the monomer source is stable, which solves the problem of high cost of polyamide elastomers, broadens the application scenarios of elastomers, and has high commercial value.
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Abstract
本发明公开了一种奇数碳聚酰胺弹性体及其制备方法，该奇数碳聚酰胺弹性体以生物法制备的戊二胺和十三碳二酸为单体制备得到。本发明的聚酰胺弹性体性能优异，聚合单体来源稳定，解决了聚酰胺弹性体成本过高的问题，拓宽了弹性体的使用场景，具有很高的商业化价值。
Description
本发明涉及了一种奇数碳聚酰胺弹性体及其制备方法。
热塑性弹性体以聚氨酯类、聚苯乙烯类、聚烯烃类、聚酯类、聚酰胺类等各种树脂组合物的形式上市销售。聚酰胺热塑性弹性体(TPAE)属于热塑性弹性体家族中的一员，其相对于广泛应用的热塑性聚氨酯弹性体(TPU)、热塑性聚烯烃弹性体(TPO)、苯乙烯热塑性弹性体(SBC)、热塑性聚氯乙烯弹性体(TPVC)以及热塑性聚醚酯弹性体(TPEE)等，TPAE的制备和应用起步较晚。聚酰胺弹性体由于其弹性高、比重低、伸缩性高、低温性能好等特性，在汽车、运动器材、医疗用具、密封件、机械零部件等方面具有广泛的应用。
聚酰胺热塑性弹性体(TPAE)主要是由聚酰胺硬段与聚醚或聚酯软段组成的共聚物，其中作为硬段的聚酰胺主要有PA6、PA66、PA11、PA12等，该硬段部分主要决定了聚酰胺热塑性弹性体的密度、硬度、熔点、拉伸强度、耐各种有机化学药品等特性；作为软段的部分主要有聚己内酯(PCL)、聚乙二醇(PEG)、聚环氧丙烷醚(PPG)、聚四氢呋喃(PTMEG)等，该软段部分主要决定了聚酰胺热塑性弹性体的低温特性、吸湿性、抗静电性、染色性以及对某些化学品的稳定性等特性。
聚酰胺弹性体的制备在过去几年中得到了广泛的关注，有众多公司以及科研机构利用PA6、PA11、PA12作为硬段，采取多种合成技术申请了相关专利。目前商业化的聚酰胺弹性体以PA12系最为常见，如日本宇部兴公司的XPA系列产品，法国阿科玛公司的PEBAX系列产品，德国赢创公司的VESTAMID E系列产品。PA12硬段一般是由石化方法获取的十二氨基十二烷酸或十二内酰胺制得，成本较高，且为少数公司垄断，难以稳定获取的单 体给规模化生产弹性体带来困难。PA6系弹性体的单体己内酰胺的碳链较短，相同硬度的弹性体综合性能不如长链尼龙系弹性体。
长期以来，人们期待着通过采用生物法制备的原料，来制备与现有品种性能相当的绿色弹性体，解决对化石能源的依赖，建造低碳型社会。
发明内容
本发明提供了一种以生物法制备的戊二胺、十三碳二酸、与聚醚制备得到的奇数碳(即，十三碳)聚酰胺弹性体及其制备方法，所述弹性体性能优异，聚合单体来源稳定，解决了聚酰胺弹性体成本过高的问题，拓宽了弹性体的使用场景，具有很高的商业化价值。
本发明提供了一种奇数碳聚酰胺弹性体，其含有若干通式C和通式D的结构单元，所述结构单元通过酯基连接而成；所述通式C为若干通式A和通式B的结构单元通过酰胺键连接而成；
所述通式A
所述通式B为
所述通式D为
其中，R为C
1～C
5的亚烷基，或者所述C
1～C
5的亚烷基被C
1～C
5的烷基取代。
在一些具体的实施方式中，奇数碳意指十三碳。
在一些具体的实施方式中，所述R选自甲基、乙基、丙基、正丁基、正戊基、以及它们的同分异构体中的任意一种或几种。
在一些具体的实施方式中，所述通式C和通式D在奇数碳聚酰胺弹性体中的质量含量在95％以上，优选97％以上。
在一些具体的实施方式中，所述奇数碳聚酰胺弹性体的相对粘度为1.0～2.0，更佳地为1.25～1.59。
在一些具体的实施方式中，所述奇数碳聚酰胺弹性体的数均分子量为9000～70000，进而为10000～50000。
在一些具体的实施方式中，所述奇数碳聚酰胺弹性体中，所述通式A的质量百分比为10～35％；所述通式B的质量百分比为30～70％，例如35～70％；所述通式D的质量百分比为10～60％，例如20～50％。
在一些具体的实施方式中，所述奇数碳聚酰胺弹性体中，所述通式A的质量百分比为13～25％；所述通式B的质量百分比为40～65％；所述通式D的质量百分比为12～47％。
在一些具体的实施方式中，所述奇数碳聚酰胺弹性体的原料包括戊二胺、十三碳二酸和聚醚。较佳地，所述十三碳二酸与戊二胺的摩尔比为0.9-1.8：1，进而优选为1.08-1.4：1。
在一些具体的实施方式中，所述聚醚包括聚氧化C2-C5烯烃二元醇中的一种或其混合物。
在一些具体的实施方式中，所述聚醚包括聚乙二醇(PEG)、聚环氧丙烷醚(PPG)、聚四氢呋喃(PTMEG)的一种或其混合物。
在一些具体的实施方式中，所述聚醚的数均分子量为400-5000，或者为400-2000。
在一些具体的实施方式中，所述聚醚包括PTMEG1000(1000表示PTMEG的数均分子量，下同)、PTMEG2000、PEG400或PPG1000。
本发明一具体实施方式中，所述奇数碳聚酰胺弹性体通过如下方法制备获得：先将戊二胺和十三碳二酸聚合获得预聚体，然后将预聚体与聚醚聚合获得奇数碳聚酰胺弹性体。
本发明一具体实施方式中，所述预聚体的数均分子量为500-10000，进而为900-5000。
本发明一具体实施方式中，所述预聚体与聚醚的质量比为0.1～10：1， 进而为0.6～7：1，进而为0.7～6.7：1。
本发明中，戊二胺即1,5-戊二胺，是生物体内广泛存在的具有生物活性的含氮碱，可通过化学法，将戊二腈通过一系列反应得到，也可通过赖氨酸脱羧酶作用于赖氨酸的生物法得到。本发明优选使用生物法来源的戊二胺。
本发明中，优选作为原料的戊二胺和十三碳二酸酸之一或者两者均为通过生物法制得的。
本发明一具体实施方式中，所述奇数碳聚酰胺弹性体的原料还包括添加剂，所述添加剂包括润滑剂、成核剂、抗氧剂等。所述润滑剂，包括脂肪族酰胺、脂肪族醇、脂肪族双酰胺、聚乙烯蜡等。所述成核剂，包括二氧化硅、滑石粉、高岭土、黏土等。所述抗氧剂，包括受阻酚系化合物、氢醌类化合物、对苯二酚系化合物、亚磷酸酯系化合物和它们的取代物、碘化物、铜盐等。
本发明一具体实施方式中，所述添加剂在奇数碳聚酰胺弹性体中的质量含量为5％以下，进而优选为3％以下。
本发明一具体实施方式中，所述奇数碳聚酰胺弹性体的密度为1.00～1.30g/mL，进而为1.01～1.07g/mL。
本发明一具体实施方式中，所述奇数碳聚酰胺弹性体的邵氏硬度为20D～75D，例如27D、33D、35D、45D、40D、50D、55D、60D、65D或70D。
本发明一具体实施方式中，所述奇数碳聚酰胺弹性体的断裂伸长率为200％以上，较佳地为200-1200％，例如为346％、392％、428％、693％。
本发明一具体实施方式中，所述奇数碳聚酰胺弹性体的拉伸强度为20～60MPa。
本发明一具体实施方式中，所述奇数碳聚酰胺弹性体的缺口冲击强度为10kJ/m
2以上，更佳地为NB(冲不断)。
本发明还提供了一种如前所述的奇数碳聚酰胺弹性体的制备方法，其包括如下步骤：
S1制备预聚体：将戊二胺、十三碳二酸、第一催化剂与水混合，制得 聚酰胺盐水溶液；加热所述聚酰胺盐水溶液至200～250℃，例如220℃，压力升至1.5～3.0MPa，例如1.7MPa，出水排气，当温度升高至240～270℃，例如250℃时，抽真空至-0.01～-0.3Mpa，例如-0.06MPa，保持5～60min，例如20min，获得羧基封端的预聚体；
S2制备弹性体：将步骤S1获得的预聚体和聚醚在第二催化剂存在的条件下进行聚合反应，获得奇数碳聚酰胺弹性体；所述预聚体与聚醚的质量比为0.1～10：1，进而为0.7～7：1，进而为1～6.7：1。
本发明一具体实施方式中，所述十三碳二酸与戊二胺的摩尔比为0.9-1.8：1，进而优选为1.08-1.4：1。
本发明一具体实施方式中，所述第一催化剂选自磷酸、亚磷酸、亚磷酸三甲酯、亚磷酸三苯酯、磷酸三甲酯、磷酸三苯酯、次磷酸钠、次磷酸锌、次磷酸钙、次磷酸钾中的一种或者多种。
本发明一具体实施方式中，所述第二催化剂选自钛系催化剂、锆系催化剂、锑系催化剂和锗系催化剂中的一种或多种。所述钛系催化剂较佳地为钛酸四丁酯、钛酸四乙酯和钛酸四丙酯中的一种或多种。所述锆系催化剂较佳地为锆酸四丁酯和/或锆酸四丙酯。所述锑系催化剂较佳地为乙二醇锑。所述锗系催化剂较佳地为GeO
2。
本发明一具体实施方式中，所述第一催化剂的质量，占所述戊二胺、十三碳二酸和所述第一催化剂的总量的0.01～5wt％(质量百分比)，例如0.15％。
本发明一具体实施方式中，在聚酰胺盐溶液中，还加入前述添加剂。所述添加剂占所述戊二胺、所述十三碳二酸和所述添加剂的总量的0.01～5wt％(质量百分比)。
本发明一具体实施方式中，步骤S1和步骤S2在真空、氮气或惰性气体条件下进行。所述惰性气体一般是指氖气、氩气、氪气、氙气和氡气的一种或多种。
本发明一具体实施方式中，所述聚酰胺盐溶液的质量百分浓度为30％～70％，例如60％。
本发明一具体实施方式中，步骤S1的混合在成盐釜中进行，加热在聚合釜中进行；步骤S2在聚酯釜中进行。
本发明一具体实施方式中，所述第二催化剂的质量，占所述预聚体、所述聚醚和所述第二催化剂的总量的0.01～5wt％，进而为0.1～1wt％(质量百分比)，例如为0.4wt％、0.2wt％。
本发明一具体实施方式中，步骤S2中先将预聚体和聚醚在220～260℃，例如240℃的条件下混合10-120min，例如90min，再加入第二催化剂。
本发明一具体实施方式中，步骤S2中所述聚合反应包括：在真空度为-0.01～-0.09MPa，例如-0.06MPa条件下，搅拌反应1-5h，例如2h、2.5h，然后在0.5～2h内降低绝对压力至500Pa以下(以使反应物置于高真空中)，继续反应1-5h，例如2h、3h。
本发明一具体实施方式中，步骤S2中所述聚合反应还包括充氮气至正压，再出料。
本发明还提供了一种如前所述的奇数碳聚酰胺弹性体的制备方法制得的奇数碳聚酰胺弹性体。
本发明还提供了一种如前所述的奇数碳聚酰胺弹性体的成型方法，可以采用注塑成型、吹塑成型、薄膜成型等成型方法来成型为所期望的形状。
本发明还提供了一种如前所述的奇数碳聚酰胺弹性体在鞋底、导管材料、微传动机械部件、减震材料或阻尼隔音材料方面的应用。其中，所述鞋底可为运动鞋底。其中，所述导管材料可为医用导管材料。其中，所述减震材料可为运动器材减震材料。
在符合本领域常识的基础上，上述各优选条件可任意组合，即得本发明各较佳实例。
本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于：本发明以可再生材料生物基戊二胺、以及奇数碳长链二元酸为单体制备聚酰胺弹性体，性能媲美阿科玛公司的pebax系列弹性体，弹性好，硬度高，而且具有一定的透明性；同时价格有着很大 的优势，这对于高性能聚酰胺弹性体的工业化有着巨大的推动作用，尤其是在透明导管等领域的应用。本发明的聚酰胺弹性体的制备方法成本低、原料可再生。
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
以下各实施例对比例中，邵氏D硬度根据国际标准ISO7619进行。拉伸测试(包括断裂伸长率和拉伸强度)根据国际标准ISO527进行。缺口冲击强度参照测试标准ISO 180进行。相对粘度测试采用乌氏粘度仪，流动相采用96％的浓硫酸。密度测试根据国际标准ISO 1183进行。
各实施例对比例中的原料来源：戊二胺、十三碳二酸购自凯赛(金乡)生物材料有限公司，均经由生物发酵法制得；聚四氢呋喃(PTMEG)购自长连化工(长春)；其他未特别说明的均为市售。以下各实施例中，最终获得的聚合物包括若干通式C和通式D的结构单元，所述结构单元通过酯基连接而成；所述通式C为若干通式A和通式B的结构单元通过酰胺键连接而成；
所述通式A
所述通式B为
所述通式D为
R为乙基、丙基或正丁基。
实施例1
在氮气条件下，向成盐釜内加入纯水5806g、戊二胺2000g，开启搅拌，加入十三碳二酸6710g，催化剂次磷酸钠13g，制得聚酰胺盐水溶液，浓度60％。在氮气条件下，将聚酰胺盐水溶液转移至聚合釜中，加热至220℃，釜内压力升至1.7MPa，出水排气，待釜内温度升至250℃时，抽真空至-0.06MPa，保持20min，制得羧基封端的预聚体，烘干备用，产率83％，质量6643g，数均分子量为914。
在氮气条件下，将羧基封端的预聚体4890g，PTMEG1000 4569g，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯37.8g，然后在真空度为-0.06MPa条件下，搅拌反应2h，然后在1h内降低绝对压力至500Pa以下，继续反应2h，充氮气至正压，出料切粒，得到聚酰胺弹性体，烘干后重量5942g，产率64％，数均分子量为35759；R为正丁基，通式A的质量百分比13％，通式B的质量百分比40％，通式D的质量百分比47％，性能测试如表2。
实施例2
在氮气条件下，向成盐釜内加入纯水5186g、戊二胺2040g，开启搅拌，加入十三碳二酸5739g，催化剂次磷酸钠11.7g，制得聚酰胺盐水溶液，浓度60％。在氮气条件下，将聚酰胺盐水溶液转移至聚合釜中。加热至220℃，釜内压力升至1.7MPa，出水排气，待釜内温度升至250℃时，抽真空至-0.06MPa，保持20min，制得羧基封端的预聚体，烘干备用，产率82％，质量5788g，数均分子量为1905。
在氮气条件下，将羧基封端的预聚体5126g，PTMEG1000 2761g倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯15.3g，然后在真空度为-0.06MPa条件下，搅拌反应2h，然后在1h内降低绝对压力至500Pa以下，继续反应2h，充氮气至正压，出料切粒，得到聚酰胺弹性体，烘干后重量5066g，产率65％，数均分子量为37109；R为正丁基，通式A的质量百 分比18％，通式B质量百分比48％，通式D的质量百分比34％，性能测试如表2。
实施例3
在氮气条件下，向成盐釜内加入纯水4940g、戊二胺2030g，开启搅拌，加入十三碳二酸5380g，催化剂次磷酸钠11.1g，制得聚酰胺盐水溶液，浓度60％。在氮气条件下，将聚酰胺盐水溶液转移至聚合釜中。加热至220℃，釜内压力升至1.7MPa，出水排气，待釜内温度升至250℃时，抽真空至-0.06MPa，保持20min，制得羧基封端的预聚体，烘干备用，产率87％，质量5823g，数均分子量为3017。
在氮气条件下，将羧基封端的预聚体5102g，PTMEG1000 1916g倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯16.0g，然后在真空度为-0.06MPa条件下，搅拌反应2h，然后在1h内降低绝对压力至500Pa以下，继续反应2h，充氮气至正压，出料切粒，得到聚酰胺弹性体，烘干后重量4378g，产率63％，数均分子量为23877；R为正丁基，通式A的质量百分比21％，通式B质量百分比53％，通式D的质量百分比26％，性能测试如表2。
实施例4
在氮气条件下，向成盐釜内加入纯水4725g、戊二胺1980g，开启搅拌，加入十三碳二酸5108g，催化剂次磷酸钠10.6g，制得聚酰胺盐水溶液，浓度60％。在氮气条件下，将聚酰胺盐水溶液转移至聚合釜中。加热至220℃，釜内压力升至1.7MPa，出水排气，待釜内温度升至250℃时，抽真空至-0.06MPa，保持20min，制得羧基封端的预聚体，烘干备用，产率84％，质量5367g，数均分子量为4096。
在氮气条件下，将羧基封端的预聚体5021g，PTMEG2000 2760g倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯13.6g，然后在真空 度为-0.06MPa条件下，搅拌反应2h，然后在1h内降低绝对压力至500Pa以下，继续反应2h，充氮气至正压，出料切粒，得到聚酰胺弹性体，烘干后重量4875g，产率63％，数均分子量为40191；R为正丁基，通式A的质量百分比19％，通式B质量百分比47％，通式D的质量百分比34％，性能测试如表2。
实施例5
在氮气条件下，向成盐釜内加入纯水4959g、戊二胺2030g，开启搅拌，加入十三碳二酸5408g，催化剂次磷酸钙11.2g，制得聚酰胺盐水溶液，浓度60％。在氮气条件下，将聚酰胺盐水溶液转移至聚合釜中。加热至220℃，釜内压力升至1.7MPa，出水排气，待釜内温度升至250℃时，抽真空至-0.06MPa，保持20min，制得羧基封端的预聚体，烘干备用，产率86％，质量5780g，数均分子量为2871。
在氮气条件下，将羧基封端的预聚体5060g，PEG400 760g倒入反应釜内，在250℃下混合90min，加入催化剂钛酸四丁酯12g，然后在真空度为-0.06MPa条件下，搅拌反应3h，然后在1h内降低绝对压力至500Pa以下，继续反应3h，充氮气至正压，出料切粒，得到聚酰胺弹性体，烘干后重量3738g，产率65％，数均分子量为28169；R为乙基，通式A的质量百分比25％，通式B的质量百分比63％，通式D的质量百分比12％，性能测试如表2。
实施例6
在氮气条件下，向成盐釜内加入纯水4907g、戊二胺2010g，开启搅拌，加入十三碳二酸5350g，催化剂次磷酸钠11g，制得聚酰胺盐水溶液，浓度60％。在氮气条件下，将聚酰胺盐水溶液转移至聚合釜中。加热至220℃，釜内压力升至1.7MPa，出水排气，待釜内温度升至250℃时，抽真空至-0.06MPa，保持20min，制得预聚体，烘干备用，产率84％，质量5586g， 数均分子量为2985。
在氮气条件下，将预聚体5120g，PPG1000 1940g倒入反应釜内，在245℃下混合90min，加入催化剂钛酸四丁酯12.9g，然后在真空度为-0.06MPa条件下，搅拌反应2.5h，然后在1h内降低绝对压力至500Pa以下，继续反应3h，充氮气至正压，出料切粒，得到聚酰胺弹性体，烘干后重量4689g，产率67％，数均分子量为31342；R为丙基，通式A的质量百分比20％，通式B质量百分比50％，通式D的质量百分比30％，性能测试如表2。
实施例7
在氮气条件下，向成盐釜内加入纯水6911g、戊二胺2017g，开启搅拌，加入十三碳二酸6430g，催化剂次磷酸钠8.9g，制得聚酰胺盐水溶液，浓度55％。在氮气条件下，将聚酰胺盐水溶液转移至聚合釜中。加热至220℃，釜内压力升至1.7MPa，出水排气，待釜内温度升至250℃时，抽真空至-0.06MPa，保持30min，制得预聚体，烘干备用，产率87％，质量6731g，数均分子量为1164。
在氮气条件下，将预聚体4503g，PTMEG1000 4509g倒入反应釜内，在245℃下混合30min，加入催化剂钛酸四丁酯18.9g，然后在真空度为-0.06MPa条件下，搅拌反应2.5h，然后在1h内降低绝对压力至500Pa以下，继续反应4h，充氮气至正压，出料切粒，得到聚酰胺弹性体，烘干后重量6903g，产率78％，数均分子量为25135；R为正丁基，通式A的质量百分比13％，通式B质量百分比36％，通式D的质量百分比51％，性能测试如表2。
实施例8
在氮气条件下，向成盐釜内加入纯水8790g、戊二胺2031g，开启搅拌，加入十三碳二酸5160g，催化剂次磷酸钠7.1g，制得聚酰胺盐水溶液，浓度45％。在氮气条件下，将聚酰胺盐水溶液转移至聚合釜中。加热至220℃，釜内压力升至1.7MPa，出水排气，待釜内温度升至250℃时，抽真空至 -0.06MPa，保持30min，制得预聚体，烘干备用，产率85％，质量5497g，数均分子量为5061。
在氮气条件下，将预聚体5316g，PTMEG1000 762g倒入反应釜内，在245℃下混合30min，加入催化剂钛酸四丁酯17.6g，然后在真空度为-0.06MPa条件下，搅拌反应2.5h，然后在1h内降低绝对压力至500Pa以下，继续反应4h，充氮气至正压，出料切粒，得到聚酰胺弹性体，烘干后重量4910g，产率81％，数均分子量为17664；R为正丁基，通式A的质量百分比27％，通式B质量百分比60％，通式D的质量百分比13％，性能测试如表2。
实施例9
在氮气条件下，向成盐釜内加入纯水7377g、戊二胺2028g，开启搅拌，加入十三碳二酸5349g，催化剂次磷酸钠3.6g，制得聚酰胺盐水溶液，浓度50％。在氮气条件下，将聚酰胺盐水溶液转移至聚合釜中。加热至220℃，釜内压力升至1.7MPa，出水排气，待釜内温度升至250℃时，抽真空至-0.06MPa，保持30min，制得预聚体，烘干备用，产率85％，质量5636g，数均分子量为3207。
在氮气条件下，将预聚体5366g，PTMEG1000 1395g倒入反应釜内，在245℃下混合30min，加入催化剂钛酸四丁酯23.6g，然后在真空度为-0.06MPa条件下，搅拌反应2.5h，然后在1h内降低绝对压力至1000Pa以下，继续反应4h，充氮气至正压，出料切粒，得到聚酰胺弹性体，烘干后重量5541g，产率83％，数均分子量为15694；R为正丁基，通式A的质量百分比24％，通式B质量百分比56％，通式D的质量百分比20％，性能测试如表2。
实施例10
在氮气条件下，向成盐釜内加入纯水4926g、戊二胺1650g，开启搅拌，加入十三碳二酸5738g，催化剂次磷酸钠1.4g，制得聚酰胺盐水溶液，浓度60％。在氮气条件下，将聚酰胺盐水溶液转移至聚合釜中。加热至220℃， 釜内压力升至1.7MPa，出水排气，待釜内温度升至250℃时，抽真空至-0.06MPa，保持30min，制得预聚体，烘干备用，产率89％，质量6072g，数均分子量为881。
在氮气条件下，将预聚体3600g，PTMEG1000 4933g倒入反应釜内，在245℃下混合30min，加入催化剂钛酸四丁酯45.1g，然后在真空度为-0.06MPa条件下，搅拌反应2h，然后在1h内降低绝对压力至1000Pa以下，继续反应4h，充氮气至正压，出料切粒，得到聚酰胺弹性体，烘干后重量7594g，产率91％，数均分子量为11672；R为正丁基，通式A的质量百分比10％，通式B质量百分比31％，通式D的质量百分比59％，性能测试如表2。
对比例1
在氮气条件下，向成盐釜内加入纯水5016g、己二胺2245g，开启搅拌，加入十三碳二酸5280g，催化剂次磷酸钠11.3g，制得聚酰胺盐水溶液，浓度60％。在氮气条件下，将聚酰胺盐水溶液转移至聚合釜中。加热至220℃，釜内压力升至1.7MPa，出水排气，待釜内温度升至250℃时，抽真空至-0.06MPa，保持20min，制得预聚体，烘干备用，产率83％，质量5667g，数均分子量为2887。
在氮气条件下，将预聚体5090g，PPG1000 1930g倒入反应釜内，在245℃下混合90min，加入催化剂钛酸四丁酯14.1g，然后在真空度为-0.06MPa条件下，搅拌反应2.5h，然后在1h内降低绝对压力至500Pa以下，继续反应3h，充氮气至正压，出料切粒，得到聚合物，烘干后重量5079g，产率73％，数均分子量为14835，性能测试如表1。
表1实施例和对比例获得的产物测试性能表
从上述实施例和对比例可以看出，本发明使用戊二胺、十三碳二酸为单体，制备得到的聚酰胺弹性体比使用己二胺为单体原料获得的聚合物性能优异，单体来源稳定，解决了聚酰胺弹性体成本过高的问题，拓宽了弹性体的使用场景，具有很高的商业化价值。
Claims (10)
- 一种奇数碳聚酰胺弹性体，其特征在于，其含有若干通式C和通式D的结构单元，所述结构单元通过酯基连接而成；所述通式C为若干通式A和通式B的结构单元通过酰胺键连接而成；所述通式A
所述通式B为
所述通式D为
其中，R为C 1～C 5的亚烷基，或者所述C 1～C 5的亚烷基被C 1～C 5的烷基取代；和/或，所述奇数碳聚酰胺弹性体的相对粘度为1.0～2.0；和/或，所述奇数碳聚酰胺弹性体的数均分子量为9000～70000，进而为10000～50000。 - 根据权利要求1所述的奇数碳聚酰胺弹性体，其特征在于，所述通式A的质量百分比为10～35％；所述通式B的质量百分比为30～70％；所述通式D的质量百分比为10～60％。
- 根据权利要求1所述的奇数碳聚酰胺弹性体，其特征在于，所述奇数碳聚酰胺弹性体的原料包括戊二胺、十三碳二酸和聚醚；较佳地，所述十三碳二酸与戊二胺的摩尔比为0.9-1.8：1。
- 根据权利要求1所述的奇数碳聚酰胺弹性体，其特征在于，所述聚醚包括聚氧化C2-C5烯烃二元醇中的一种或其混合物；较佳地，所述聚醚包括聚乙二醇(PEG)、聚环氧丙烷醚(PPG)、聚四氢呋喃(PTMEG)中的一种或其混合物；较佳地，所述聚醚的数均分子量为400-5000，或者为400-2000。
- 根据权利要求1所述的奇数碳聚酰胺弹性体，其特征在于，所述奇数 碳聚酰胺弹性体的密度为1.00～1.30g/mL；和/或，所述奇数碳聚酰胺弹性体的邵氏硬度为20D～75D；和/或，所述奇数碳聚酰胺弹性体的断裂伸长率为200％以上，较佳地为200-1200％；和/或，所述奇数碳聚酰胺弹性体的拉伸强度为20～60MPa；和/或，所述奇数碳聚酰胺弹性体的缺口冲击强度为10kJ/m 2以上，更佳地为NB(冲不断)。
- 一种权利要求1～5任意一项所述奇数碳聚酰胺弹性体的制备方法，其特征在于，其包括如下步骤：S1制备预聚体：将戊二胺、十三碳二酸、第一催化剂与水混合，制得聚酰胺盐水溶液；加热所述聚酰胺盐水溶液至200～250℃，压力升至1.5～3.0MPa，出水排气，当温度升高至240～270℃，抽真空至-0.01～-0.3Mpa，保持5～60min，获得羧基封端的预聚体；S2制备弹性体：将步骤S1获得的预聚体和聚醚在第二催化剂存在的条件下进行聚合反应，获得奇数碳聚酰胺弹性体；所述预聚体与聚醚的质量比为0.1～10：1；和/或，所述十三碳二酸与戊二胺的摩尔比为0.9-1.8：1；和/或，所述第一催化剂选自磷酸、亚磷酸、亚磷酸三甲酯、亚磷酸三苯酯、磷酸三甲酯、磷酸三苯酯、次磷酸钠、次磷酸锌、次磷酸钙、次磷酸钾中的一种或者多种；和/或，所述第二催化剂选自钛系催化剂、锆系催化剂、锑系催化剂和锗系催化剂中的一种或多种。
- 根据权利要求6所述的奇数碳聚酰胺弹性体的制备方法，其特征在于，所述第一催化剂的质量，占所述戊二胺、十三碳二酸和所述第一催化剂的总量的0.01～5wt％。
- 根据权利要求6所述的奇数碳聚酰胺弹性体的制备方法，其特征在于，所述第二催化剂的质量，占所述预聚体、所述聚醚和所述第二催化剂的总量 的0.01～5wt％。
- 根据权利要求6所述的奇数碳聚酰胺弹性体的制备方法，其特征在于，步骤S2中先将预聚体和聚四氢呋喃在220～260℃的条件下混合10-120min，再加入第二催化剂。
- 根据权利要求6所述的奇数碳聚酰胺弹性体的制备方法，其特征在于，步骤S2中所述聚合反应包括：在真空度为-0.01～-0.09MPa条件下，搅拌反应1-5h，然后在0.5～2h内降低绝对压力至500Pa以下，继续反应1-5h。
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