WO2023025284A1 - 一种生物基聚酰胺弹性体及其制备方法 - Google Patents
一种生物基聚酰胺弹性体及其制备方法 Download PDFInfo
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- WO2023025284A1 WO2023025284A1 PCT/CN2022/115128 CN2022115128W WO2023025284A1 WO 2023025284 A1 WO2023025284 A1 WO 2023025284A1 CN 2022115128 W CN2022115128 W CN 2022115128W WO 2023025284 A1 WO2023025284 A1 WO 2023025284A1
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- WIPO (PCT)
- Prior art keywords
- general formula
- bio
- polyamide elastomer
- acid
- based polyamide
- Prior art date
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 86
- 239000000806 elastomer Substances 0.000 title claims abstract description 86
- 229920006021 bio-based polyamide Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004952 Polyamide Substances 0.000 claims abstract description 62
- 229920002647 polyamide Polymers 0.000 claims abstract description 62
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims description 56
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 54
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 32
- 239000012266 salt solution Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 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 21
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 20
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 claims description 14
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 14
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 6
- QCNWZROVPSVEJA-UHFFFAOYSA-N Heptadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCC(O)=O QCNWZROVPSVEJA-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
- 239000002253 acid Substances 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
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-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
- 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
- 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
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 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
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 2
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 2
- 125000004185 ester group Chemical group 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
- 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 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
- 239000000376 reactant Substances 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 abstract description 7
- 238000010170 biological method Methods 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 6
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 108
- 229910052757 nitrogen Inorganic materials 0.000 description 54
- 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 14
- 238000011056 performance test Methods 0.000 description 13
- 238000012546 transfer Methods 0.000 description 13
- 239000008188 pellet Substances 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229920006345 thermoplastic polyamide Polymers 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920002614 Polyether block amide Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 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
- 239000002667 nucleating agent Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-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
- 108010048581 Lysine decarboxylase Proteins 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 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
- 229910052799 carbon Inorganic materials 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
- 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
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 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
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-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
- -1 polyethylene Polymers 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
- 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
- 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
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
- A43B23/02—Uppers; Boot legs
-
- 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
Definitions
- the invention relates to a bio-based 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 a polyamide elastomer prepared by using pentamethylenediamine prepared by a biological method, a long-chain (C10 to C18) aliphatic diacid, and a specific proportion of polytetrahydrofuran as raw materials, as well as its preparation method and application.
- the above-mentioned elastomer has excellent performance and a stable source of polymerized monomers, which solves the problem of high cost of polyamide elastomers, broadens the application scenarios of elastomers, and has high commercial value.
- the present invention provides a bio-based polyamide elastomer, which contains structural units of general formula C and general formula D, and the structural units of general formula C and general formula D are connected through ester groups; said general formula C contains The structural units of general formula A and general formula B, and the structural units of general formula A and general formula B are connected by amide bonds;
- x 8-16, and x is an integer
- the relative viscosity of the bio-based polyamide elastomer is 1.0-2.0, more preferably 1.1-1.7, more preferably 1.3-1.7.
- the bio-based polyamide elastomer is a block copolymer.
- the number average molecular weight of the general formula C is 800-12000, further 850-7000, more preferably 1400-7000, such as 1406, 2140, 2935, 4948, 2554, 3763, 852, 1494, 4973, 3162, 4778.
- the number average molecular weight of the bio-based polyamide elastomer is 10000-70000, further 10000-40000, more preferably 30000-40000, such as 39596, 34507, 35880, 39022, 38158, 31860 , 22739, 19659 or 18749, 33711, 18159.
- the number average molecular weight of the general formula D is 500-5000, such as 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500.
- the general formula C also contains a structural unit of the general formula E, and the structural units of the general formula A, the general formula B and the general formula E are connected by an amide bond, and the general formula E is
- the molar percentage of the general formula A is 10-40%; the molar percentage of the general formula B is 15-40%; the molar percentage of the general formula D is 35% to 65%; the sum of the molar percentages of the general formulas A, B and D is 100%.
- the molar percentage of the general formula A is 15-30%; the molar percentage of the general formula B is 20-35%; the general formula The molar percentage of D is 40-65%; the sum of the molar percentages of the general formulas A, B and D is 100%.
- the molar ratio of the general formula A, general formula B, general formula E and general formula D is 18-25:18-30:1-10:40-65.
- the molar ratio of the general formula A to the general formula B is 1:1.0-1.5.
- the mass content of the structural units of the general formula C and the general formula D in the bio-based polyamide elastomer is more than 95%, preferably more than 97%.
- the raw material of the bio-based polyamide elastomer includes pentanediamine, diacid and polytetrahydrofuran, and the diacid is selected from the group consisting of decadioic acid, undecanedioic acid, dodecanedioic acid, and polytetrahydrofuran. Any one or more of diacid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecandioic acid, heptadecandioic acid or octadecanedioic acid.
- the diacid also includes adipic acid.
- the bio-based polyamide elastomer is prepared by the following method: first polymerize pentamethylenediamine and diacid to obtain a prepolymer, and then polymerize the prepolymer with polytetrahydrofuran to obtain a bio-based polyamide elastomer.
- the molar ratio of the prepolymer to polytetrahydrofuran is 0.7-2:1, further 0.8-1.5:1, preferably 0.7-1.3, more preferably 0.8-1.2, for example 0.94:1, 0.92:1, 1.12:1, 0.84:1, 1.10:1, 0.87:1, 0.93:1, 1.14:1, 1.48:1, 0.86:1, 1.45:1.
- the number average molecular weight of the polytetrahydrofuran is 500-5000, such as PTMEG 1000 with a molecular weight of 1000 and PTMEG 2000 with a molecular weight of 2000.
- one or both of the pentamethylenediamine and the long-chain aliphatic diacid used as raw materials are prepared by biological methods.
- pentamethylenediamine is obtained biologically by the action of lysine decarboxylase on lysine.
- the raw materials for preparing the bio-based polyamide elastomer may optionally include 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 bio-based polyamide elastomer is less than 5%, more preferably less than 3%, such as 0.1-3%.
- the density of the bio-based polyamide elastomer is 1.01-1.2 g/mL, further 1.01-1.07 g/mL.
- the Shore hardness of the bio-based polyamide elastomer is 25D-80D, such as 33D, 45D, 52D, 63D, 35D, 42D, 67D, 50D, 71D.
- the elongation at break of the bio-based polyamide elastomer is above 200%, preferably 300-1200%, such as 382%, 539%, 680%, 730%, 426% %, 566%, 387%.
- the tensile strength of the bio-based polyamide elastomer is 15-60 MPa, further 17-50 MPa or 20-60 MPa.
- the notched impact strength of the bio-based polyamide elastomer is above 8 kJ/m 2 , more preferably NB (Non-impact).
- the present invention also provides a kind of preparation method of bio-based polyamide elastomer as described above, it comprises the steps:
- the diacid is selected from the group consisting of decanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecandioic acid, Any one or more of heptadecandioic acid or octadecanedioic acid.
- the first catalyst is selected from phosphoric acid, phosphorous acid, trimethyl phosphite, triphenyl phosphite, trimethyl phosphate, triphenyl phosphate, sodium hypophosphite, sodium hypophosphite, zinc hypophosphite, calcium hypophosphite , one or more of potassium hypophosphite, preferably sodium hypophosphite and/or sodium hypophosphite.
- the second catalyst is 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 molar ratio of pentamethylenediamine to diacid is 1:1.0-1.5, preferably 1:1.0-1.2.
- the added amount of the first catalyst accounts for 0.001-5% (mole percentage) of the total amount of the pentamethylenediamine, the diacid and the first catalyst, and further 1-2%, For example 1.4%, 1.5%.
- the added amount of the second catalyst accounts for 0.001-3% (molar percentage) of the total amount of the prepolymer, the polytetrahydrofuran and the second catalyst, and further 0.01-1.4%, For example 1%, 1.15%.
- the aforementioned additives are also added to the polyamide salt solution.
- the additive accounts for 0.001-5% (mole percentage) of the total amount of the pentamethylenediamine, the diacid 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.
- step S1 is performed in a salt-forming tank, and the heating is performed in a polymerization tank; step S2 is performed in a polyester tank.
- the molar ratio of the prepolymer to polytetrahydrofuran is 0.7-2:1, further 0.8-1.5:1, preferably 0.7-1.3, more preferably 0.8-1.2, such as 0.94:1, 0.92:1, 1.12:1, 0.84:1, 1.10:1, 0.87:1, 0.93:1, 1.14:1, 1.48:1, 0.86:1, 1.45:1.
- the polytetrahydrofuran has a number average molecular weight of 500-5000, such as PTMEG 1000 with a molecular weight of 1000 and PTMEG 2000 with a molecular weight of 1000. .
- step S2 the prepolymer and polytetrahydrofuran 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: stirring the reaction for 1 to 5 hours, such as 2 hours, under the condition of vacuum degree of -0.01 to -0.09 MPa, such as -0.06 MPa, and then reducing the absolute pressure to within 0.5 to 2 hours. Below 500Pa, the reaction is continued for 1 ⁇ 10h, preferably 1.5 ⁇ 5h, more preferably 1 ⁇ 5h, for example 1.5h, 2h, 2.5h, 3.5h.
- the polymerization reaction in step S2 also includes charging nitrogen to a positive pressure before discharging.
- the molding method of the bio-based polyamide elastomer can be molded into a desired shape by using molding methods such as injection molding, blow molding, and film molding.
- the bio-based polyamide elastomer of the present invention can be popularized and applied in the field of shoe materials such as ski boots, soccer shoes, running shoes and the like.
- shoe materials such as ski boots, soccer shoes, running shoes and the like.
- the ski boots are shoe shells
- the soccer shoes are soles
- the running shoes are midsoles.
- the reagents and raw materials used in the present invention are all commercially available.
- the positive progress effect of the present invention lies in: the present invention uses pentamethylenediamine prepared by biological method, long-chain (C10 to C18) aliphatic diacid and specific proportion of polytetrahydrofuran as raw materials to prepare polyamide elastomer, and its performance is comparable to that of Arkema
- the pebax series elastomers have good elasticity, high hardness and wide range; 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 field of footwear.
- 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.
- Sources of raw materials in each embodiment and comparative example pentanediamine, decadioic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecandioic acid Purchased from Cathay (Jinxiang) Biomaterials Co., Ltd., all produced by biological method; polytetrahydrofuran (PTMEG) was purchased from Changlian Chemical (Changchun).
- examples 1 to 11 of the present invention pentamethylenediamine, long-chain (C10 to C18) aliphatic diacids and polytetrahydrofuran in a specific proportion are used as raw materials prepared by biological methods,
- the prepared polyamide elastomer has excellent performance and a stable monomer source, which solves the problem of high cost of the polyamide elastomer, broadens the application scenarios of the elastomer, and has high commercial value.
- Comparative Example 1 In contrast, in Comparative Example 1, only adipic acid was used, but no long-chain (C10 to C18) aliphatic diacid was used, and the obtained polyamide elastomer had too high viscosity and low elongation at break. Comparative Example 2 uses excessive polytetrahydrofuran as a raw material, and the obtained polyamide elastomer has too high Shore hardness D, too low elongation at break, and too high tensile strength.
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Abstract
本发明公开了一种生物基聚酰胺弹性体及其制备方法，该生物基聚酰胺弹性体以生物法制备的戊二胺和特定的脂肪族二酸为单体制备得到。本发明的聚酰胺弹性体性能优异且聚合单体来源稳定，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
本发明涉及了一种生物基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、长链(C10至C18)脂肪族二酸、与特定比例的聚四氢呋喃为原料制备得到的聚酰胺弹性体及其制备方法与应用，所述弹性体性能优异，且聚合单体来源稳定，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。
本发明提供了一种生物基聚酰胺弹性体，其含有通式C和通式D的结构单元，且通式C和通式D的结构单元通过酯基连接而成；所述通式C含有通式A和通式B的结构单元，且通式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，x＝8-16，且x为整数；
其中，所述生物基聚酰胺弹性体的相对粘度为1.0～2.0，更佳地为1.1～1.7，更佳地为1.3～1.7。
本发明一具体实施方式中，所述生物基聚酰胺弹性体为嵌段共聚物。
本发明一具体实施方式中，所述通式C的数均分子量为800～12000，进 而为850～7000，更优选为1400～7000，例如1406、2140、2935、4948、2554、3763、852、1494、4973、3162、4778。
本发明一具体实施方式中，所述生物基聚酰胺弹性体的数均分子量为10000～70000，进而为10000～40000，更优选为30000～40000，例如39596、34507、35880、39022、38158、31860、22739、19659或18749、33711、18159。
本发明一具体实施方式中，所述通式D的数均分子量为500～5000，例如为1000、1500、2000、2500、3000、3500、4000、4500。
本发明一具体实施方式中，所述通式C还含有通式E的结构单元，且通式A、通式B和通式E的结构单元通过酰胺键连接而成，所述通式E为
较佳地，所述生物基聚酰胺弹性体中，所述通式A的摩尔百分比为10～40％；所述通式B的摩尔百分比为15～40％；所述通式D的摩尔百分比为35～65％；所述通式A、B和D的摩尔百分比之和为100％。
在一些具体的实施方式中，所述生物基聚酰胺弹性体中，所述通式A的摩尔百分比为15～30％；所述通式B的摩尔百分比为20～35％；所述通式D的摩尔百分比为40～65％；所述通式A、B和D的摩尔百分比之和为100％。
在一些具体的实施方式中，所述通式A、通式B、通式E与通式D的摩尔比例为18～25：18～30：1～10：40～65。
较佳地，所述通式A和通式B的摩尔比为1:1.0～1.5。
较佳地，所述通式C和通式D的结构单元在生物基聚酰胺弹性体中的质量含量在95％以上，优选97％以上。
本发明一具体实施方式中，所述生物基聚酰胺弹性体的原料包括戊二胺、二酸和聚四氢呋喃，所述二酸选自十碳二元酸、十一碳二酸、十二碳二酸、十三碳二酸、十四碳二酸、十五碳二酸、十六碳二酸、十七碳二酸或十八碳 二酸中的任意一种或几种。
本发明一具体实施方式中，所述二酸还包括己二酸。
本发明一具体实施方式中，所述生物基聚酰胺弹性体通过如下方法制备获得：先将戊二胺和二酸聚合获得预聚体，然后将预聚体与聚四氢呋喃聚合获得生物基聚酰胺弹性体。
本发明一具体实施方式中，所述预聚体与聚四氢呋喃的摩尔比为0.7～2:1，进而为0.8～1.5:1，优选0.7～1.3，更优选0.8～1.2，例如0.94:1、0.92:1、1.12:1、0.84:1、1.10:1、0.87:1、0.93:1、1.14:1、1.48:1、0.86:1、1.45:1。
本发明一具体实施方式中，所述聚四氢呋喃的数均分子量为500～5000，例如为分子量为1000的PTMEG 1000、分子量为2000的PTMEG 2000。
本发明一具体实施方式中，作为原料的戊二胺和长链脂肪族二酸之一或者两者均为通过生物法制得的。例如，戊二胺通过赖氨酸脱羧酶作用于赖氨酸的生物法得到。
本发明一具体实施方式中，制备所述生物基聚酰胺弹性体的原料还任选包括添加剂，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，所述添加剂在生物基聚酰胺弹性体中的质量含量为5％以下，进而优选为3％以下，例如0.1～3％。
本发明一具体实施方式中，所述生物基聚酰胺弹性体的密度为1.01～1.2g/mL，进而为1.01～1.07g/mL。
本发明一具体实施方式中，所述生物基聚酰胺弹性体的邵氏硬度为25D～80D，例如33D、45D、52D、63D、35D、42D、67D、50D、71D。
本发明一具体实施方式中，所述生物基聚酰胺弹性体的断裂伸长率为 200％以上，较佳地为300-1200％，例如为382％、539％、680％、730％、426％、566％、387％。
本发明一具体实施方式中，所述生物基聚酰胺弹性体的拉伸强度为15～60MPa，进而为17～50MPa或者20～60MPa。
本发明一具体实施方式中，所述生物基聚酰胺弹性体的缺口冲击强度为8kJ/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生物基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、二酸与第一催化剂和水混合，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获得的预聚体和聚四氢呋喃在第二催化剂的存在下进行聚合反应，获得聚酰胺弹性体。
其中，所述二酸选自十碳二元酸、十一碳二酸、十二碳二酸、十三碳二酸、十四碳二酸、十五碳二酸、十六碳二酸、十七碳二酸或十八碳二酸中的任意一种或几种。
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、次亚磷酸钠、次磷酸锌、次磷酸钙、次磷酸钾中的一种或者多种，优选为次磷酸钠和/或次亚磷酸钠。
所述第二催化剂为钛系催化剂、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。
较佳地，所述戊二胺和二酸的摩尔比为的摩尔比为1:1.0～1.5，优选 1:1.0～1.2。
较佳地，所述第一催化剂的加入量，占所述戊二胺、所述二酸和所述第一催化剂的总量的0.001～5％(摩尔百分比)，进而为1～2％，例如1.4％、1.5％。
较佳地，所述第二催化剂的加入量，占所述预聚体、所述聚四氢呋喃和所述第二催化剂的总量的0.001～3％(摩尔百分比)，进而为0.01～1.4％，例如1％、1.15％。
较佳地，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、所述二酸和所述添加剂的总量的0.001～5％(摩尔百分比)。
较佳地，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。
较佳地，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。
较佳地，所述预聚体与聚四氢呋喃的摩尔比为0.7～2:1，进而为0.8～1.5:1，优选0.7～1.3，更优选0.8～1.2，例如0.94:1、0.92:1、1.12:1、0.84:1、1.10:1、0.87:1、0.93:1、1.14:1、1.48:1、0.86:1、1.45:1。
较佳地，所述聚四氢呋喃的数均分子量为500～5000，例如为为分子量为1000的PTMEG 1000、分子量为1000的PTMEG 2000。。
较佳地，步骤S2中先将预聚体和聚四氢呋喃在220～260℃，例如240℃的条件下混合10～120min，例如90min，再加入第二催化剂。
较佳地，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，然后在0.5-2h内降低绝对压力至500Pa以下，继续反应1～10h，优选为1.5～5h，更优选为1～5h，例如1.5h、2h、2.5h、3.5h。
较佳地，步骤S2中所述聚合反应还包括充氮气至正压，再出料。
所述生物基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。
本发明所述生物基聚酰胺弹性体可以在滑雪鞋、足球鞋、跑步鞋等鞋材领域推广应用。其中所述滑雪鞋为鞋外壳，足球鞋为鞋底，跑步鞋为鞋中底。
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：本发明以生物法制备的戊二胺、长链(C10至C18)脂肪族二酸与特定比例的聚四氢呋喃为原料制备聚酰胺弹性体，性能媲美阿科玛公司的pebax系列弹性体，弹性好，硬度高且范围广；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，尤其是在鞋类领域的应用。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。
以下各实施例和对比例中，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。
各实施例和对比例中的原料来源：戊二胺、十碳二元酸、十一碳二酸、十二碳二酸、十四碳二酸、十五碳二酸、十六碳二酸购自凯赛(金乡)生物材料有限公司，均经由生物法制得；聚四氢呋喃(PTMEG)购自长连化工(长春)。
实施例1
在氮气条件下，向成盐釜内加入纯水366.94mol、戊二胺19.41mol，开启搅拌，加入十一碳二酸19.41mol，己二酸4.35mol，催化剂次磷酸钠0.65mol，制得聚酰胺盐水溶液。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3.69mol，烘干备用，产率85％，数均分子量为1406。
在氮气条件下，将羧基封端的预聚体3.48mol，PTMEG10003.69mol，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯71.7mmol，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0.13mol，产率60％，数均分子量为39596，其含有的结构单元及摩尔比例如表1，性能测试如表3。
实施例2
在氮气条件下，向成盐釜内加入纯水360.23mol、戊二胺19.51mol，开启搅拌，加入十四碳二酸22.87mol，催化剂次磷酸钠0.63mol，制得聚酰胺盐水溶液。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2.75mol，烘干备用，产率82％，数均分子量为2140。
在氮气条件下，将羧基封端的预聚体2.40mol，PTMEG10002.62mol，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯50.2mmol，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0.15mol，产率66％，数均分子量为34507，其含有的结构单元及摩尔比例如 表1，性能测试如表3。
实施例3
在氮气条件下，向成盐釜内加入纯水347.39mol、戊二胺19.22mol，开启搅拌，加入十五碳二酸21.65mol，催化剂次磷酸钠0.61mol，制得聚酰胺盐水溶液。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2.10mol，烘干备用，产率86％，数均分子量为2935。
在氮气条件下，将羧基封端的预聚体1.74mol，PTMEG20001.55mol，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯32.9mmol，然后在真空度为-0.06MPa条件下，搅拌反应2h，然后在2h内降低绝对压力至500Pa以下，继续反应1.5h，充氮气至正压，出料切粒，得到聚酰胺弹性体0.14mol，产率68％，数均分子量为35880，其含有的结构单元及摩尔比例如表1，性能测试如表3。
实施例4
在氮气条件下，向成盐釜内加入纯水332.01mol、戊二胺18.82mol，开启搅拌，加入十六碳二酸20.24mol，催化剂次磷酸钠0.58mol，制得聚酰胺盐水溶液。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1.19mol，烘干备用，产率84％，数均分子量为4948。
在氮气条件下，将羧基封端的预聚体1.01mol，PTMEG20001.20mol，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯22.1mmol，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0.19mol，产率65％，数均分子量为39022，其含有的结构单元及摩尔比例如表1，性能测试如表3。
实施例5
在氮气条件下，向成盐釜内加入纯水341.02mol、戊二胺18.92mol，开启搅拌，加入十一碳二酸21.20mol，催化剂次磷酸钠0.60mol，制得聚酰胺盐水溶液。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1.99mol，烘干备用，产率87％，数均分子量为2554。
在氮气条件下，将羧基封端的预聚体2.03mol，PTMEG10001.85mol，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯15.8mmol，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2.5h，充氮气至正压，出料切粒，得到聚酰胺弹性体0.12mol，产率65％，数均分子量为38160，其含有的结构单元及摩尔比例如表1，性能测试如表3。
实施例6
在氮气条件下，向成盐釜内加入纯水346.63mol、戊二胺19.61mol，开启搅拌，加入十一碳二酸21.17mol，催化剂次磷酸钠0.61mol，制得聚酰胺盐水溶液。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1.34mol，烘干备用，产率86％，数均分子量为3763。
在氮气条件下，将羧基封端的预聚体1.41mol，PTMEG10001.63mol， 倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯35.4mmol，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0.15mol，产率69％，数均分子量为31860，其含有的结构单元及摩尔比例如表1，性能测试如表3。
实施例7
在氮气条件下，向成盐釜内加入纯水339.76mol、戊二胺19.57mol，开启搅拌，加入十一碳二酸29.36mol，催化剂次磷酸钠0.10mol，制得聚酰胺盐水溶液。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8.35mol，烘干备用，产率85％，数均分子量为852。
在氮气条件下，将羧基封端的预聚体1.49mol，PTMEG10001.61mol，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯6.21mmol，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3h，充氮气至正压，出料切粒，得到聚酰胺弹性体0.08mol，产率67.2％，数均分子量为22739，其含有的结构单元及摩尔比例如表1，性能测试如表3。
实施例8
在氮气条件下，向成盐釜内加入纯水431.78mol、戊二胺15.66mol，开启搅拌，加入十四碳二酸19.48mol，催化剂次磷酸钠0.07mol，制得聚酰胺盐水溶液。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3.30mol，烘干备用，产率 86％，数均分子量为1494。
在氮气条件下，将羧基封端的预聚体1.13mol，PTMEG10000.99mol，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯8.5mmol，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2.5h，充氮气至正压，出料切粒，得到聚酰胺弹性体0.10mol，产率72％，数均分子量为19659，其含有的结构单元及摩尔比例如表1，性能测试如表3。
实施例9
在氮气条件下，向成盐釜内加入纯水328.06mol、戊二胺17.62mol，开启搅拌，加入十六碳二酸18.92mol，催化剂次磷酸钠0.24mol，制得聚酰胺盐水溶液。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1.07mol，烘干备用，产率82％，数均分子量为4973。
在氮气条件下，将羧基封端的预聚体0.46mol，PTMEG20000.31mol，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯1.54mmol，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3h，充氮气至正压，出料切粒，得到聚酰胺弹性体0.12mol，产率78％，数均分子量为18749，其含有的结构单元及摩尔比例如表1，性能测试如表3。
实施例10
在氮气条件下，向成盐釜内加入纯水258.7mol、戊二胺17.62mol，开启搅拌，加入十碳二酸19.23mol，催化剂次磷酸钠0.061mol，制得聚酰胺盐水溶液。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1.35mol，烘干备用，产率83％，数均分子量为3162。
在氮气条件下，将羧基封端的预聚体0.81mol，PTMEG20000.94mol，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯5.25mmol，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3h，充氮气至微正压，出料切粒，得到聚酰胺弹性体0.09mol，产率70％，数均分子量为33711，其含有的结构单元及摩尔比例如表2，性能测试如表3。
实施例11
在氮气条件下，向成盐釜内加入纯水309.16mol、戊二胺19.57mol，开启搅拌，加入十二碳二酸20.85mol，催化剂次磷酸钠0.08mol，制得聚酰胺盐水溶液。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1.03mol，烘干备用，产率81％，数均分子量为4778。
在氮气条件下，将羧基封端的预聚体0.45mol，PTMEG20000.31mol，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯7.6mmol，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3h，充氮气至微正压，出料切粒，得到聚酰胺弹性体0.0mol，产率76％，数均分子量为18159，其含有的结构单元及摩尔比例如表2，性能测试如表3。
对比例1
在氮气条件下，向成盐釜内加入纯水588.2mol、戊二胺33.82mol，开启 搅拌，加入己二酸35.38mol，催化剂次磷酸钠0.69mol，制得聚酰胺盐水溶液。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1.34mol，烘干备用，产率86％，数均分子量为4762。
在氮气条件下，将羧基封端的预聚体1.29mol，PTMEG10001.48mol，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯41.6mmol，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0.13mol，产率69％，数均分子量为39170，其含有的结构单元及摩尔比例如表2，性能测试如表3。
对比例2
在氮气条件下，向成盐釜内加入纯水393.12mol、戊二胺22.97mol，开启搅拌，加入十一碳二酸23.28mol，催化剂次磷酸钠0.46mol，制得聚酰胺盐水溶液。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0.27mol，烘干备用，产率86％，数均分子量为20989。
在氮气条件下，将羧基封端的预聚体0.25mol，PTMEG10001.16mol，己二酸0.48mol，倒入反应釜内，在240℃下混合90min，加入催化剂钛酸四丁酯21.1mmol，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0.29mol，产率68％，数均分子量为15112，其含有的结构单元及摩尔比例如表2，性能测试如表3。
表1
表2
表3
从上述实施例和对比例可以看出，根据本发明的实施例1～11使用以生物法制备的戊二胺、长链(C10至C18)脂肪族二酸与特定比例的聚四氢呋喃为原料，制备得到的聚酰胺弹性体性能优异，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。与之相对地，对比例1只采用己二酸，而没有采用长链(C10至C18)脂肪族二酸，制得的聚酰胺弹性体粘度过高，断裂伸长率过低。对比例2采用过量的聚四氢呋喃作为原料，制得的聚酰胺弹性体邵氏硬度D过高，断裂伸长率过低，拉伸强度过高。
Claims (10)
- 一种生物基聚酰胺弹性体，其特征在于，其含有通式C和通式D的结构单元，且通式C和通式D的结构单元通过酯基连接而成；所述通式C含有通式A和通式B的结构单元，且通式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，x＝8-16，且x为整数；其中，所述生物基聚酰胺弹性体的相对粘度为1.0～2.0，更佳地为1.1～1.7，和/或，所述通式C的数均分子量为800～12000，和/或，所述生物基聚酰胺弹性体的数均分子量为10000～70000，和/或，所述通式D的数均分子量为500～5000。 - 根据权利要求1所述的生物基聚酰胺弹性体，其特征在于，所述通式C还含有通式E的结构单元，且通式A、通式B和通式E的结构单元通过酰胺键连接而成，所述通式E为
- 根据权利要求1所述的生物基聚酰胺弹性体，其特征在于，所述通式A的摩尔百分比为10～40％；所述通式B的摩尔百分比为15～40％；所述通式D的摩尔百分比为35～65％；所述通式A、B和D的摩尔百分比之和为100％；较佳地，所述通式A和通式B的摩尔比为1:1.0～1.5。
- 根据权利要求1所述的生物基聚酰胺弹性体，其特征在于，所述生物基聚酰胺弹性体的原料包括戊二胺、二酸和聚四氢呋喃，所述二酸选自十碳 二元酸、十一碳二酸、十二碳二酸、十三碳二酸、十四碳二酸、十五碳二酸、十六碳二酸、十七碳二酸或十八碳二酸中的任意一种或几种；较佳地，所述预聚体与聚四氢呋喃的摩尔比为0.7-2:1。
- 根据权利要求1所述的生物基聚酰胺弹性体，其特征在于，所述生物基聚酰胺弹性体的密度为1.01～1.2g/mL，和/或，所述生物基聚酰胺弹性体的邵氏硬度为25D～80D，和/或，所述生物基聚酰胺弹性体的断裂伸长率为200％以上，和/或，所述生物基聚酰胺弹性体的拉伸强度为15～60MPa，优选17～50MPa或20～60MPa，和/或，所述生物基聚酰胺弹性体的缺口冲击强度为8kJ/m 2以上，更佳地为NB(冲不断)。
- 一种权利要求1～5中任意一项所述生物基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、二酸与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获得的预聚体和聚四氢呋喃在第二催化剂的存在下进行聚合反应，获得聚酰胺弹性体；其中，所述二酸选自十碳二元酸、十一碳二酸、十二碳二酸、十三碳二酸、十四碳二酸、十五碳二酸、十六碳二酸、十七碳二酸或十八碳二酸中的任意一种或几种；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、次亚磷酸钠、次磷酸锌、次磷酸钙、次磷酸钾中的一种或者多种，优选为次磷酸钠和/或次亚磷酸钠；和/或，所述第二催化剂为钛系催化剂、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所述的生物基聚酰胺弹性体的制备方法，其特征在于，所述第一催化剂的加入量，占所述戊二胺、所述二酸和所述第一催化剂的总量的0.001～5摩尔％；和/或，所述第二催化剂的加入量，占所述预聚体、所述聚四氢呋喃和所述第二催化剂的总量的0.001～3摩尔％。
- 根据权利要求6所述的生物基聚酰胺弹性体的制备方法，其特征在于，所述预聚体与聚四氢呋喃的摩尔比为0.7～1.3:1。
- 根据权利要求6所述的生物基聚酰胺弹性体的制备方法，其特征在于，所述戊二胺和二酸的摩尔比为1:1.0～1.5，优选1:1.0～1.2。
- 根据权利要求6所述的生物基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；和/或，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，以使反应物置于高真空中，继续反应1-10h。
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| JP2010222396A (ja) * | 2009-03-19 | 2010-10-07 | Ube Ind Ltd | ポリエーテルアミドエラストマー組成物 |
| CN102046697A (zh) * | 2008-10-06 | 2011-05-04 | 阿肯马法国公司 | 由可再生材料获得的嵌段共聚物和用于制备这种嵌段共聚物的方法 |
| CN102918082A (zh) * | 2010-04-07 | 2013-02-06 | 阿肯马法国公司 | 由可再生材料获得的嵌段共聚物和用于制备这种嵌段共聚物的方法 |
| CN107955163A (zh) * | 2016-10-17 | 2018-04-24 | 上海杰事杰新材料(集团)股份有限公司 | 超韧聚酰胺树脂及其制备方法 |
| CN108148198A (zh) * | 2017-12-22 | 2018-06-12 | 山东凯恩新材料科技有限公司 | 一种可低压注塑聚酰胺热熔胶及其制备方法 |
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| CN102046697A (zh) * | 2008-10-06 | 2011-05-04 | 阿肯马法国公司 | 由可再生材料获得的嵌段共聚物和用于制备这种嵌段共聚物的方法 |
| JP2010222396A (ja) * | 2009-03-19 | 2010-10-07 | Ube Ind Ltd | ポリエーテルアミドエラストマー組成物 |
| CN102918082A (zh) * | 2010-04-07 | 2013-02-06 | 阿肯马法国公司 | 由可再生材料获得的嵌段共聚物和用于制备这种嵌段共聚物的方法 |
| CN107955163A (zh) * | 2016-10-17 | 2018-04-24 | 上海杰事杰新材料(集团)股份有限公司 | 超韧聚酰胺树脂及其制备方法 |
| CN108148198A (zh) * | 2017-12-22 | 2018-06-12 | 山东凯恩新材料科技有限公司 | 一种可低压注塑聚酰胺热熔胶及其制备方法 |
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