CN106832817A - Excellent polyester thermoplastic elastomer of S. E. A. and preparation method thereof - Google Patents
Excellent polyester thermoplastic elastomer of S. E. A. and preparation method thereof Download PDFInfo
- Publication number
- CN106832817A CN106832817A CN201710069757.XA CN201710069757A CN106832817A CN 106832817 A CN106832817 A CN 106832817A CN 201710069757 A CN201710069757 A CN 201710069757A CN 106832817 A CN106832817 A CN 106832817A
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- CN
- China
- Prior art keywords
- kettle
- slurrying
- antioxidant
- thermoplastic elastomer
- polyester thermoplastic
- Prior art date
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- 229920000728 polyester Polymers 0.000 title claims abstract description 55
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 35
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 35
- 239000003381 stabilizer Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 24
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 150000002334 glycols Chemical class 0.000 claims abstract description 12
- 239000004615 ingredient Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 48
- 239000002002 slurry Substances 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- -1 Methyl alcohol ester Chemical class 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 230000032050 esterification Effects 0.000 claims description 24
- 238000005886 esterification reaction Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000010792 warming Methods 0.000 claims description 23
- 230000008719 thickening Effects 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 19
- 150000007942 carboxylates Chemical class 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 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 8
- 229920001971 elastomer Polymers 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N iso-butyl alcohol Natural products CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- NWLUZGJDEZBBRH-UHFFFAOYSA-N 2-(propan-2-yloxymethyl)oxirane Chemical compound CC(C)OCC1CO1 NWLUZGJDEZBBRH-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-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
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 2
- 150000003377 silicon compounds Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical group C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to polyester thermoplastic elastomer technical field, it is excellent polyester thermoplastic elastomer of a kind of S. E. A. and preparation method thereof, its raw material includes polyether Glycols 30% to 70%, the catalyst compounded A50ppm to 300ppm of rare earth coated, mixing antioxidant C100ppm to 1000ppm, toughener D100ppm to 1000ppm, stabilizer E30ppm to 1000ppm, stabilizer F10ppm to 500ppm, the major ingredient of surplus.The excellent polyester thermoplastic elastomer of S. E. A. of the invention its stable performance, elastic absorptivity is excellent, significantly better than the preferable like product of the using effect of current market, the excellent polyester thermoplastic elastomer of S. E. A. of the invention is obtained using the inventive method, its preparation process is reasonable, method is simple, it is easy to operate, its good stability for preparing melt in process.
Description
Technical field
It is a kind of excellent polyester thermoplastic's bullet of S. E. A. the present invention relates to polyester thermoplastic elastomer technical field
Gonosome and preparation method thereof.
Background technology
Polyester thermoplastic elastomer has excellent mechanical performance, such as toughness, fatigue resistance, intensity, wearability.Cause
The range of application of this polyester thermoplastic elastomer in recent years is constantly widened, between polymer modification, buffering part, hydraulic hose, footwear material,
Anticorrosion antiwear in rotational forming tire, gear, flexible joint, noise reduction gear, elevator slideway, chemical industry equipment pipeline valve is resistance to
All it is well received by the public in the fields such as height adiabator.
Polyester thermoplastic elastomer material is used as padded coaming, and its energy absorption is outstanding；While its mechanical performance pair
Temperature and not clear sense, with temperature in use very wide；And service life star is to more long.Buffered compared to rubber and elastic cement
Material, polyester thermoplastic elastomer material capacity is big, S. E. A. is high, simple structure, maintenance convenience, applies more and more
In fields such as locomotive both domestic and external, lorry and railcars.
But, the less stable of current polyester thermoplastic elastomer melt during polymerization process is very easy to
Degraded so that its viscosity declines causes melt strength to be deteriorated, while can also generate the volatile byproducts such as tetrahydrofuran causes system
Bubble and Odor stimulation are formed in product.
The content of the invention
The invention provides the polyester thermoplastic elastomer that a kind of S. E. A. is excellent, above-mentioned prior art is which overcomed
Deficiency, its elastic performance is excellent, long service life, present invention also offers the polyester thermoplastic that a kind of S. E. A. is excellent
Method for producing elastomers, this method can solve the problem that the less stable of the melt during polymerization process, be very easy to degraded
Problem.
One of technical scheme is realized by following measures：A kind of excellent polyester heat of S. E. A.
Thermoplastic elastic, its raw material include polyether Glycols 30% to 70%, the catalyst compounded A50ppm to 300ppm of rare earth coated,
Mixing antioxidant C100ppm to 1000ppm, toughener D100ppm to 1000ppm, stabilizer E30ppm to 1000ppm, stabilization
The major ingredient of agent F10ppm to 500ppm, surplus, major ingredient include Isosorbide-5-Nitrae butanediol and terephthalic acid (TPA), wherein, Isosorbide-5-Nitrae butanediol with it is right
The mol ratio of phthalic acid is 1:1 to 100:1.
Here is the further optimization and/or improvements to one of foregoing invention technical scheme：
Above-mentioned polyether Glycols are one or more of PolyTHF, polyethylene glycol and polypropylene glycol；Or/and, rare earth
The catalyst compounded A of coated be more than one rare earth metal oxide or more than one rare earth metal salt, it is a kind of with
On organic titanic compound and more than one organo-silicon compound compound, wherein, rare earth metal be lanthanum, samarium, cerium, praseodymium,
Neodymium, organic titanic compound is different metatitanic acid tetramethyl alcohol ester, metatitanic acid tetrem alcohol ester, the propyl alcohol ester of metatitanic acid four, the butyl alcohol ester of metatitanic acid four, metatitanic acid four
Propyl ester, the isobutyl alcohol ester of metatitanic acid four, organo-silicon compound are hexadecyl trimethoxy silane, methyl silicate, silester, silicic acid
Propyl ester, butyl silicate；Or/and, mixing antioxidant C is the organic phosphates antioxygen of 10% to 90% Hinered phenols antioxidant and surplus
The mixture of agent, wherein, Hinered phenols antioxidant is antioxidant 246, antioxidant 1010, antioxidant 1076, antioxidant 1096, anti-
One or more of oxygen agent 300；Organic phosphates antioxidant is Trimethyl phosphite, triethyl phosphite, triethyl phosphite, Asia
One or more of triphenyl phosphate；Or/and, toughener D is Sodium Polyacrylate, polyacrylic acid potassium, calcium polyacrylate (CPA), polypropylene
One or more of sour zinc；Or/and, stabilizer E is glycidol, isopropyl glycidyl ether, n-butyl glycidyl ether, just
One or more of octyl glycidyl ether；Or/and, stabilizer F is trimethyl phosphate, triethyl phosphate, diethyl phosphate, phosphorus
One or more of sour tributyl, triphenyl phosphate, tricresyl phosphate.
It is above-mentioned to obtain as follows：The first step, slurrying first carries out nitrogen protection, to slurrying kettle in control slurrying kettle absolutely
It is 1MPa to pressure, by Isosorbide-5-Nitrae butanediol, terephthalic acid (TPA), polyether Glycols, the catalyst compounded A of rare earth coated, mixing antioxygen
Agent C and toughener D to be added be well mixed in slurrying kettle and obtained slurries, and with the programming rate of 3 DEG C/min to 7 DEG C/min by slurries
It is warming up to 80 DEG C to 100 DEG C；
Slurries after first step constant temperature are moved into esterifying kettle and carry out nitrogen protection, in esterifying kettle by second step, esterification
Absolute pressure is controlled in 60KPa to 80KPa, and slurries then are warming up into 150 DEG C with the programming rate of 3 DEG C/min to 7 DEG C/min
To 180 DEG C of esterifications 1 hour, then slurries are warming up to 230 DEG C to 250 DEG C with the programming rate of 0.5 DEG C/min to 1 DEG C/min
Continue esterification and obtain carboxylate in 4 hours；
3rd step, precondensation, second step is obtained carboxylate feeding preshrunk reactor, be added thereto to stabilizer E and
Stabilizer F, after stirring 10 minutes to 20 minutes, rises to 230 DEG C to 250 DEG C by preshrunk reactor temperature rapidly, while will be pre-
In 500Pa to 200Pa, keeping temperature is constant with pressure, carries out prepolymerization reaction 4 hours extremely for absolute pressure control in contracting reactor
Obtain prepolymer within 9 hours；
4th step, thickening, the prepolymer feeding thickening kettle that the 3rd step is obtained rapidly rises to preshrunk reactor temperature
230 DEG C to 250 DEG C, while by absolute pressure control is in 50Pa to 100Pa in preshrunk reactor, keeping temperature is constant with pressure,
Constant temperature and pressure final minification reaction is carried out, the reaction time is 2 hours to 6 hours, and reaction terminates to obtain the excellent polyester of S. E. A.
Thermoplastic elastomer (TPE).
In the above-mentioned first step, slurrying kettle uses Q235A vertical elliptical end socket tank reactors, the direct tube section of slurrying kettle
Blade diameter length ratio is 1：1.2,1.2 times to 1.4 times of inventory for needed for, the agitating paddle in slurrying kettle is Q235A for the volume of slurrying kettle
Anchor frame type agitating blade processed；In second step, esterifying kettle uses packed tower, and the blade diameter length ratio of the packing section of packed tower is 1:15, esterifying kettle
Volume 1.2 times to 1.4 times of inventory for needed for；In 3rd step, preshrunk reactor uses Q235A vertical elliptical end socket kettles
Formula reactor, the blade diameter length ratio of the direct tube section of preshrunk reactor is 1:1.5, the volume of preshrunk reactor for needed for inventory 1.2
Again to 1.4 times, the agitating paddle in preshrunk reactor is Q235A anchor frame type agitating blades；In 4th step, thickening kettle uses Q235A
Horizontal reactor processed, the blade diameter length ratio for viscosifying the direct tube section of kettle is 1:4, viscosify the volume of kettle 1.2 times to 1.4 of inventory for needed for
Times, inside there is Q235 cages basket formula Dropbox spiral pushing tack producing device, whole process spiral pushing frequency is 30HZ.
In the above-mentioned first step, overall process stirring is carried out using the stirring frequency of 20Hz；In 3rd step, using the stirring of 20Hz
Frequency carries out overall process stirring.
The two of technical scheme are realized by following measures：It is a kind of according to one of technical scheme
The preparation method of the excellent polyester thermoplastic elastomer of S. E. A., is carried out in the steps below：The first step, slurrying, first to system
Slurry kettle carries out nitrogen protection, and it is 1MPa to control absolute pressure in slurrying kettle, by Isosorbide-5-Nitrae butanediol, terephthalic acid (TPA), polyethers binary
It is well mixed in alcohol, the catalyst compounded A of rare earth coated, mixing antioxidant C and toughener D addition slurrying kettles and obtains slurries, and
Slurries are warming up to 80 DEG C to 100 DEG C with the programming rate of 3 DEG C/min to 7 DEG C/min；
Slurries after first step constant temperature are moved into esterifying kettle and carry out nitrogen protection, in esterifying kettle by second step, esterification
Absolute pressure is controlled in 60KPa to 80KPa, and slurries then are warming up into 150 DEG C with the programming rate of 3 DEG C/min to 7 DEG C/min
To 180 DEG C of esterifications 1 hour, then slurries are warming up to 230 DEG C to 250 DEG C with the programming rate of 0.5 DEG C/min to 1 DEG C/min
Continue esterification and obtain carboxylate in 4 hours；
3rd step, precondensation, second step is obtained carboxylate feeding preshrunk reactor, be added thereto to stabilizer E and
Stabilizer F, after stirring 10 minutes to 20 minutes, rises to 230 DEG C to 250 DEG C by preshrunk reactor temperature rapidly, while will be pre-
In 500Pa to 200Pa, keeping temperature is constant with pressure, carries out prepolymerization reaction 4 hours extremely for absolute pressure control in contracting reactor
Obtain prepolymer within 9 hours；
4th step, thickening, the prepolymer feeding thickening kettle that the 3rd step is obtained rapidly rises to preshrunk reactor temperature
230 DEG C to 250 DEG C, while by absolute pressure control is in 50Pa to 100Pa in preshrunk reactor, keeping temperature is constant with pressure,
Constant temperature and pressure final minification reaction is carried out, the reaction time is 2 hours to 6 hours, and reaction terminates to obtain the excellent polyester of S. E. A.
Thermoplastic elastomer (TPE).
Here is the further optimization and/or improvements to the two of foregoing invention technical scheme：
In the above-mentioned first step, slurrying kettle uses Q235A vertical elliptical end socket tank reactors, the direct tube section of slurrying kettle
Blade diameter length ratio is 1：1.2,1.2 times to 1.4 times of inventory for needed for, the agitating paddle in slurrying kettle is Q235A for the volume of slurrying kettle
Anchor frame type agitating blade processed；In second step, esterifying kettle uses packed tower, and the blade diameter length ratio of the packing section of packed tower is 1:15, esterifying kettle
Volume 1.2 times to 1.4 times of inventory for needed for；In 3rd step, preshrunk reactor uses Q235A vertical elliptical end socket kettles
Formula reactor, the blade diameter length ratio of the direct tube section of preshrunk reactor is 1:1.5, the volume of preshrunk reactor for needed for inventory 1.2
Again to 1.4 times, the agitating paddle in preshrunk reactor is Q235A anchor frame type agitating blades；In 4th step, thickening kettle uses Q235A
Horizontal reactor processed, the blade diameter length ratio for viscosifying the direct tube section of kettle is 1:4, viscosify the volume of kettle 1.2 times to 1.4 of inventory for needed for
Times, inside there is Q235 cages basket formula Dropbox spiral pushing tack producing device, whole process spiral pushing frequency is 30HZ.
In the above-mentioned first step, overall process stirring is carried out using the stirring frequency of 20Hz；In 3rd step, using the stirring of 20Hz
Frequency carries out overall process stirring.
The excellent polyester thermoplastic elastomer of S. E. A. of the invention its stable performance, elastic absorptivity is excellent, bright
The aobvious preferable like product of using effect for being better than current market, obtains S. E. A. of the invention excellent using the inventive method
Different polyester thermoplastic elastomer, rationally, method is simple, it is easy to operate for its preparation process, melt in its preparation process
Good stability.
Specific embodiment
The present invention is not limited by following embodiments, can technology according to the present invention scheme and actual conditions determine specifically
Implementation method.Various chemical reagent and chemical article are previously mentioned in the present invention unless otherwise specified, are known in existing technology
Public chemical reagent and chemical article；Percentage in the present invention is as without specified otherwise, being mass percent；The present invention
In water as being running water or pure water without specified otherwise；If the solution in the present invention is without specified otherwise, being solvent is
The aqueous solution of water, for example, hydrochloric acid solution is aqueous hydrochloric acid solution；Normal temperature in the present invention refers generally to 15 DEG C to 25 DEG C of temperature,
It is commonly defined as 25 DEG C.
With reference to embodiment, the invention will be further described：
Embodiment 1, the raw material of the excellent polyester thermoplastic elastomer of the S. E. A. include polyether Glycols 30% to
70%th, the catalyst compounded A50ppm to 300ppm of rare earth coated, mixing antioxidant C100ppm to 1000ppm, toughener
D100ppm to 1000ppm, stabilizer E30ppm to 1000ppm, stabilizer F10ppm to 500ppm, the major ingredient of surplus, major ingredient bag
Isosorbide-5-Nitrae butanediol and terephthalic acid (TPA) are included, wherein, Isosorbide-5-Nitrae butanediol is 1 with the mol ratio of terephthalic acid (TPA):1 to 100:1.According to this
Excellent polyester thermoplastic elastomer its stable performance of the S. E. A. that obtains of invention, elastic absorptivity is excellent, hence it is evident that be better than
The preferable like product of using effect of current market.
Embodiment 2, the raw material of the excellent polyester thermoplastic elastomer of the S. E. A. include polyether Glycols 30% or
70%th, rare earth coated catalyst compounded A50ppm or 300ppm, mixing antioxidant C100ppm or 1000ppm, toughener
D100ppm or 1000ppm, stabilizer E30ppm or 1000ppm, stabilizer F10ppm or 500ppm, the major ingredient of surplus, major ingredient bag
Isosorbide-5-Nitrae butanediol and terephthalic acid (TPA) are included, wherein, Isosorbide-5-Nitrae butanediol is 1 with the mol ratio of terephthalic acid (TPA):1 or 100:1.
Embodiment 3, as the optimization of above-described embodiment, polyether Glycols are PolyTHF, polyethylene glycol and poly- the third two
One or more of alcohol；Or/and, the catalyst compounded A of rare earth coated is the oxide or one kind of more than one rare earth metal
The compound of the salt, more than one organic titanic compound and more than one organo-silicon compound of rare earth metal above, its
In, rare earth metal is lanthanum, samarium, cerium, praseodymium, neodymium, and organic titanic compound is metatitanic acid tetramethyl alcohol ester, metatitanic acid tetrem alcohol ester, metatitanic acid 4 third
Alcohol ester, the butyl alcohol ester of metatitanic acid four, tetraisopropyl titanate, the isobutyl alcohol ester of metatitanic acid four, organo-silicon compound are hexadecyl trimethoxy
Silane, methyl silicate, silester, silicic acid propyl ester, butyl silicate；Or/and, mixing antioxidant C is 10% to 90% hindered phenol
The mixture of the organic phosphates antioxidant of kind antioxidant and surplus, wherein, Hinered phenols antioxidant is antioxidant 246, antioxidant
1010th, one or more of antioxidant 1076, antioxidant 1096, antioxidant 300；Organic phosphates antioxidant is phosphorous acid front three
One or more of ester, triethyl phosphite, triethyl phosphite, triphenyl phosphite；Or/and, toughener D is polyacrylic acid
One or more of sodium, polyacrylic acid potassium, calcium polyacrylate (CPA), polyacrylic acid zinc；Or/and, stabilizer E is glycidol, isopropyl
One or more of base glycidol ether, n-butyl glycidyl ether, n-octyl glycidyl ether, are with being easy to carboxyl reaction
Simple function group or polyfunctional group glycidyl compound；Or/and, stabilizer F be trimethyl phosphate, triethyl phosphate,
One or more of diethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, stabilizer F are easy to capture polycondensation
React the thermal degradation side reaction that the free radical for producing suppresses polymer.
Embodiment 4, as the optimization of above-described embodiment, the excellent polyester thermoplastic elastomer of the S. E. A. is by following
Preparation method is obtained：The first step, slurrying first carries out nitrogen protection to slurrying kettle, and it is 1MPa to control absolute pressure in slurrying kettle, will
1,4 butanediols, terephthalic acid (TPA), polyether Glycols, the catalyst compounded A of rare earth coated, mixing antioxidant C and toughener D add
Enter to be well mixed in slurrying kettle and obtain slurries, and slurries are warming up to 80 DEG C extremely with the programming rate of 3 DEG C/min to 7 DEG C/min
100℃；
Slurries after first step constant temperature are moved into esterifying kettle and carry out nitrogen protection, in esterifying kettle by second step, esterification
Absolute pressure is controlled in 60KPa to 80KPa, and slurries then are warming up into 150 DEG C with the programming rate of 3 DEG C/min to 7 DEG C/min
To 180 DEG C of esterifications 1 hour, then slurries are warming up to 230 DEG C to 250 DEG C with the programming rate of 0.5 DEG C/min to 1 DEG C/min
Continue esterification and obtain carboxylate in 4 hours；
3rd step, precondensation, second step is obtained carboxylate feeding preshrunk reactor, be added thereto to stabilizer E and
Stabilizer F, after stirring 10 minutes to 20 minutes, rises to 230 DEG C to 250 DEG C by preshrunk reactor temperature rapidly, while will be pre-
In 500Pa to 200Pa, keeping temperature is constant with pressure, carries out prepolymerization reaction 4 hours extremely for absolute pressure control in contracting reactor
Obtain prepolymer within 9 hours；
4th step, thickening, the prepolymer feeding thickening kettle that the 3rd step is obtained rapidly rises to preshrunk reactor temperature
230 DEG C to 250 DEG C, while by absolute pressure control is in 50Pa to 100Pa in preshrunk reactor, keeping temperature is constant with pressure,
Constant temperature and pressure final minification reaction is carried out, the reaction time is 2 hours to 6 hours, and reaction terminates to obtain the excellent polyester of S. E. A.
Thermoplastic elastomer (TPE).The excellent polyester thermoplastic elastomer of S. E. A. of the invention is obtained using the method, it was prepared
Cheng Heli, method is simple, it is easy to operate, its good stability for preparing melt in process.
Embodiment 5, the excellent polyester thermoplastic elastomer of the S. E. A. is obtained by following preparation methods：The first step,
Slurrying, first carries out nitrogen protection to slurrying kettle, and it is 1MPa to control absolute pressure in slurrying kettle, by Isosorbide-5-Nitrae butanediol, terephthaldehyde
Acid, polyether Glycols, the catalyst compounded A of rare earth coated, mixing antioxidant C and toughener D are well mixed in adding slurrying kettle
Slurries are obtained, and slurries are warming up to 80 DEG C or 100 DEG C with the programming rate of 3 DEG C/min or 7 DEG C/min；
Slurries after first step constant temperature are moved into esterifying kettle and carry out nitrogen protection, in esterifying kettle by second step, esterification
Absolute pressure is controlled in 60KPa or 80KPa, and slurries then are warming up into 150 DEG C with the programming rate of 3 DEG C/min or 7 DEG C/min
Or 180 DEG C of esterifications 1 hour, then slurries are warming up to 230 DEG C or 250 DEG C with the programming rate of 0.5 DEG C/min or 1 DEG C/min
Continue esterification and obtain carboxylate in 4 hours；
3rd step, precondensation, second step is obtained carboxylate feeding preshrunk reactor, be added thereto to stabilizer E and
Stabilizer F, after stirring 10 minutes or 20 minutes, rises to 230 DEG C or 250 DEG C by preshrunk reactor temperature rapidly, while will be pre-
In contracting reactor absolute pressure control in 500Pa or 200Pa, keeping temperature is constant with pressure, carry out prepolymerization reaction 4 hours or
Obtain prepolymer within 9 hours；
4th step, thickening, the prepolymer feeding thickening kettle that the 3rd step is obtained rapidly rises to preshrunk reactor temperature
230 DEG C or 250 DEG C, while by absolute pressure control is in 50Pa or 100Pa in preshrunk reactor, keeping temperature is constant with pressure,
Constant temperature and pressure final minification reaction is carried out, the reaction time is 2 hours or 6 hours, and reaction terminates to obtain the excellent polyester of S. E. A.
Thermoplastic elastomer (TPE).
Embodiment 6, used as the optimization of embodiment 4 and embodiment 5, in the first step, slurrying kettle uses Q235A vertical ellipticals
End socket tank reactor, the blade diameter length ratio of the direct tube section of slurrying kettle is 1：1.2, the volume of slurrying kettle is 1.2 times of inventory for needed for
To 1.4 times, preferably 1.2 times, agitating paddle is Q235A anchor frame type agitating blades；In second step, esterifying kettle uses packed tower, filler
The blade diameter length ratio of the packing section of tower is 1:15, the volume of esterifying kettle is 1.2 times to 1.4 times, preferably 1.2 times of inventory for needed for；The
In three steps, preshrunk reactor uses Q235A vertical elliptical end socket tank reactors, the blade diameter length ratio of the direct tube section of preshrunk reactor
It is 1:1.5,1.2 times to 1.4 times of inventory for needed for, preferably 1.2 times, agitating paddle is Q235A systems for the volume of preshrunk reactor
Anchor frame type agitating blade；In 4th step, thickening kettle uses Q235A horizontal reactors, and the blade diameter length ratio for viscosifying the direct tube section of kettle is 1:
4, the volume of kettle is viscosified 1.2-1.4 times of inventory for needed for, preferably 1.2 times, inside there is Q235 cages basket formula Dropbox spiral pushing
Tack producing device, whole spiral pushing frequency of crossing is 30HZ.It is used to prepare energy of the invention using the equipment described in the present embodiment
The excellent polyester thermoplastic elastomer of amount absorptivity, its better adaptability, but the present invention are not limited only to cited by the present embodiment
Equipment, naturally it is also possible to using with the present embodiment have same effect and act on equipment, and protection scope of the present invention it
It is interior.
Embodiment 7, as the optimization of embodiment 4, embodiment 5 and embodiment 6, in the first step, using 20Hz stirring frequently
Rate carries out overall process stirring；In 3rd step, overall process stirring is carried out using the stirring frequency of 20Hz.Using stirring in the first step,
Can mix material more uniform, using stirring in the 3rd step, prepolymerization reaction can be made more abundant, reaction is more permanent steady
It is fixed.
Embodiment 8, the excellent polyester thermoplastic elastomer of the S. E. A. is obtained by following preparation methods：The first step,
Slurrying, first carries out nitrogen protection to slurrying kettle, and it is 1MPa to control absolute pressure in slurrying kettle, by Isosorbide-5-Nitrae butanediol 2kg, to benzene two
Formic acid 2.46kg, PolyTHF (molecular weight is 2000) 3.26kg (accounting for carboxylate mass fraction 50%), lanthana, metatitanic acid four
Propyl alcohol ester, hexadecyl trimethoxy silane and methyl silicate compound the catalyst compounded A0.625g of rare earth coated, anti-to be formed
Oxygen agent 246 compounds mixing antioxidant C6.25g, the toughener D calcium polyacrylate (CPA)s 6.25g to be formed with triphenyl phosphite and adds system
It is well mixed in slurry kettle and obtains slurries, and slurries is warming up to 100 DEG C with the programming rate of 5 DEG C/min；
Slurries after first step constant temperature are moved into esterifying kettle and carry out nitrogen protection, in esterifying kettle by second step, esterification
Absolute pressure is controlled in 60KPa or 80KPa, and slurries then are warming up into 180 DEG C of esterifications 1 with the programming rate of 5 DEG C/min
Hour, then with the programming rate of 0.5 DEG C/min or 1 DEG C/min by slurries be warming up to 250 DEG C continue esterifications obtain ester within 4 hours
Compound；
3rd step, precondensation, the carboxylate feeding preshrunk reactor that second step is obtained is added thereto to stabilizer E contractings
Water glycerine 5.625g and stabilizer F tricresyl phosphate 1.875g, after stirring 10 minutes or 20 minutes, rapidly by preshrunk reactor
Interior temperature rises to 250 DEG C, while by absolute pressure control in preshrunk reactor in 500Pa or 200Pa, keeping temperature is permanent with pressure
It is fixed, carry out prepolymerization reaction and obtain prepolymer in 9 hours, melt viscosity is about 1.1dl to 1.3dl；
4th step, thickening, the prepolymer feeding thickening kettle that the 3rd step is obtained rapidly rises to preshrunk reactor temperature
250 DEG C, while, in 50Pa or 100Pa, keeping temperature is constant with pressure, carries out constant temperature by absolute pressure control in preshrunk reactor
Constant pressure final minification reacts, and the reaction time is 4 hours, and reaction terminates to obtain the excellent polyester thermoplastic elastomer of S. E. A..
Embodiment 9, the excellent polyester thermoplastic elastomer of the S. E. A. is obtained by following preparation methods：The first step,
Slurrying, first carries out nitrogen protection to slurrying kettle, and it is 1MPa to control absolute pressure in slurrying kettle, by Isosorbide-5-Nitrae butanediol 2kg, to benzene two
Formic acid 2.46kg, PolyTHF (molecular weight is 2000) 3.26kg (accounting for carboxylate mass fraction 50%), lanthana, metatitanic acid four
Propyl alcohol ester, hexadecyl trimethoxy silane and methyl silicate compound the catalyst compounded A0.625g of rare earth coated, anti-to be formed
Oxygen agent 246 compounds mixing antioxidant C6.25g, the toughener D calcium polyacrylate (CPA)s 6.25g to be formed with triphenyl phosphite and adds system
It is well mixed in slurry kettle and obtains slurries, and slurries is warming up to 80 DEG C with the programming rate of 5 DEG C/min；
Slurries after first step constant temperature are moved into esterifying kettle and carry out nitrogen protection, in esterifying kettle by second step, esterification
Absolute pressure is controlled in 60KPa or 80KPa, and slurries then are warming up into 180 DEG C of esterifications 1 with the programming rate of 5 DEG C/min
Hour, then with the programming rate of 0.5 DEG C/min or 1 DEG C/min by slurries be warming up to 230 DEG C continue esterifications obtain ester within 4 hours
Compound；
3rd step, precondensation, the carboxylate feeding preshrunk reactor that second step is obtained is added thereto to stabilizer E contractings
Water glycerine 5.625g and stabilizer F tricresyl phosphate 1.875g, after stirring 10 minutes or 20 minutes, rapidly by preshrunk reactor
Interior temperature rises to 230 DEG C, while by absolute pressure control in preshrunk reactor in 500Pa or 200Pa, keeping temperature is permanent with pressure
It is fixed, carry out prepolymerization reaction and obtain prepolymer in 9 hours, melt viscosity is about 1.1dl to 1.3dl；
4th step, thickening, the prepolymer feeding thickening kettle that the 3rd step is obtained rapidly rises to preshrunk reactor temperature
250 DEG C, while, in 50Pa or 100Pa, keeping temperature is constant with pressure, carries out constant temperature by absolute pressure control in preshrunk reactor
Constant pressure final minification reacts, and the reaction time is 4 hours, and reaction terminates to obtain the excellent polyester thermoplastic elastomer of S. E. A..
Contrast 1 is company of South Korea like product BT-1055D, and contrast 2 is the country certain company like product DH5525, should
Two class products are current market sale preferably, customer satisfaction two kinds of products higher, using two kinds of products and the present invention
The excellent polyester thermoplastic elastomer of S. E. A. that embodiment is obtained is compared, with stronger convincingness.
Polymer elastomer molecular chain rupture after the heating, THF small molecules increase, and melt index is raised, and small molecule is more,
Melt index is higher, and thermal degradation is bigger, and heat endurance is more bad, from data in table 1, the energy that the embodiment of the present invention is obtained
Melt index is suitable with the melt index for contrasting 1 after processing for the excellent polyester thermoplastic elastomer of amount absorptivity, but its
THF small molecules after processing illustrate the excellent polyester thermoplastic of the S. E. A. that the embodiment of the present invention is obtained significantly lower than contrast 1
Property elastomer heat endurance better than contrast 1 in the prior art stability, the S. E. A. that the embodiment of the present invention is obtained is excellent
Polyester thermoplastic elastomer after processing melt index be significantly less than contrast 2 melt index, small point of its THF after processing
Son illustrates the excellent polyester thermoplastic elastomer of the S. E. A. that the embodiment of the present invention is obtained in processing significantly lower than contrast 2
During melt heat endurance better than in the prior art contrast 2 stability；
Polymer elastomer aging speed is faster, resilience is poorer, compression set rate is bigger, service life is shorter,
Aging speed is slower, resilience is better, compression set rate is smaller, service life is more long.Can be calculated by data in table 1
Aging speed under different situations, can be learnt by table 1, and contrast 1 and 2 aging speed under three kinds of different situations of contrast are faster than
Aging speed of the excellent polyester thermoplastic elastomer of S. E. A. that the embodiment of the present invention is obtained under three kinds of different situations,
It follows that the excellent polyester thermoplastic elastomer service life of the S. E. A. that obtains of the embodiment of the present invention is longer than contrast 1
With contrast 2；
Meanwhile, the energy absorption of the excellent polyester thermoplastic elastomer of the S. E. A. that obtains according to embodiments of the present invention
Rate is substantially better than contrast 1 and contrast 2, illustrates the excellent polyester thermoplastic's bullet of the S. E. A. for obtaining according to embodiments of the present invention
More preferably, it more disclosure satisfy that using effect to the damping effect of gonosome as padded coaming.
Therefore, excellent polyester thermoplastic elastomer its stable performance of the embodiment of the present invention is obtained S. E. A., bullet
Property absorptivity is excellent, hence it is evident that be better than the preferable like product of using effect of current market, this hair is obtained using the inventive method
The excellent polyester thermoplastic elastomer of bright S. E. A., rationally, method is simple, it is easy to operate for its preparation process, its preparation
The good stability of melt in process.
Above technical characteristic constitutes embodiments of the invention, and it has stronger adaptability and implementation result, can basis
The non-essential technical characteristic of increase and decrease is actually needed to meet the demand of different situations.
Claims (8)
1. the excellent polyester thermoplastic elastomer of a kind of S. E. A., it is characterised in that raw material include polyether Glycols 30% to
70%th, the catalyst compounded A50ppm to 300ppm of rare earth coated, mixing antioxidant C100ppm to 1000ppm, toughener
D100ppm to 1000ppm, stabilizer E30ppm to 1000ppm, stabilizer F10ppm to 500ppm, the major ingredient of surplus, major ingredient bag
Isosorbide-5-Nitrae butanediol and terephthalic acid (TPA) are included, wherein, Isosorbide-5-Nitrae butanediol is 1 with the mol ratio of terephthalic acid (TPA):1 to 100:1.
2. the excellent polyester thermoplastic elastomer of S. E. A. according to claim 1, it is characterised in that polyethers binary
Alcohol is one or more of PolyTHF, polyethylene glycol and polypropylene glycol；Or/and, the catalyst compounded A of rare earth coated is one
Plant the oxide of the rare earth metal of the above or the salt of more than one rare earth metal, more than one organic titanic compound and one kind
The compound of organo-silicon compound above, wherein, rare earth metal is lanthanum, samarium, cerium, praseodymium, neodymium, and organic titanic compound is metatitanic acid four
Methyl alcohol ester, metatitanic acid tetrem alcohol ester, the propyl alcohol ester of metatitanic acid four, the butyl alcohol ester of metatitanic acid four, tetraisopropyl titanate, the isobutyl alcohol ester of metatitanic acid four, have
Organic silicon compound is hexadecyl trimethoxy silane, methyl silicate, silester, silicic acid propyl ester, butyl silicate；Or/and, mix
The mixture that antioxidant C is 10% to 90% Hinered phenols antioxidant and the organic phosphates antioxidant of surplus is closed, wherein, hindered phenol
Kind antioxidant is one or more of antioxidant 246, antioxidant 1010, antioxidant 1076, antioxidant 1096, antioxidant 300；Have
The Phosphorus antioxidant of machine be in Trimethyl phosphite, triethyl phosphite, triethyl phosphite, triphenyl phosphite it is a kind of with
On；Or/and, toughener D is one or more of Sodium Polyacrylate, polyacrylic acid potassium, calcium polyacrylate (CPA), polyacrylic acid zinc；Or/
With stabilizer E is in glycidol, isopropyl glycidyl ether, n-butyl glycidyl ether, n-octyl glycidyl ether
More than kind；Or/and, stabilizer F be trimethyl phosphate, triethyl phosphate, diethyl phosphate, tributyl phosphate, triphenyl phosphate,
One or more of tricresyl phosphate.
3. the excellent polyester thermoplastic elastomer of S. E. A. according to claim 1 and 2, it is characterised in that by following
Method is obtained：The first step, slurrying first carries out nitrogen protection to slurrying kettle, and it is 1MPa to control absolute pressure in slurrying kettle, by Isosorbide-5-Nitrae
Butanediol, terephthalic acid (TPA), polyether Glycols, the catalyst compounded A of rare earth coated, mixing antioxidant C and toughener D add system
It is well mixed in slurry kettle and obtains slurries, and slurries is warming up to 80 DEG C to 100 DEG C with the programming rate of 3 DEG C/min to 7 DEG C/min；
Slurries after first step constant temperature are moved into esterifying kettle and carry out nitrogen protection by second step, esterification, absolute in esterifying kettle
Then slurries are warming up to 150 DEG C to 180 by Stress control in 60KPa to 80KPa with the programming rate of 3 DEG C/min to 7 DEG C/min
DEG C esterification 1 hour, then slurries are warming up to by 230 DEG C to 250 DEG C continuation with the programming rate of 0.5 DEG C/min to 1 DEG C/min
Esterification obtains carboxylate in 4 hours；
3rd step, precondensation, the carboxylate feeding preshrunk reactor that second step is obtained is added thereto to stabilizer E and stabilization
Agent F, after stirring 10 minutes to 20 minutes, rises to 230 DEG C to 250 DEG C, while preshrunk is anti-by preshrunk reactor temperature rapidly
Answer in kettle absolute pressure control in 500Pa to 200Pa, keeping temperature is constant with pressure, carry out prepolymerization reaction 4 hours to 9 small
When obtain prepolymer；
Preshrunk reactor temperature is risen to 230 by the 4th step, thickening, the prepolymer feeding thickening kettle that the 3rd step is obtained rapidly
DEG C to 250 DEG C, while, in 50Pa to 100Pa, keeping temperature is constant with pressure, carries out by absolute pressure control in preshrunk reactor
Constant temperature and pressure final minification reacts, and the reaction time is 2 hours to 6 hours, and reaction terminates to obtain the excellent polyester thermoplastic of S. E. A.
Property elastomer.
4. the excellent polyester thermoplastic elastomer of S. E. A. according to claim 3, it is characterised in that in the first step,
Slurrying kettle uses Q235A vertical elliptical end socket tank reactors, and the blade diameter length ratio of the direct tube section of slurrying kettle is 1：1.2, slurrying kettle
Volume 1.2 times to 1.4 times of inventory for needed for, the agitating paddle in slurrying kettle is Q235A anchor frame type agitating blades；Second step
In, esterifying kettle uses packed tower, and the blade diameter length ratio of the packing section of packed tower is 1:15, the volume of the esterifying kettle inventory for needed for
1.2 times to 1.4 times；In 3rd step, preshrunk reactor uses Q235A vertical elliptical end socket tank reactors, preshrunk reactor
Direct tube section blade diameter length ratio be 1:1.5, the volume of preshrunk reactor 1.2 times to 1.4 times of inventory for needed for, preshrunk reactor
Interior agitating paddle is Q235A anchor frame type agitating blades；In 4th step, thickening kettle uses Q235A horizontal reactors, thickening kettle
The blade diameter length ratio of direct tube section is 1:4, the volume of kettle is viscosified 1.2 times to 1.4 times of inventory for needed for, inside there is Q235 cages basket formula net
Disk spiral pushing tack producing device, whole process spiral pushing frequency is 30HZ.
5. the excellent polyester thermoplastic elastomer of S. E. A. according to claim 3 or 4, it is characterised in that the first step
In, overall process stirring is carried out using the stirring frequency of 20Hz；In 3rd step, overall process is carried out using the stirring frequency of 20Hz and is stirred
Mix.
6. the preparation method of the excellent polyester thermoplastic elastomer of a kind of S. E. A. according to claim 1 and 2, its
It is characterised by carrying out in the steps below：The first step, slurrying first carries out nitrogen protection, absolute pressure in control slurrying kettle to slurrying kettle
Power is 1MPa, by Isosorbide-5-Nitrae butanediol, terephthalic acid (TPA), polyether Glycols, the catalyst compounded A of rare earth coated, mixing antioxidant C
To add be well mixed in slurrying kettle with toughener D and obtain slurries, and with the programming rate of 3 DEG C/min to 7 DEG C/min by slurries liter
Temperature is to 80 DEG C to 100 DEG C；
Slurries after first step constant temperature are moved into esterifying kettle and carry out nitrogen protection by second step, esterification, absolute in esterifying kettle
Then slurries are warming up to 150 DEG C to 180 by Stress control in 60KPa to 80KPa with the programming rate of 3 DEG C/min to 7 DEG C/min
DEG C esterification 1 hour, then slurries are warming up to by 230 DEG C to 250 DEG C continuation with the programming rate of 0.5 DEG C/min to 1 DEG C/min
Esterification obtains carboxylate in 4 hours；
3rd step, precondensation, the carboxylate feeding preshrunk reactor that second step is obtained is added thereto to stabilizer E and stabilization
Agent F, after stirring 10 minutes to 20 minutes, rises to 230 DEG C to 250 DEG C, while preshrunk is anti-by preshrunk reactor temperature rapidly
Answer in kettle absolute pressure control in 500Pa to 200Pa, keeping temperature is constant with pressure, carry out prepolymerization reaction 4 hours to 9 small
When obtain prepolymer；
Preshrunk reactor temperature is risen to 230 by the 4th step, thickening, the prepolymer feeding thickening kettle that the 3rd step is obtained rapidly
DEG C to 250 DEG C, while, in 50Pa to 100Pa, keeping temperature is constant with pressure, carries out by absolute pressure control in preshrunk reactor
Constant temperature and pressure final minification reacts, and the reaction time is 2 hours to 6 hours, and reaction terminates to obtain the excellent polyester thermoplastic of S. E. A.
Property elastomer.
7. the preparation method of the excellent polyester thermoplastic elastomer of S. E. A. according to claim 6, its feature exists
In the first step, slurrying kettle uses Q235A vertical elliptical end socket tank reactors, and the blade diameter length ratio of the direct tube section of slurrying kettle is 1：
1.2,1.2 times to 1.4 times of inventory for needed for, agitating paddle in slurrying kettle is stirred for Q235A anchor frames for the volume of slurrying kettle
Mix oar；In second step, esterifying kettle uses packed tower, and the blade diameter length ratio of the packing section of packed tower is 1:15, the volume of esterifying kettle is institute
Need 1.2 times to 1.4 times of inventory；In 3rd step, preshrunk reactor uses Q235A vertical elliptical end socket tank reactors,
The blade diameter length ratio of the direct tube section of preshrunk reactor is 1:1.5, the volume of preshrunk reactor 1.2 times to 1.4 times of inventory for needed for,
Agitating paddle in preshrunk reactor is Q235A anchor frame type agitating blades；In 4th step, thickening kettle uses Q235A horizontal reactings
Device, the blade diameter length ratio for viscosifying the direct tube section of kettle is 1:4, the volume of kettle is viscosified 1.2 times to 1.4 times of inventory for needed for, inside have
Q235 cages basket formula Dropbox spiral pushing tack producing device, whole process spiral pushing frequency is 30HZ.
8. the preparation method of the excellent polyester thermoplastic elastomer of S. E. A. according to claim 6 or 7, its feature
It is in the first step, overall process stirring to be carried out using the stirring frequency of 20Hz；In 3rd step, carried out using the stirring frequency of 20Hz
Overall process is stirred.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493560A (en) * | 2020-04-08 | 2021-10-12 | 中国石油化工股份有限公司 | Low-melting-point modified copolyester and preparation method and application thereof |
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| CN113493560A (en) * | 2020-04-08 | 2021-10-12 | 中国石油化工股份有限公司 | Low-melting-point modified copolyester and preparation method and application thereof |
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