CN118290690A - Thermoplastic polyurethane for large-caliber extrusion and preparation method thereof - Google Patents
Thermoplastic polyurethane for large-caliber extrusion and preparation method thereof Download PDFInfo
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- CN118290690A CN118290690A CN202310012315.7A CN202310012315A CN118290690A CN 118290690 A CN118290690 A CN 118290690A CN 202310012315 A CN202310012315 A CN 202310012315A CN 118290690 A CN118290690 A CN 118290690A
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- diisocyanate
- thermoplastic polyurethane
- chain extender
- caliber
- catalyst
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 49
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 49
- 238000001125 extrusion Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000004970 Chain extender Substances 0.000 claims description 59
- -1 siloxane chain Chemical group 0.000 claims description 56
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 229920001296 polysiloxane Polymers 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 229920001228 polyisocyanate Polymers 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000004611 light stabiliser Substances 0.000 claims description 9
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 4
- 150000007514 bases Chemical class 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 claims description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- LSYBWANTZYUTGJ-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl-methylamino]ethanol Chemical compound CN(C)CCN(C)CCO LSYBWANTZYUTGJ-UHFFFAOYSA-N 0.000 claims description 2
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- 239000012971 dimethylpiperazine Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007246 mechanism Effects 0.000 claims description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 claims 1
- 125000002524 organometallic group Chemical group 0.000 claims 1
- 150000004756 silanes Chemical class 0.000 claims 1
- 238000005299 abrasion Methods 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 12
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ABMKWMASVFVTMD-UHFFFAOYSA-N 1-methyl-2-(2-methylphenyl)benzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1C ABMKWMASVFVTMD-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of high polymer materials, and discloses thermoplastic polyurethane suitable for extruding large-caliber pipes and a preparation method thereof, wherein the thermoplastic polyurethane material has good extrusion stability, the fluctuation of the size of pipe products in the extrusion process is less than 2%, and the thermoplastic polyurethane material has the characteristics of 15-5mm 3 abrasion loss, proper friction coefficient and the like obtained according to an ISO 4649 test.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of thermoplastic polyurethane.
Background
Along with economic rapid development, logistics industry also gets into high-speed development period, and logistics sorting conveying system's requirement is more and more high, and sorting conveying system is mostly steel roller structure at present, but transportation article direct contact steel roller can cause obvious wearing and tearing and collide with the steel roller, greatly reduced steel roller life, consequently need wrap up one deck sheath in the steel roller outside, prolongs its life. Taking this as an example, as such applications increase, the demand for large gauge extruded tubing increases significantly.
At present, the main flow material of the large-caliber pipe is rubber or polyvinyl chloride (PVC), and the rubber has wide application in the large-caliber pipe industry due to the characteristics of wide hardness range, excellent strength, excellent rebound and wear resistance, but has poor heat resistance, oil resistance, weather resistance and the like, cannot meet the requirements of increasingly complex environmental performance, is not easy to color, has single appearance and poor aesthetic property; PVC has relatively high environmental resistance, makes up the poor environmental resistance of rubber, has relatively wide application in the large-caliber pipe industry, but has limited working temperature, relatively low compression set resistance and rebound resilience, and reduces the service life. Therefore, the preparation of the novel sheath material with excellent wear resistance and stable extrusion tends to be a great trend.
The thermoplastic polyurethane is a thermoplastic polymer with a main chain comprising repeated-NHCOO-structural units, has excellent wear resistance, medium resistance and environmental resistance, can be used for preparing various colors and meets the appearance requirement, and has wide application in industries such as conveyor belts in recent years due to the fact that the molecular structure can be regulated to meet different application requirements. Because the large-caliber pipe is large in diameter, thick in wall thickness and low in extrusion speed, the TPU is poor in heat resistance, degradation can be caused due to long residence time in a screw, and product defects are caused by fluctuation in the extrusion process, the TPU is not applied to the field of large-caliber extruded pipes, and the improvement of the heat stability of the TPU is a core technical point of applying the TPU to the field. Patent CN 110885550B discloses a method for modifying thermoplastic polyurethane elastomer by organic silicon, the composition of elastomer is as follows: 20-30 parts of polyether polyol, 20-30 parts of hydroxyl-terminated polysiloxane, 8-13 parts of diisocyanate, 20-25 parts of polycarbonate, 4-10 parts of chain extender and 1-2 parts of catalyst, wherein a high bond energy silicon-oxygen bond is introduced into the product to improve the heat resistance of the product, phenyl in the siloxane enhances the rigidity of the product to further improve the heat stability of the product, but the processing temperature of the product is too high due to the excessively high rigidity, the processing performance is reduced, and the product is limited in certain application fields.
Disclosure of Invention
Aiming at the defects of the existing materials, the invention aims to provide a preparation method of thermoplastic polyurethane suitable for extruding large-caliber pipes. According to the invention, the TPU with more excellent performance is adopted to replace rubber and PVC to prepare the large-caliber pipe and the special-requirement sheath, the problem of poor heat-resistant stability of the TPU is solved by adjusting the structure and the proportion of the chain extender, the extrusion stability is improved, the wear resistance and the skid resistance of the TPU are adjusted, the thermoplastic polyurethane with excellent comprehensive performance is obtained, the application range and the service life of the material are greatly optimized, and the thermoplastic polyurethane has a relatively wide application prospect.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides thermoplastic polyurethane for large-caliber extruded pipes, which comprises the following raw materials:
(a) Oligomer polyol: 50-80 parts, preferably 55-70 parts;
(b) Polyisocyanates: 8-45 parts, preferably 10-40 parts:
(c) Chain extender: 6-30 parts, preferably 8-25 parts;
(d) An antioxidant: 0.5 to 8 parts, preferably 0.5 to 6 parts;
(e) Light stabilizers: 0.5 to 8 parts, preferably 0.5 to 6 parts;
Wherein the chain extender comprises a siloxane chain extender, optionally a small molecule diol or diamine, the siloxane chain extender having a structure as shown in the following formula (1) and/or formula (2):
In the invention, the ratio of the siloxane chain extender to the small molecular dihydric alcohol or diamine is 1:0-1:10, and the ratio of the siloxane chain extender in the formula (1) to the formula (2) is 1:0 to 0:1.
In the invention, the oligomer polyol is one or more of polyether glycol, polycarbonate glycol and polycaprolactone glycol;
The polyether glycol comprises: one or more of polyethylene oxide glycol, polypropylene oxide glycol, polytetramethylene glycol having molecular weight of 800-4000g/mol, more preferably polytetramethylene glycol having molecular weight of 1000-4000 g/mol;
The polycarbonate diol is a macromolecular polymer which is prepared by taking small molecular diol as an initiator and reacting with aliphatic carbonic acid esters such as dimethyl carbonate, diethyl carbonate, ethylene carbonate and the like, wherein both ends of a long chain molecule are provided with terminal hydroxyl groups, and a main chain is provided with a repeated unit carbonate group; typical initiators include 1, 2-ethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, etc., preferably 1, 2-ethylene glycol, 1, 4-butanediol, neopentyl glycol; preferably the molecular weight is in the range 500-4000g/mol, more preferably 1000-4000g/mol;
The polycaprolactone diol is prepared by ring-opening polymerization of epsilon-caprolactone in the presence of a catalyst and an initiator, and common initiators comprise ethylene glycol, diethylene glycol, neopentyl glycol and the like, and the molecular weight is preferably in the range of 500-4000g/mol, more preferably 800-4000g/mol;
In the invention, the polyisocyanate is one or more of aliphatic polyisocyanate, alicyclic polyisocyanate and aromatic polyisocyanate; including one or more of 1, 6-hexamethylene diisocyanate, 1, 10-decane diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, 2, 4-hexahydrotoluene diisocyanate, 2, 6-hexahydrotoluene diisocyanate, 4' -dicyclohexylmethane diisocyanate, 2' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2, 4-diphenylmethane isocyanate, 4' -diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, 1, 4-naphthalene diisocyanate, m-xylylene diisocyanate, diphenylmethane-3, 3' -dimethoxy-4, 4' -diisocyanate, preferably 4,4' -diphenylmethane diisocyanate, 2, 6-toluene diisocyanate;
In the invention, the micromolecular dihydric alcohol chain extender comprises one or more of ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol and diethylene glycol; the diamine chain extender comprises one or more of 1, 3-propylene diamine, 1, 4-butylene diamine, p-phenylenediamine, biphenyl diamine and 3,3' -dimethyl-4, 4-biphenyl diamine; preferably one or more of 1, 4-butanediol, 1, 6-hexanediol, 3' -dimethyl-4, 4-biphenyldiamine;
In the invention, the siloxane chain extender is a series of chain extenders modified by silane, which are prepared by performing hydrosilylation reaction on 1, 4-butylene glycol and polysiloxane with a silicon hydrogen structure end-capped by the siloxane chain extender, and the reaction mechanism is as follows:
Wherein n is more than or equal to 1, preferably more than or equal to 1 and less than or equal to 8; the molar ratio range of the raw materials during the synthesis of the siloxane chain extender is as follows: n (butylene glycol): n (polysiloxane) =1.05 to 2.2; preferably, the molar ratio ranges: n (butylene glycol): n (polysiloxane) =1.10 to 2.0;
In the invention, the catalyst used in the synthesis of the siloxane chain extender is selected from a platinum metal catalyst, a rhodium metal catalyst, a ruthenium metal catalyst and a palladium metal catalyst;
In the invention, the reaction temperature is 80-120 ℃ and the reaction time is 4-8h when the siloxane chain extender is synthesized, and unreacted monomers are removed by reduced pressure distillation after the reaction is completed, so as to obtain the siloxane chain extender;
In the invention, the thermoplastic polyurethane raw material is also accompanied by a catalyst, wherein the catalyst is selected from alkaline compounds or organic metal catalysts; the basic compound is selected from tertiary amine compounds, preferably triethylenediamine, triethylamine, N-methyldicyclohexylamine, N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, N-N '-dimethylpiperazine, N-N' -diethylpiperazine, 1, 3-tetramethylpiperidine, bis (2-dimethylaminoethyl) ether, tetramethylbutanediamine, dimethylethanolamine, trimethylhydroxyethyl ethylenediamine, pentamethyldipropylene triamine, 2,4,6 tris (dimethylaminomethyl) phenol; the organic metal catalyst is selected from stannous octoate, dibutyl tin dilaurate, zinc iso-octoate, zinc oleate, zinc naphthenate, bismuth naphthenate and cobalt naphthenate; preferred are triethylenediamine, triethylamine, N-dimethylcyclohexylamine, stannous octoate, dibutyltin dilaurate, bismuth naphthenate; further, the preferred amount of catalyst based on thermoplastic polyurethane ranges from 20ppm to 150ppm;
preferably, the isocyanate index in the thermoplastic polyurethane is preferably in the range of 0.97 to 1.03, the isocyanate index being the molar ratio of NCO groups to OH groups in the starting material.
Preferably, the antioxidant is selected from one or more of triethylene glycol bis- [3- (3-tertiary butyl-4 hydroxy-5 methylphenyl) propionate ], pentaerythritol tetrakis [ beta- (3, 5-di-tertiary butyl-4-hydroxyphenyl) propionate ] and 2, 6-di-tertiary butyl-4-methylphenol; the light stabilizer is selected from benzotriazole light stabilizer or hindered amine light stabilizer.
On the other hand, the invention also provides a preparation method of the thermoplastic polyurethane for extruding the large-caliber pipe, which comprises the following steps:
Step 1): mixing the siloxane chain extender with small molecular dihydric alcohol or diamine in proportion, storing in a chain extender heat-preserving tank, maintaining the temperature at 50-60 ℃, and fully stirring for 10-20min to obtain a mixture 1 for later use;
Step 2): adding an antioxidant, a light stabilizer, a catalyst and an oligomer polyol into a heat preservation tank, maintaining the temperature at 100-120 ℃, and fully stirring for 10-20min to obtain a mixture 2 for later use;
step 3): simultaneously injecting the mixture 1, the mixture 2 and the polyisocyanate into a double-screw extruder for reaction to obtain TPU melt, and carrying out underwater granulation to obtain a thermoplastic polyurethane material suitable for large-caliber extrusion;
Preferably, the ratio of the siloxane chain extender to the small molecular diol or diamine in the step 1) is 1:9-1:1, and the stirring speed is 50-250RPM;
Preferably, the stirring speed in the step 2) is 80-180RPM;
Preferably, the twin-screw extruder of step 3) is divided into 10 temperature zones, the extruder temperature ranges from 80 to 250 ℃, the extruder screw aspect ratio ranges from 50 to 120:1, preferably from 50 to 75:1, the rotation speed of the screw is 80-500RPM;
The beneficial effects of the invention are as follows:
(1) The thermoplastic polyurethane material provided by the invention is characterized in that the silicon-containing structure is bonded into the chain extender through chemical reaction, and is further introduced onto the thermoplastic polyurethane main chain through synthetic reaction, so that the surface energy of the thermoplastic polyurethane material can be reduced, and the anti-fouling and wear-resistant performances are improved.
(2) The siloxane chain extender used by the thermoplastic polyurethane material provided by the invention introduces high bond energy siloxane bonds into the thermoplastic polyurethane molecular chain, so that the thermal stability of the thermoplastic polyurethane molecular chain is improved, and meanwhile, the structure of the thermoplastic polyurethane molecular chain can be adjusted by changing the raw material proportion during synthesis to play the role of a cross-linking agent, so that the cross-linking degree of the thermoplastic polyurethane is adjusted, the heat resistance and viscosity stability of the product are further improved, and the extrusion stability is improved.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Raw materials
Examples 1 to 5: the feed ratios for preparing the polyurethane raw materials are shown in the following table:
Synthesis of a siloxane chain extender:
The siloxane chain extender is prepared from the following raw materials in the synthesis step: 1, 4-butene diol and silicone having a degree of polymerization of 1, 4-butene diol end-capped with a hydrosilylation structure, the 1, 4-butene diol and the silicone being in a molar ratio n (butene diol): n (polysiloxane) =1.05 was added to the reactor to be preheated, a platinum metal catalyst was added to the reactor in an amount of 25ppm when the preheating temperature reached 75 ℃, then the reaction was carried out for 8 hours in a temperature range of 100 ℃, the reaction was stopped, and the unreacted excess monomer was removed by distillation under reduced pressure to obtain a siloxane chain extender 1.
1) Siloxane chain extenders 2-5, each for examples 2-5, were prepared as described above using a silicone-hydrogen terminated polysiloxane having a degree of polymerization of 2, 4, 8, 12, respectively; the raw materials for synthesizing the siloxane chain extender are as follows: n (butylene glycol): n (polysiloxane) =1.05.
The structure of the synthetic siloxane chain extender is shown below:
n＝1,2,3……8；
2) The molar ratio of raw materials in the synthesis of the siloxane chain extender is adjusted, and the raw material ratios in the synthesis of the siloxane chain extender used in examples 6 to 9 are respectively as follows: n (butylene glycol): n (polysiloxane) =1.3, 1.6, 1.9, 2.2. The degree of polymerization of the siloxane used was 1;
3) Examples 9-12 the ratio of chain extender 1 (diol) to silicone chain extender was adjusted as follows: 1:1, 5:1, 10:1, 15:1 to give TPU11-14; wherein the silicone extender is synthesized by using polysiloxane polymerization degree n=1, and the raw material molar ratio is n (butylene glycol): n (polysiloxane) =1.30;
the preparation method of the embodiment comprises the following steps:
Storing the siloxane chain extender and dihydric alcohol (added in examples 10-13) in a chain extender heat-preserving tank, maintaining the temperature at 55 ℃, and fully stirring for 10-20min to obtain a mixture 1 for later use;
Adding the required auxiliary agent into an oligomer polyol heat-preserving tank, maintaining the temperature at 110 ℃, and fully stirring for 200min to obtain a mixture 2 for later use;
simultaneously injecting the mixture 1, the mixture 2 and the polyisocyanate into a double-screw extruder to react at the temperature of 100-200 ℃ to generate TPU melt, and carrying out underwater granulation to obtain a thermoplastic polyurethane material suitable for large-caliber extrusion, wherein the length-diameter ratio of the extruder is 52:1, 10 temperature zones are divided, wherein the temperature zones 1-3 are mixing sections, the temperature zones 4-7 are reaction sections, the temperature zones 8-10 are conveying sections, the temperature of the mixing sections of the 1-3 zones are 110 ℃, 130 ℃, 140 ℃, the temperature of the reaction sections of the 4-7 zones are 160 ℃, 180 ℃, 185 ℃, 190 ℃ and the temperature of the conveying sections of the 8-10 zones are 185 ℃, 180 ℃ in sequence;
| component/% | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| POL | 59 | 59 | 59 | 59 | 59 | 59 |
| Diisocyanate (BI) | 28.1 | 26.3 | 23.9 | 21.2 | 20.0 | 33.3 |
| Chain extender 1 | -- | -- | -- | -- | -- | 6.6 |
| Silicone chain extenders | 11.8 | 13.6 | 16.0 | 18.9 | 19.9 | -- |
| Antioxidant | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 |
| Light stabilizers | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Obtaining | TPU1 | TPU2 | TPU3 | TPU4 | TPU5 | TPU6 |
Wherein POL: PTMEG-1000; a diisocyanate: MDI; chain extender 1: BDO;
The products TPU1 to 5 obtained in examples 1 to 5 were tested in comparison with comparative example 1 (TPU 6) and the experimental results are as follows:
| Test item | TPU1 | TPU2 | TPU3 | TPU4 | TPU5 | TPU6 |
| Abrasion/mm 3 | 14.3 | 13.1 | 13.9 | 11.3 | 9.5 | 41.5 |
| Coefficient of friction/10 -3 | 0.95 | 0.83 | 0.68 | 0.57 | 0.39 | 1.42 |
| Tensile Strength/MPa | 30.8 | 28.3 | 26.8 | 21.6 | 18.3 | 31.6 |
As can be seen from the comparison of the group, when n in the polysiloxane is more than 8, the friction coefficient of the product is lower, the strength is obviously reduced along with the increase of n, and the polymerization degree of the polysiloxane is preferably n less than or equal to 8 when the siloxane chain extender is synthesized in consideration of comprehensive performance;
The preparation of examples 6-9 was repeated for example 1 with the following feed ratios:
| component/% | Example 6 | Example 7 | Example 8 | Example 9 | Example 1 | Comparative example 1 |
| POL | 59 | 59 | 59 | 59 | 59 | 59 |
| Diisocyanate (BI) | 27.9 | 27.5 | 26.5 | 26.0 | 28.1 | 33.3 |
| Chain extender 1 | -- | -- | -- | -- | -- | 6.6 |
| Silicone chain extenders | 12.0 | 12.4 | 13.4 | 13.9 | 11.8 | -- |
| Antioxidant | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 |
| Light stabilizers | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Obtaining | TPU7 | TPU8 | TPU9 | TPU10 | TPU1 | TPU6 |
And (3) POL: PTMEG-1000; a diisocyanate: MDI; chain extender 1: BDO;
The products TPU7-10 obtained in examples 6-9 were tested in comparison with comparative example 1 and example 1, and the experimental results are as follows:
| Test item | TPU7 | TPU8 | TPU9 | TPU10 | TPU1 | TPU6 |
| Abrasion/mm 3 | 13.2 | 13.5 | 12.5 | 11.8 | 14.3 | 41.5 |
| Coefficient of friction/10 -3 | 0.83 | 0.90 | 1.01 | 0.96 | 0.95 | 1.42 |
| Tensile Strength/MPa | 35.8 | 37.3 | 41.2 | 44.2 | 30.8 | 31.6 |
| Thermal decomposition temperature/. Degree.C | 294 | 298 | 303 | 307 | 290 | 280 |
The comparison of the group of experiments shows that the tensile strength of the product is obviously increased along with the increase of the molar ratio of the raw materials in the synthesis of polysiloxane s, the friction coefficient and the abrasion are not affected, and the thermal decomposition temperature of the product is obviously increased; in comprehensive consideration, the molar ratio range of the raw materials during the synthesis of the polysiloxane is as follows: n (butylene glycol): n (polysiloxane) =1.10 to 2.0.
The preparation of examples 10-13 was repeated for example 1, with the specific feed ratios shown in the following table:
| component/% | Example 10 | Example 11 | Example 12 | Example 13 | Example 6 | Comparative example 1 |
| POL | 59 | 59 | 59 | 59 | 59 | 59 |
| Diisocyanate (BI) | 31.3 | 32.7 | 33.0 | 33.1 | 28.1 | 33.3 |
| Chain extender 1 | 4.8 | 6.0 | 6.3 | 6.4 | -- | 6.6 |
| Silicone chain extenders | 4.8 | 1.2 | 0.6 | 0.4 | 11.8 | -- |
| Antioxidant | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 |
| Light stabilizers | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Obtaining | TPU11 | TPU12 | TPU13 | TPU14 | TPU1 | TPU6 |
And (3) POL: PTMEG-1000; a diisocyanate: MDI; chain extender 1: BDO;
The products TPU11-14 obtained in examples 10-13 are compared with comparative example 1 and example 1, and the experimental results are as follows:
| Test item | TPU11 | TPU12 | TPU13 | TPU14 | TPU1 | TPU6 |
| Abrasion/mm 3 | 13.3 | 13.1 | 14.3 | 18.3 | 14.3 | 41.5 |
| Coefficient of friction/10 -3 | 0.94 | 0.99 | 1.01 | 1.15 | 0.95 | 1.42 |
| Tensile Strength/MPa | 36.9 | 34.3 | 33.1 | 31.4 | 30.8 | 31.6 |
| Thermal decomposition temperature/. Degree.C | 296 | 292 | 288 | 285 | 290 | 280 |
As can be seen from the comparison of the group of experiments, the abrasion and friction coefficient of the product are increased along with the reduction of the proportion of the siloxane chain extender, and the strength and the thermal decomposition temperature are gradually reduced; the mixing ratio of the chain extender 1 to the siloxane chain extender is less than or equal to 10:1 in consideration of comprehensive performance.
The TPU11-14 and TPU1, TPU6 obtained in examples 10-13 were subjected to an extrusion stability test, 1m tubing was cut out, and the dimensional fluctuation was calibrated for each 10cm of test tube diameter, with the following results:
| Test item | TPU11 | TPU12 | TPU13 | TPU14 | TPU1 | TPU6 |
| Size fluctuation | 1.2％ | 1.5％ | 1.7％ | 1.7％ | 0.9％ | 3.5％ |
The invention improves the disadvantages of poor heat resistance, poor wear resistance, higher friction coefficient and the like of the traditional TPU product through the design of the chain extender structure and the adjustment of the mixing proportion, and the TPU prepared by the method can be widely applied to large-caliber pipe extrusion and has excellent product performance.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way; those skilled in the art will appreciate that many modifications, adaptations, and variations of the present invention are possible in light of the above teachings without departing from the scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the present invention.
Claims (10)
1. A thermoplastic polyurethane for large-caliber extruded pipes, which comprises the following raw materials:
Wherein the chain extender comprises a siloxane chain extender, optionally a small molecule diol or diamine, the siloxane chain extender having a structure as shown in the following formula (1) and/or formula (2):
2. The thermoplastic polyurethane for large-caliber extruded pipes according to claim 1, wherein the oligomer polyol is one or more of polyether glycol, polycarbonate glycol, and polycaprolactone glycol.
3. The thermoplastic polyurethane for large-caliber extruded tubing according to claim 1 or 2, wherein the polyisocyanate is one or more of aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate; including one or more of 1, 6-hexamethylene diisocyanate, 1, 10-decane diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, 2, 4-hexahydrotoluene diisocyanate, 2, 6-hexahydrotoluene diisocyanate, 4' -dicyclohexylmethane diisocyanate, 2' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2, 4-diphenylmethane isocyanate, 4' -diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, 1, 4-naphthalene diisocyanate, m-xylylene diisocyanate, diphenylmethane-3, 3' -dimethoxy-4, 4' -diisocyanate, preferably 4,4' -diphenylmethane diisocyanate, 2, 6-toluene diisocyanate.
4. A thermoplastic polyurethane for large diameter extruded pipe according to any one of claims 1 to 3 wherein the silicone chain extender is a series of silane modified chain extenders prepared by hydrosilylation of 1,4 butene diol with a silicone terminated by a hydrosilylation structure, the reaction mechanism being as follows:
wherein n is more than or equal to 1, preferably more than or equal to 1 and less than or equal to 8; the molar ratio range of the raw materials during the synthesis of the siloxane chain extender is as follows: n (butylene glycol): n (polysiloxane) =1.05 to 2.2; preferably, the molar ratio ranges: n (butylene glycol): n (polysiloxane) =1.10 to 2.0.
5. The thermoplastic polyurethane for large-diameter extruded tubes according to claim 4, wherein the catalyst used in the synthesis of the siloxane chain extender is selected from the group consisting of platinum metal catalyst, rhodium metal catalyst, ruthenium metal catalyst and palladium metal catalyst.
6. The thermoplastic polyurethane for large-caliber extruded pipes as claimed in claim 4 or 5, wherein the reaction temperature of the siloxane chain extender during synthesis is 80-120 ℃ and the reaction time is 4-8h.
7. The thermoplastic polyurethane for large-caliber extruded tubing as claimed in any one of claims 1 to 6, wherein a catalyst is further contained in the thermoplastic polyurethane raw material, and the catalyst is selected from a basic compound or an organometallic catalyst; the basic compound is selected from tertiary amine compounds, preferably one or more of triethylenediamine, triethylamine, N-methyl dicyclohexylamine, N-dimethyl cyclohexylamine, N-methyl morpholine, N-ethyl morpholine, N-N '-dimethyl piperazine, N-N' -diethyl piperazine, 1, 3-tetramethyl piperidine, bis (2-dimethylaminoethyl) ether, tetramethyl butanediamine, dimethyl ethanolamine, trimethyl hydroxyethyl ethylenediamine, pentamethyl dipropylene triamine, 2,4,6 tris (dimethylaminomethyl) phenol; the organic metal catalyst is selected from stannous octoate, dibutyl tin dilaurate, zinc iso-octoate, zinc oleate, zinc naphthenate, bismuth naphthenate and cobalt naphthenate; preferably one or more of triethylenediamine, triethylamine, N-dimethylcyclohexylamine, stannous octoate, dibutyltin dilaurate and bismuth naphthenate.
8. A process for the preparation of thermoplastic polyurethane for large diameter extruded tubing as claimed in any one of claims 1 to 7, wherein the process comprises the steps of:
Step 1): mixing the siloxane chain extender with small molecular dihydric alcohol or diamine in proportion, storing in a chain extender heat-preserving tank, maintaining the temperature at 50-60 ℃, and fully stirring for 10-20min to obtain a mixture 1 for later use;
Step 2): adding an antioxidant, a light stabilizer, a catalyst and an oligomer polyol into a heat preservation tank, maintaining the temperature at 100-120 ℃, and fully stirring for 10-20min to obtain a mixture 2 for later use;
Step 3): and simultaneously injecting the mixture 1, the mixture 2 and the polyisocyanate into a double-screw extruder for reaction to obtain TPU melt, and carrying out underwater granulation to obtain the thermoplastic polyurethane material suitable for large-caliber extrusion.
9. The method of claim 8, wherein the ratio of the silicone chain extender to the small molecular diol or diamine in step 1) is 1:9 to 1:1, and the stirring speed is 50 to 250RPM;
and/or, the stirring rotating speed in the step 2) is 80-180RPM.
10. The process according to claim 8 or 9, wherein the twin-screw extruder of step 3) is divided into 10 temperature zones, the extruder temperature ranges from 80 to 250 ℃, the extruder screw aspect ratio ranges from 50 to 120:1, preferably from 50 to 75:1, and the rotating speed of the screw is 80-500RPM.
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