CN111647382A - Preparation method and application of TPU (thermoplastic polyurethane) adhesive - Google Patents
Preparation method and application of TPU (thermoplastic polyurethane) adhesive Download PDFInfo
- Publication number
- CN111647382A CN111647382A CN202010618020.0A CN202010618020A CN111647382A CN 111647382 A CN111647382 A CN 111647382A CN 202010618020 A CN202010618020 A CN 202010618020A CN 111647382 A CN111647382 A CN 111647382A
- Authority
- CN
- China
- Prior art keywords
- tpu
- temperature
- screw extrusion
- chain
- continuous screw
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 31
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004433 Thermoplastic polyurethane Substances 0.000 title description 95
- 229920002803 thermoplastic polyurethane Polymers 0.000 title description 95
- 238000001125 extrusion Methods 0.000 claims abstract description 65
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 46
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 46
- 229920005862 polyol Polymers 0.000 claims abstract description 45
- 150000003077 polyols Chemical class 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 41
- 239000000498 cooling water Substances 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 20
- 230000008018 melting Effects 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 230000009471 action Effects 0.000 claims abstract description 14
- 238000010008 shearing Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims description 48
- 239000004744 fabric Substances 0.000 claims description 34
- 229920005906 polyester polyol Polymers 0.000 claims description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 30
- 125000001931 aliphatic group Chemical group 0.000 claims description 26
- 238000007789 sealing Methods 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 17
- 238000005520 cutting process Methods 0.000 claims description 17
- 150000002009 diols Chemical class 0.000 claims description 17
- -1 small molecule diol Chemical class 0.000 claims description 15
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 12
- 238000007605 air drying Methods 0.000 claims description 11
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 9
- 229940099427 potassium bisulfite Drugs 0.000 claims description 9
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 9
- 239000002981 blocking agent Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 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 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 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 5
- 239000007788 liquid Substances 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 229940035437 1,3-propanediol Drugs 0.000 claims description 3
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 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 3
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- 239000000565 sealant Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000012298 atmosphere Substances 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 20
- 239000001361 adipic acid Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 230000035484 reaction time Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000004806 packaging method and process Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 230000001502 supplementing effect Effects 0.000 description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 229920002334 Spandex Polymers 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000004759 spandex Substances 0.000 description 3
- AFSHUZFNMVJNKX-UHFFFAOYSA-N 1,2-di-(9Z-octadecenoyl)glycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCCC=CCCCCCCCC AFSHUZFNMVJNKX-UHFFFAOYSA-N 0.000 description 2
- AFSHUZFNMVJNKX-LLWMBOQKSA-N 1,2-dioleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](CO)OC(=O)CCCCCCC\C=C/CCCCCCCC AFSHUZFNMVJNKX-LLWMBOQKSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- SBKRBXBQFDKYSO-UHFFFAOYSA-N (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C)=C(O)C(C(C)(C)C)=C1 SBKRBXBQFDKYSO-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- UZUNCLSDTUBVCN-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-(2-phenylpropan-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C(O)C=1C(C)(C)C1=CC=CC=C1 UZUNCLSDTUBVCN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- BBJZBUKUEUXKDJ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n-[1-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoylamino]hexyl]propanamide Chemical compound C=1C(C(C)(C)C)=C(O)C(C(C)(C)C)=CC=1CCC(=O)NC(CCCCC)NC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BBJZBUKUEUXKDJ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-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
- 239000004831 Hot glue Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007789 gas Substances 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
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 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 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M17/00—Producing multi-layer textile fabrics
- D06M17/04—Producing multi-layer textile fabrics by applying synthetic resins as adhesives
- D06M17/10—Polyurethanes polyurea
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method and application of a TPU adhesive, wherein the method comprises the following steps: step 1, adding organic polyisocyanate, polymer polyol and micromolecular dihydric alcohol into a first section of a continuous screw extrusion reactor, mixing, melting and reacting under the shearing action of a screw; step 2, continuously feeding the substance obtained in the step 1 into a second section of continuous screw extrusion reactor, and adding micromolecular monohydric alcohol into the rear section of the second section of continuous screw extrusion reactor to obtain the TPU in a molten state; and 3, granulating the molten TPU obtained in the step 2 in an underwater granulating system, and drying the particles through a cooling water circulation system by cold air to obtain the TPU particles. The product has obvious low temperature performance at the bonding temperature, can be bonded at 90-135 ℃ and even within the range of 90-120 ℃, does not need high-temperature dissociation, has excellent initial peel strength, and finally shows very excellent bonding performance.
Description
Technical Field
The invention relates to a method for continuously preparing TPU (thermoplastic polyurethane) adhesive products and a processed product thereof, and also relates to application of the TPU adhesive processed product in the aspect of fabric attachment.
Background
The preparation and processing technology of TPU is developed so far, and the terminal market of the application field of TPU covers a plurality of fields. The TPU adhesive is a type of application form which is developed rapidly in recent years, has unique corrosion resistance, hydrolysis resistance, flexing resistance and excellent thermal adhesion, has carbonyl and amino in the structure, and can interact with a plurality of polar groups to form hydrogen bonds, so the TPU adhesive has excellent adsorption adhesion, and has the advantages of performance and environmental protection, so the TPU adhesive is unique in a plurality of adhesives. The TPU adhesive mainly comprises a hot melt adhesive, a solvent adhesive and the like according to different using methods, can be processed into a plurality of forms such as films and net films according to the requirements of specific application fields, and is finally applied to industries such as clothes, shoe materials, automobiles, hygienic products, packaging, electronics and the like. Among them, the fabric for clothing has more stringent requirements for adhesive products: the adhesive has excellent thermal bonding property and elasticity, and provides possibility for a seamless attaching technology; the operation can be carried out in a lower temperature range, and the fabric which is not high in temperature resistance cannot be damaged; and the phenomenon of degumming of the attached fabric after multiple times of washing is ensured.
At present, the main problems of the adhesive products for fabric bonding including other types of adhesives are to maintain excellent bonding strength and to meet the requirements of water washing after bonding at a lower temperature. For the conventional fabrics in the market, particularly elastic fabrics, the development of products which can be laminated at low temperature, are resistant to washing, have high bonding strength and good elasticity still has obvious technical bottlenecks, and the expansion of the bonding agent in the field of fabric lamination is limited to a great extent. For example, by using an adhesive with a relatively high bonding temperature, part of the fabric with a relatively poor temperature resistance is easily damaged during high-temperature bonding; the TPU particles with high crystallization, high melting point and good bonding strength are blended with the TPU particles with low melting point to reduce the bonding temperature, but the problems of partial bonding temperature higher, peeling strength deviation and the like caused by insufficient blending are easy to occur; the product can be adhered at low temperature, and the normal-temperature or high-temperature water washing resistance of the product is poor, so that the fabric is easy to degum in the long-term water washing process, the service life of the finished product is shortened, and the like.
Disclosure of Invention
The technical problem is as follows: in view of the above technical problems, the present invention aims to provide a method for continuously preparing a TPU adhesive product, and a processed product thereof, which is applied to the field of fabric bonding, especially elastic fabric.
The technical scheme is as follows: the preparation method of the TPU adhesive comprises the following steps:
step 1, adding polymer polyol containing organic polyisocyanate, with the number average molecular weight of 700-1000 g/mol and micromolecule diol with the number average molecular weight of 60-150 g/mol into the front section of a first-section continuous screw extrusion reactor, mixing, melting and reacting under the shearing action of a screw;
wherein the molar weight ratio of the organic polyisocyanate NCO groups to the OH groups of the polymer polyol and the small molecule diol is NCO: OH is 1.2-1.5;
step 2, continuously feeding the substance finally obtained in the step 1 into a second-section continuous screw extrusion reactor, adding a sealant into the front section of the second-section continuous screw extrusion reactor for continuous reaction, and adding micromolecule monohydric alcohol into the rear section of the second-section continuous screw extrusion reactor to obtain the molten TPU;
and 3, cutting the TPU in the molten state obtained in the step 2 into particles in an underwater cutting system, enabling the particles to pass through a cooling water circulation system, further forming the particles in the cooling process, fully washing off the sealing agent on the surfaces of the particles by cooling water, and finally drying the particles by cold air to obtain the TPU particles.
Wherein,
the first section of continuous screw extrusion reactor is connected with the second section of continuous screw extrusion reactor; the temperature of the first stage continuous screw extrusion reactor is controlled above the melting temperature of the material and below the decomposition temperature thereof, and the temperature of the second stage continuous screw extrusion reactor of step 2 is controlled above the melting temperature of the material and below 100 ℃.
The reactions of the step 1, the step 2 and/or the step 3 are carried out under the protection of inert gases which have no reactivity with raw materials; step 1 and/or step 2 are/is carried out in the presence of a catalyst; adding an additive during the step 1 and/or the step 2 and/or the step 3.
Inert gas without reactivity comprises one or more of nitrogen and argon;
the addition auxiliary agent comprises one or more of antioxidant, light stabilizer and release agent;
the temperature of the cooling water in the step 3 is controlled to be 0-10 ℃, the drying temperature of the cold air is controlled to be 8-15 ℃, and the moisture content of the dried TPU particles is controlled to be below 100 ppm.
The organic polyisocyanate comprises at least one aromatic polyisocyanate and/or at least one aliphatic polyisocyanate.
The aromatic polyisocyanate at least contains 2 NCO groups and at least contains one of toluene diisocyanate TDI, diphenylmethane diisocyanate MDI, naphthalene diisocyanate NDI, xylylene diisocyanate XDI and isomers thereof.
The aliphatic polyisocyanate at least contains 2 NCO groups and at least contains one of isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI) and isomers thereof.
The polymer polyol at least contains one of polyester polyol or polyether polyol.
The polyester polyol is a linear polyester polyol and a branched polyester polyol, and the mass ratio of the linear polyester polyol to the branched polyester polyol is 12: 1-4;
the straight-chain polyester polyol is obtained by polycondensing at least one aliphatic dibasic acid and straight-chain aliphatic micromolecular diol, wherein the main molecular chain contains ester bond chain, the tail end of the ester bond chain is hydroxyl, the average hydroxyl functionality is 2, and the molecular chain is straight-chain polyester polyol;
the branched polyester polyol is prepared by polycondensing at least one aliphatic dibasic acid with at least one branched chain type aliphatic micromolecular dihydric alcohol and/or straight chain type aliphatic micromolecular aliphatic dihydric alcohol to obtain the polyester polyol with an ester bond chain end as a hydroxyl end, an average hydroxyl functionality of 2 and a branched chain as a molecular chain.
The polyether polyol takes micromolecular dihydric alcohol as an initiator to be condensed with ethylene oxide and/or propylene oxide to obtain polyether polyol with the average hydroxyl functionality of 2;
the micromolecular dihydric alcohol is straight-chain dihydric alcohol and comprises one or more than one of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol and 1, 8-octanediol.
The blocking agent reacts with NCO groups below 90 ℃ and is deblocked with the NCO groups above 90 ℃, and the molar ratio of the addition amount of the blocking agent to the residual NCO groups is 1.5-2.0: 1.
The sealant is selected from one or more of potassium bisulfite and sodium bisulfite.
The micromolecule monohydric alcohol is liquid at room temperature and is a straight chain or branched chain monohydric alcohol with a boiling point of 80-140 ℃.
The TPU adhesive prepared by the method is applied as a thermal adhesive for bonding fabrics, particularly elastic fabrics; the film-like adhesive product formed by the dissolving and coating process in a solvent can be heat laminated to the fabric or can be laminated to the fabric by a casting machine process.
Has the advantages that: the TPU granular product for hot bonding can be directly and rapidly obtained by a continuous preparation method, on one hand, the product can be stored in a granular state for a long time, on the other hand, the TPU granular product can be processed without adding a solvent which causes great environmental pollution, and the solvent-free direct bonding is realized. Applicants have found that the product exhibits excellent wash-off resistance and resiliency after heat-bonding to fabric, which far exceeds conventional TPU adhesives and is particularly suited for the bonding of elastic fabrics. The product has obvious low temperature performance at the bonding temperature, can be bonded at 90-135 ℃ and even within the range of 90-120 ℃, does not need high-temperature dissociation, has excellent initial peel strength, and finally shows very excellent bonding performance.
Detailed Description
In a preferred embodiment of the present invention, a process for the continuous preparation of a TPU product in the presence of a catalyst comprises:
(1) in a first-stage continuous screw extrusion reactor with the temperature controlled between 80 and 120 ℃, the method comprises
An organic polyisocyanate, and
a polymer polyol having a number average molecular weight of 700 to 1000g/mol, and
micromolecular dihydric alcohol with number average molecular weight of 60-150 g/mol
Adding the mixture into the front section of the reactor, mixing, melting and reacting under the shearing action of a screw;
wherein the molar weight ratio of the organic polyisocyanate NCO groups to the OH groups of the polymer polyol and the small molecule diol is NCO: OH is 1.2-1.5;
in some preferred embodiments, the small molecule dihydric alcohol accounts for 0.5-1% of the total mass except the catalyst in the step (1);
(2) continuously feeding the substance obtained in the step (1) into a second-stage continuous screw extrusion reactor with the temperature controlled at 60-80 ℃, adding a sealing agent into the front section of the second-stage continuous screw extrusion reactor for continuous reaction, and adding micromolecule monohydric alcohol into the rear section of the second-stage continuous screw extrusion reactor to obtain molten TPU;
(3) cutting the molten TPU into granules in an underwater granulating system through a die head, enabling the granules to pass through a cooling water circulation system, further forming in the particle cooling process, fully washing the sealing agent on the surfaces of the granules by cooling water, and drying by cold air to obtain TPU granules;
wherein, the first section of continuous screw extrusion reactor is connected with the second section of continuous screw extrusion reactor, and the screws are in a same-direction double-screw structure;
wherein, the reactions of the step (1) and the step (2) are carried out under the protection of inert gas, and the inert gas refers to a gas which has no reactivity with the raw material in the invention, such as one or more of nitrogen and argon;
further, during the step (1) and/or the step (2) and/or the step (3), additives known by persons skilled in the art can be optionally added to improve or increase other properties of the product, such as one or more of antioxidants, light stabilizers and mold release agents;
further, the temperature of the cooling water in the step (3) is controlled to be 0-10 ℃, the temperature of cold air drying is controlled to be 8-15 ℃, and the moisture content of the dried TPU particles is controlled to be below 100 ppm;
in some of the more preferred embodiments of the present invention,
the length-diameter ratio of screws of the first section of continuous screw extrusion reactor and the second section of continuous screw extrusion reactor is 40-50: 1 respectively;
controlling the reaction time of the material in the first section of continuous screw extrusion reactor to be 1-4 min, and controlling the reaction time of the material in the second section of continuous screw extrusion reactor to be 2-5 min;
controlling the temperature of the die head to be 90-110 ℃, and controlling the grain cutting rotating speed of the underwater grain cutting system to be 1500-5000 rpm;
the inert gas is nitrogen, and the adding amount of the nitrogen is 1-3% of the total weight of the organic polyisocyanate, the polymer polyol and the micromolecular diol;
examples of the antioxidant include 264(2, 6-di-tert-butyl-4-methylphenol), 245 (triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate), 1010 (pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1076 (N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine), and the like;
light stabilizers including ultraviolet absorber UV-928(2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol), ultraviolet absorber UV-234(2- (2' -hydroxy-3 ',5' bis (a, a-dimethylbenzyl) phenyl) benzotriazole), ultraviolet absorber UV-531 (2-hydroxy-4-n-octoxybenzophenone), ultraviolet absorber UV-P (2- (2-hydroxy-5-benzyl) benzotriazole), and the like;
the release agent comprises inorganic release agent, organic release agent and composite release agent formed by organic release agent and emulsifier, for example, the organic release agent or the inorganic release agent comprises one or more of diglycerol oleate, talcum powder, oleic acid, oleamide and fatty acid;
in a more preferred embodiment of the invention, the release agent is a mixture of glycerol dioleate and an emulsifier Lutensol TO-3, and the mass ratio of the glycerol dioleate TO the emulsifier Lutensol TO-3 is 1: 7-9;
as an example, an antioxidant, a light stabilizer may be added in step (1) and/or step (2), and a mold release agent may be added in step (3);
the inventor unexpectedly finds that in some embodiments of the invention, the TPU thermal adhesive product obtained by the method of the invention can maintain excellent water resistance after being attached to an elastic fabric without adding an additional hydrolysis resistance auxiliary agent which can improve the water resistance of the material, and the phenomena of degumming, peeling strength reduction and the like do not occur for many times even under higher water temperature;
the organic polyisocyanate comprises at least one aromatic polyisocyanate and/or at least one aliphatic polyisocyanate;
the aromatic polyisocyanate at least contains 2 NCO groups and comprises at least one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Naphthalene Diisocyanate (NDI), Xylylene Diisocyanate (XDI) and isomers thereof;
the aliphatic polyisocyanate at least contains 2 NCO groups and comprises at least one of isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI) and isomers thereof;
the polymer polyol at least contains one of polyester polyol or polyether polyol;
further, the polymer polyol comprises a branched polyester polyol and/or a linear polyester polyol;
the straight-chain polyester polyol is obtained by polycondensing at least one aliphatic dibasic acid and straight-chain aliphatic micromolecule aliphatic dibasic alcohol, wherein the main molecular chain contains ester bond chain, the tail end of the ester bond chain is hydroxyl, the average hydroxyl functionality is 2, and the molecular chain is straight-chain polyester polyol;
the branched polyester polyol is prepared by polycondensing at least one aliphatic dibasic acid with at least one branched aliphatic micromolecular aliphatic dihydric alcohol and/or straight aliphatic micromolecular aliphatic dihydric alcohol to obtain polyester polyol with an ester bond chain end as a hydroxyl end, an average hydroxyl functionality of 2 and a branched chain as a molecular chain;
polyether polyol with the average hydroxyl functionality of 2 is obtained by polycondensation of polyether polyol micromolecule dihydric alcohol serving as an initiator and ethylene oxide and/or propylene oxide;
in some more preferred embodiments, the polymer polyol is a mixture of a linear polyester polyol and a branched polyester polyol, the mass ratio of linear polyester polyol to branched polyester polyol being 12: 1-4;
as an example, the linear polyester polyol is 1.6-adipate 1.4-butanediol diol and the branched polyester polyol is 1.6-adipate neopentyl glycol ester diol;
the micromolecular dihydric alcohol is straight-chain dihydric alcohol and comprises one or more than one of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol and 1, 8-octanediol;
the blocking agent can react with NCO groups below 90 ℃ and can be deblocked with NCO groups above 90 ℃;
in more preferred embodiments, the molar ratio of the added amount of the blocking agent to the residual NCO groups is 1.5-2.0: 1;
further, the sealing agent is selected from one or more of potassium bisulfite and sodium bisulfite;
the micromolecule monohydric alcohol is liquid at room temperature and is a straight chain or branched chain monohydric alcohol with a boiling point of 80-140 ℃;
in more preferred embodiments, the hydroxyl group of the small molecule monohydric alcohol is located at the end of the molecular chain, with one or more of n-propanol, n-butanol, 1-pentanol being particularly preferred;
in some more preferred embodiments, the addition amount of the small molecule monohydric alcohol is 0.2-1% based on the total mass of the material in the step (1);
in a preferred embodiment of the invention, the polyurethane particle product obtained by the method of the invention can be dissolved in a solvent and coated on a release paper, and the solvent is volatilized to form a film-shaped adhesive product which is attached to a fabric substrate in a hot attaching manner;
the TPU particle product obtained by the method can also be molten by a casting machine and then is sprayed on the fabric, the processing temperature of the casting machine is controlled to be 90-120 ℃, and then the TPU particle product is directly compounded with the elastic fabric.
In order to make the technical scheme of the invention clearer, a part of examples and comparative examples of the invention are given below to further illustrate the advantages and beneficial effects of the invention;
in order to reduce the influence of other factors on the product performance, the following specific examples and comparative examples react in the presence of a stannous octoate catalyst, wherein stannous octoate is added to the front section of a first-stage continuous screw extrusion reactor and the rear section of a second-stage continuous screw extrusion reactor through an additional feeding port, and the total addition amount of the stannous octoate is 0.01-0.05% of the total weight of the obtained TPU;
example 1
(1) In a first stage continuous screw extrusion reactor with the temperature controlled at 100 ℃ and the screw length-diameter ratio of 50:1, the method comprises
4, 4' -MDI, and
1.6-adipic acid 1.4-butanediol ester diol having a number average molecular weight of 700g/mol and a number average molecular weight of 700g/mol, in a mass ratio of 56:5, and 1.6-adipic acid neopentyl glycol ester diol mixture, and
1, 4-butanediol
Adding the mixture into the front section of the reactor, adding a stannous octoate catalyst accounting for 0.02% of the total weight of the obtained TPU, adding an antioxidant 1010 accounting for 0.3% and a UV-234 accounting for 0.3% of the total weight of the TPU except the catalyst in the step, mixing, melting and reacting under the shearing action of a screw, wherein the reaction time is 3 min;
the molar weight ratio of the organic polyisocyanate NCO groups to the OH groups of the polymer polyol and small molecule diol is NCO: OH is 1.45;
the small molecular dihydric alcohol accounts for 0.7 percent of the total mass of the substances except the catalyst in the step (1);
(2) continuously feeding the substance obtained in the step (1) into a second-stage continuous screw extrusion reactor with a screw length-diameter ratio of 50:1 controlled at 60 ℃, supplementing a stannous octoate catalyst accounting for 0.02% of the total weight of the obtained TPU, adding sodium bisulfite into the front section of the second-stage continuous screw extrusion reactor, wherein the molar ratio of the added amount of the sodium bisulfite to the residual NCO groups is 1.54:1, adding n-propanol accounting for 0.2% of the total weight of the materials except the catalyst in the step (1) into the rear section of the second-stage continuous screw extrusion reactor, and reacting for 5min to obtain the molten TPU;
wherein the adding amount of the nitrogen in the step (1) and the step (2) is 3 percent of the total weight of the organic polyisocyanate, the polymer polyol and the micromolecular diol;
(3) cutting the molten TPU into granules in an underwater granulating system through a die head, enabling the granules to pass through a cooling water circulation system, further forming in the particle cooling process, fully washing the sealing agent on the surfaces of the granules by cooling water, and drying by cold air to obtain TPU granules;
wherein the temperature of the die head is controlled at 90 ℃, and the granulating rotating speed of the underwater granulating system is controlled at 3000 rpm;
controlling the temperature of cooling water at 0 ℃, controlling the temperature of cold air drying in a nitrogen atmosphere at 10 ℃, controlling the moisture content of dried TPU particles below 100ppm, and sealing and packaging.
Example 2
(1) In a first stage continuous screw extrusion reactor with the temperature controlled at 120 ℃ and the screw length-diameter ratio of 45:1, the reactor comprises
4, 4' -MDI, and
1.6-adipic acid 1.4-butanediol ester diol having a number average molecular weight of 1000g/mol and a number average molecular weight of 1000g/mol of a 1.6-adipic acid neopentyl glycol ester diol mixture in a mass ratio of 53:18, and
1, 6-hexanediol
Adding the mixture into the front section of the reactor, adding a stannous octoate catalyst which is 0.02 percent of the total weight of the obtained TPU, mixing, melting and reacting under the shearing action of a screw rod, wherein the reaction time is 1 min;
the molar weight ratio of the organic polyisocyanate NCO groups to the OH groups of the polymer polyol and small molecule diol is NCO: OH is 1.32;
the small molecular dihydric alcohol accounts for 0.8 percent of the total mass of the substances except the catalyst in the step (1);
(2) continuously feeding the substance obtained in the step (1) into a second-stage continuous screw extrusion reactor with the screw length-diameter ratio of 50:1 controlled at 70 ℃, supplementing a stannous octoate catalyst accounting for 0.02% of the total weight of the obtained TPU, adding potassium bisulfite into the front section of the second-stage continuous screw extrusion reactor, wherein the molar ratio of the added amount of the potassium bisulfite to the residual NCO groups is 1.53:1, adding n-butyl alcohol accounting for 0.5% of the total weight of the materials except the catalyst in the step (1) into the rear section of the second-stage continuous screw extrusion reactor, and reacting for 5min to obtain the molten TPU;
wherein, the adding amount of the nitrogen in the step (1) and the step (2) is 3 percent of the total weight of the organic polyisocyanate, the polymer polyol and the micromolecular diol;
(3) cutting the molten TPU into granules in an underwater granulating system through a die head, enabling the granules to pass through a cooling water circulation system, further forming in the particle cooling process, fully washing the sealing agent on the surfaces of the granules by cooling water, and drying by cold air to obtain TPU granules;
wherein the temperature of the die head is controlled at 110 ℃, and the granulating rotating speed of the underwater granulating system is controlled at 5000 rpm;
controlling the temperature of cooling water at 0 ℃, controlling the temperature of cold air drying in a nitrogen atmosphere at 15 ℃, controlling the moisture content of dried TPU particles below 100ppm, and sealing and packaging.
Example 3
(1) In a first stage continuous screw extrusion reactor with the temperature controlled at 80 ℃ and the screw length-diameter ratio of 50:1, the method comprises
4, 4' -MDI, and
1.6-adipic acid 1.4-butanediol ester diol having a number average molecular weight of 1000g/mol and 1.6-adipic acid neopentyl glycol ester diol mixture having a number average molecular weight of 700g/mol in a mass ratio of 60:9, and
1, 6-hexanediol
Adding the mixture into the front section of the reactor, adding a stannous octoate catalyst which is 0.02 percent of the total weight of the obtained TPU, mixing, melting and reacting under the shearing action of a screw rod, wherein the reaction time is 4 min;
the molar weight ratio of the organic polyisocyanate NCO groups to the OH groups of the polymer polyol and small molecule diol is NCO: OH 1.39;
the small molecular dihydric alcohol accounts for 0.8 percent of the total mass of the substances except the catalyst in the step (1);
(2) continuously feeding the substance obtained in the step (1) into a second-stage continuous screw extrusion reactor with the screw length-diameter ratio of 40:1 controlled at 80 ℃, supplementing a stannous octoate catalyst accounting for 0.02% of the total weight of the obtained TPU, adding potassium bisulfite into the front section of the second-stage continuous screw extrusion reactor, wherein the molar ratio of the added amount of the potassium bisulfite to the residual NCO groups is 1.97:1, adding 0.4% of 1-pentanol into the rear section of the second-stage continuous screw extrusion reactor, and obtaining the TPU in a molten state, wherein the reaction time is 2min based on the total weight of the materials except the catalyst in the step (1);
wherein, the adding amount of the nitrogen in the step (1) and the step (2) is 3 percent of the total weight of the organic polyisocyanate, the polymer polyol and the micromolecular diol;
(3) cutting the molten TPU into granules in an underwater granulating system through a die head, enabling the granules to pass through a cooling water circulation system, further forming in the particle cooling process, fully washing the sealing agent on the surfaces of the granules by cooling water, and drying by cold air to obtain TPU granules;
wherein the temperature of the die head is controlled at 100 ℃, and the granulating rotating speed of the underwater granulating system is controlled at 4000 rpm;
controlling the temperature of cooling water at 0 ℃, controlling the temperature of cold air drying in a nitrogen atmosphere at 8 ℃, controlling the moisture content of dried TPU particles below 100ppm, and sealing and packaging.
Example 4
(1) In a first stage continuous screw extrusion reactor with the temperature controlled at 80 ℃ and the screw length-diameter ratio of 50:1, the method comprises
4, 4' -MDI, and
1.6-adipic acid 1.4-butanediol ester diol having a number average molecular weight of 700g/mol and a number average molecular weight of 1000g/mol, in a mass ratio of 58:8, and
1, 4-butanediol
Adding the mixture into the front section of the reactor, adding a stannous octoate catalyst which is 0.02 percent of the total weight of the obtained TPU, mixing, melting and reacting under the shearing action of a screw rod, wherein the reaction time is 3 min;
the molar weight ratio of the organic polyisocyanate NCO groups to the OH groups of the polymer polyol and small molecule diol is NCO: OH ═ 1.22;
the small molecular dihydric alcohol accounts for 0.8 percent of the total mass of the substances except the catalyst in the step (1);
(2) continuously feeding the substance obtained in the step (1) into a second-stage continuous screw extrusion reactor with the screw length-diameter ratio of 45:1 controlled at 80 ℃, supplementing a stannous octoate catalyst accounting for 0.02% of the total weight of the obtained TPU, adding sodium bisulfite into the front section of the second-stage continuous screw extrusion reactor, wherein the molar ratio of the added amount of the sodium bisulfite to the residual NCO groups is 1.81:1, adding 1% of n-butyl alcohol into the rear section of the second-stage continuous screw extrusion reactor, calculating the total mass of the materials except the catalyst in the step (1), and reacting for 3min to obtain the molten TPU;
wherein, the adding amount of the nitrogen in the step (1) and the step (2) is 3 percent of the total weight of the organic polyisocyanate, the polymer polyol and the micromolecular diol;
(3) cutting the molten TPU into granules in an underwater granulating system through a die head, enabling the granules to pass through a cooling water circulation system, further forming in the particle cooling process, fully washing the sealing agent on the surfaces of the granules by cooling water, and drying by cold air to obtain TPU granules;
wherein the temperature of the die head is controlled at 90 ℃, and the granulating rotating speed of the underwater granulating system is controlled at 1500 rpm;
controlling the temperature of cooling water at 10 ℃, controlling the temperature of cold air drying at 15 ℃ in a nitrogen atmosphere, controlling the moisture content of dried TPU particles below 100ppm, and sealing and packaging.
Example 5
(1) In a first stage continuous screw extrusion reactor with the temperature controlled at 100 ℃ and the screw length-diameter ratio of 50:1, the method comprises
4, 4' -MDI, and
1.6-adipic acid 1.4-butanediol ester diol having a number average molecular weight of 700g/mol and a number average molecular weight of 1000g/mol in a mass ratio of 57:6, and
the mass ratio is 1:1, 4-butanediol and 1, 6-hexanediol mixture
Adding the mixture into the front section of the reactor, adding a stannous octoate catalyst which is 0.02 percent of the total weight of the obtained TPU, mixing, melting and reacting under the shearing action of a screw rod, wherein the reaction time is 2 min;
the molar weight ratio of organic polyisocyanate NCO groups to OH groups of the polymer polyol and small molecule diol is NCO: OH 1.43;
the small molecular dihydric alcohol accounts for 0.8 percent of the total mass of the substances except the catalyst in the step (1);
(2) continuously feeding the substance obtained in the step (1) into a second-stage continuous screw extrusion reactor with a screw length-diameter ratio of 50:1 controlled at 90 ℃, supplementing a stannous octoate catalyst accounting for 0.02% of the total weight of the obtained TPU, adding sodium bisulfite into the front section of the second-stage continuous screw extrusion reactor, wherein the molar ratio of the added amount of the sodium bisulfite to the residual NCO groups is 1.99:1, adding n-propanol accounting for 0.8% of the total weight of the materials except the catalyst in the step (1), and reacting for 5min to obtain the molten TPU;
wherein, the adding amount of the nitrogen in the step (1) and the step (2) is 3 percent of the total weight of the organic polyisocyanate, the polymer polyol and the micromolecular diol;
(3) cutting the molten TPU into granules in an underwater granulating system through a die head, enabling the granules to pass through a cooling water circulation system, further forming in the particle cooling process, fully washing the sealing agent on the surfaces of the granules by cooling water, and drying by cold air to obtain TPU granules;
wherein the temperature of the die head is controlled at 100 ℃, and the granulating rotating speed of the underwater granulating system is controlled at 5000 rpm;
controlling the temperature of cooling water at 0 ℃, controlling the temperature of cold air drying in a nitrogen atmosphere at 10 ℃, controlling the moisture content of dried TPU particles below 100ppm, and sealing and packaging.
Example 6
(1) In a first stage continuous screw extrusion reactor with the temperature controlled at 120 ℃ and the screw length-diameter ratio of 45:1, the reactor comprises
4, 4' -MDI, and
1, 6-adipic acid 1, 4-butanediol ester diol having a number-average molecular weight of 1000g/mol,
and 1, 6-hexanediol
Adding the mixture into the front section of the reactor, adding a stannous octoate catalyst which is 0.02 percent of the total weight of the obtained TPU, mixing, melting and reacting under the shearing action of a screw rod, wherein the reaction time is 1 min;
the molar weight ratio of organic polyisocyanate NCO groups to OH groups of the polymer polyol is NCO: OH is 1.32;
the small molecular dihydric alcohol accounts for 0.8 percent of the total mass of the substances except the catalyst in the step (1);
(2) continuously feeding the substance obtained in the step (1) into a second-stage continuous screw extrusion reactor with the screw length-diameter ratio of 50:1 controlled at 70 ℃, supplementing a stannous octoate catalyst accounting for 0.02% of the total weight of the obtained TPU, adding potassium bisulfite into the front section of the second-stage continuous screw extrusion reactor, wherein the molar ratio of the added amount of the potassium bisulfite to the residual NCO groups is 1.53:1, adding n-butyl alcohol accounting for 0.5% of the total weight of the materials except the catalyst in the step (1) into the rear section of the second-stage continuous screw extrusion reactor, and reacting for 5min to obtain the molten TPU;
wherein, the adding amount of the nitrogen in the step (1) and the step (2) is 3 percent of the total weight of the organic polyisocyanate, the polymer polyol and the micromolecular diol;
(3) cutting the molten TPU into granules in an underwater granulating system through a die head, enabling the granules to pass through a cooling water circulation system, further forming in the particle cooling process, fully washing the sealing agent on the surfaces of the granules by cooling water, and drying by cold air to obtain TPU granules;
wherein the temperature of the die head is controlled at 110 ℃, and the granulating rotating speed of the underwater granulating system is controlled at 5000 rpm;
controlling the temperature of cooling water at 0 ℃, controlling the temperature of cold air drying in a nitrogen atmosphere at 15 ℃, controlling the moisture content of dried TPU particles below 100ppm, and sealing and packaging.
Comparative example 1
(1) In a continuous screw extrusion reactor with the temperature controlled at 80 ℃ and the screw length-diameter ratio of 50:1, the method comprises
4, 4' -MDI, and
1.6-adipic acid 1.4-butanediol ester diol having a number average molecular weight of 700g/mol and a number average molecular weight of 1000g/mol, in a mass ratio of 58:8, and
1, 4-butanediol
Adding the mixture into the front section of the reactor, adding a stannous octoate catalyst which is 0.02 percent of the total weight of the obtained TPU, mixing, melting and reacting under the shearing action of a screw rod, wherein the reaction time is 2 min;
the molar weight ratio of the organic polyisocyanate NCO groups to the OH groups of the polymer polyol and small molecule diol is NCO: OH ═ 1.22;
the small molecular dihydric alcohol accounts for 0.8 percent of the total mass of the substances except the catalyst in the step (1);
replenishing a stannous octoate catalyst which is 0.02 percent of the total weight of the obtained TPU in the middle section of the reactor, and simultaneously adding sodium bisulfite in the middle section, wherein the molar ratio of the adding amount to the residual NCO groups is 1.81: 1;
adding 1% of n-butanol at the rear section of the reactor, calculating based on the total mass of the organic polyisocyanate, the polymer polyol and the small molecular diol, and continuing to react for 2min to obtain the TPU in a molten state;
wherein, the adding amount of the nitrogen in the step (1) is 3 percent of the total weight of the organic polyisocyanate, the polymer polyol and the micromolecular diol;
(2) and (2) directly carrying out underwater granulation on the substance obtained in the step (1), and experiments show that the material cannot be further molded, so that an underwater granulation system cannot be carried out, is in a semi-liquid state, and is directly packaged in a sealing manner.
Comparative example 2
(1) 1.6-adipic acid 1.4-butanediol ester diol having a number average molecular weight of 700g/mol and a 1.6-adipic acid neopentyl glycol ester diol mixture having a number average molecular weight of 1000g/mol in a mass ratio of 57:6 were added to a reaction vessel under nitrogen protection, followed by addition of a 1:1, 4-butanediol and 1, 6-hexanediol mixture, controlling the temperature at 120 ℃, then reducing the temperature to 80 ℃, adding 4, 4' -MDI, adding a stannous octoate catalyst accounting for 0.02 percent of the total weight of TPU, and carrying out polymerization reaction for 2 hours to obtain a prepolymer;
the molar weight ratio of the organic polyisocyanate NCO groups to the OH groups of the polymer polyol and small molecule diol is NCO: OH is 1.42;
the small molecular dihydric alcohol accounts for 0.8 percent of the total mass of the substances except the catalyst in the step (1);
(2) adding sodium bisulfite into a reaction kettle, wherein the molar ratio of the addition amount of the sodium bisulfite to the residual NCO groups is 1.99:1, controlling the reaction temperature at 70 ℃, adding 0.8 percent of n-propanol after 1.5 hours, calculating based on the total mass of the materials except the catalyst in the step (1), finally obtaining a TPU product, and sealing and packaging;
wherein, the adding amount of the nitrogen in the step (1) and the step (2) is 3 percent of the total weight of the organic polyisocyanate, the polymer polyol and the small molecular diol.
Comparative example 3
(1) In a first stage continuous screw extrusion reactor with the temperature controlled at 120 ℃ and the screw length-diameter ratio of 45:1, the reactor comprises
4, 4' -MDI, and
1.6-adipic acid 1.4-butanediol ester diol having a number average molecular weight of 1000g/mol and a number average molecular weight of 1000g/mol of a 1.6-adipic acid neopentyl glycol ester diol mixture in a mass ratio of 53:18, and
1, 6-hexanediol
Adding the mixture into the front section of the reactor, adding a stannous octoate catalyst which is 0.02 percent of the total weight of the obtained TPU, mixing, melting and reacting under the shearing action of a screw rod, wherein the reaction time is 1 min;
the molar weight ratio of the organic polyisocyanate NCO groups to the OH groups of the polymer polyol and small molecule diol is NCO: OH is 1.32;
the small molecular dihydric alcohol accounts for 0.8 percent of the total mass of the substances except the catalyst in the step (1);
(2) continuously feeding the substance obtained in the step (1) into a second-stage continuous screw extrusion reactor with the screw length-diameter ratio of 50:1 controlled at 70 ℃, supplementing a stannous octoate catalyst accounting for 0.02% of the total weight of the obtained TPU, adding n-butanol accounting for 0.5% of the total weight of the material except the catalyst in the step (1) at the rear stage of the second-stage continuous screw extrusion reactor, and obtaining the molten TPU, wherein the reaction time is 5 min;
wherein, the adding amount of the nitrogen in the step (1) and the step (2) is 3 percent of the total weight of the organic polyisocyanate, the polymer polyol and the micromolecular diol;
(3) cutting the molten TPU into granules in an underwater granulating system through a die head, enabling the granules to pass through a cooling water circulation system, further forming in the particle cooling process, fully washing the sealing agent on the surfaces of the granules by cooling water, and drying by cold air to obtain TPU granules;
wherein the temperature of the die head is controlled at 110 ℃, and the granulating rotating speed of the underwater granulating system is controlled at 5000 rpm;
controlling the temperature of cooling water at 0 ℃, controlling the temperature of cold air drying in a nitrogen atmosphere at 15 ℃, controlling the moisture content of dried TPU particles below 100ppm, and sealing and packaging.
Comparative example 4
(1) In a first stage continuous screw extrusion reactor with the temperature controlled at 120 ℃ and the screw length-diameter ratio of 45:1, the reactor comprises
4, 4' -MDI, and
1.6-adipic acid 1.4-butanediol ester diol having a number average molecular weight of 1000g/mol and a number average molecular weight of 1000g/mol of a 1.6-adipic acid neopentyl glycol ester diol mixture in a mass ratio of 53:18, and
1, 6-hexanediol
Adding the mixture into the front section of the reactor, adding a stannous octoate catalyst which is 0.02 percent of the total weight of the obtained TPU, mixing, melting and reacting under the shearing action of a screw rod, wherein the reaction time is 1 min;
the molar weight ratio of the organic polyisocyanate NCO groups to the OH groups of the polymer polyol and small molecule diol is NCO: OH is 1.32;
the small molecular dihydric alcohol accounts for 0.8 percent of the total mass of the substances except the catalyst in the step (1);
(2) continuously feeding the substance obtained in the step (1) into a second-stage continuous screw extrusion reactor with the screw length-diameter ratio of 50:1 controlled at 110 ℃, supplementing a stannous octoate catalyst accounting for 0.02% of the total weight of the obtained TPU, adding methyl ethyl ketoxime into the front section of the second-stage continuous screw extrusion reactor, wherein the molar ratio of the addition amount of the methyl ethyl ketoxime to the residual NCO groups is 1.53:1, adding n-butyl alcohol accounting for 0.5% of the total weight of the materials except the catalyst in the step (1) into the rear section of the second-stage continuous screw extrusion reactor, and reacting for 5min to obtain the molten TPU;
wherein, the adding amount of the nitrogen in the step (1) and the step (2) is 3 percent of the total weight of the organic polyisocyanate, the polymer polyol and the micromolecular diol;
(3) cutting the molten TPU into granules in an underwater granulating system through a die head, enabling the granules to pass through a cooling water circulation system, further forming in the particle cooling process, fully washing the sealing agent on the surfaces of the granules by cooling water, and drying by cold air to obtain TPU granules;
wherein the temperature of the die head is controlled at 110 ℃, and the granulating rotating speed of the underwater granulating system is controlled at 5000 rpm;
controlling the temperature of cooling water at 0 ℃, controlling the temperature of cold air drying in a nitrogen atmosphere at 15 ℃, controlling the moisture content of dried TPU particles below 100ppm, and sealing and packaging.
Comparative example 5
(1) In a first stage continuous screw extrusion reactor with the temperature controlled at 80 ℃ and the screw length-diameter ratio of 50:1, the method comprises
4, 4' -MDI, and
1.6-adipic acid 1.4-butanediol ester diol having a number average molecular weight of 1000g/mol and 1.6-adipic acid neopentyl glycol ester diol mixture having a number average molecular weight of 700g/mol in a mass ratio of 60:9, and
1, 6-hexanediol
Adding the mixture into the front section of the reactor, adding a stannous octoate catalyst which is 0.02 percent of the total weight of the obtained TPU, mixing, melting and reacting under the shearing action of a screw rod, wherein the reaction time is 4 min;
the molar weight ratio of the organic polyisocyanate NCO groups to the OH groups of the polymer polyol and small molecule diol is NCO: OH ═ 1: 1;
the small molecular dihydric alcohol accounts for 0.8 percent of the total mass of the substances except the catalyst in the step (1);
(2) continuously feeding the substance obtained in the step (1) into a second-stage continuous screw extrusion reactor with the screw length-diameter ratio of 40:1 controlled at 80 ℃, supplementing a stannous octoate catalyst accounting for 0.02% of the total weight of the obtained TPU, adding n-butanol accounting for 0.4% of the total weight of the material except the catalyst in the step (1) at the rear stage of the second-stage continuous screw extrusion reactor, and obtaining the molten TPU, wherein the reaction time is 2 min;
wherein, the adding amount of the nitrogen in the step (1) and the step (2) is 3 percent of the total weight of the organic polyisocyanate, the polymer polyol and the micromolecular diol;
(3) cutting the molten TPU into granules in an underwater granulating system through a die head, enabling the granules to pass through a cooling water circulation system, further forming in the particle cooling process, fully washing the sealing agent on the surfaces of the granules by cooling water, and drying by cold air to obtain TPU granules;
wherein the temperature of the die head is controlled at 100 ℃, and the granulating rotating speed of the underwater granulating system is controlled at 4000 rpm;
controlling the temperature of cooling water at 0 ℃, controlling the temperature of cold air drying in a nitrogen atmosphere at 8 ℃, controlling the moisture content of dried TPU particles below 100ppm, and sealing and packaging.
And respectively carrying out performance tests on the obtained TPU, wherein the specific test method comprises the following steps:
(1) bonding temperature: the products of examples 1-5 and comparative examples 3-6 were laminated on Lycra cotton by a casting machine with a film thickness of 0.05mm, and were thermally laminated with Lycra cotton by a laminating machine to determine the laminating temperature range;
dissolving the product of the comparative examples 1-2 into a solution with the solid content of 30% by a butanone solvent, then blade-coating the solution on release paper with silicon substrate, carrying out thermal lamination on the release paper with the film thickness of 0.05mm after evaporation and Lycra cotton by a laminating machine, and determining the laminating temperature range;
(2) peel strength: according to the same method of the bonding temperature test, setting the temperature of a bonding machine within the bonding temperature range of the product for hot bonding, and carrying out the peel strength test, wherein the width of a sample strip is 25mm, the stretching rate is 100mm/min, the peel angle is 180 degrees, and the test result is the average value of 3 parallel sample strips;
1) keeping the sample strip at 80 ℃ and 50% relative humidity for ten minutes, taking out the sample strip, placing the sample strip in a constant-temperature drying oven at 23 ℃ for 1 hour, and then testing the peel strength to obtain the original peel strength;
2) standing at 80 ℃ and 50% relative humidity for 3 days, taking out the sample strips, placing in a constant-temperature drying oven at 23 ℃ for 1 hour, and then carrying out peel strength test to obtain the peel strength after 3 days;
3) placing the cloth at 80 ℃ and 50% relative humidity for 3 days, taking out the attached cloth, placing the attached cloth in a constant-temperature drying oven at 23 ℃ for 1 hour, taking out the cloth or clothes with a sample band of 3-5kg, placing the cloth or clothes in a washing machine in a mixed manner, adding 5-10g of carving washing powder, washing the cloth or clothes at 60 ℃ for 45min in a machine, circularly washing the cloth for 5 times, placing the washed attached cloth in a drying oven at 50 ℃ for drying treatment, placing the sample at 23 ℃ for drying at constant temperature for 8 hours, cutting the sample band into sample bands, and testing the peel strength to obtain the peel strength after washing;
(3) rebound resilience: the products of comparative examples 1 to 2 were crushed by a crusher, and then the crushed products of examples 1 to 5 and comparative examples 3 to 6 and comparative examples 1 to 2 were produced into a film having a thickness of 0.05mm by a single screw extruder, and left at 80 ℃ under 50% relative humidity for 3 days.
The resilience of the film was tested as follows: taking a film with the width of 10mm multiplied by the length of 50mm, stretching the film to three times of the original length, namely the length of 150mm at the stretching speed of 100mm/min, keeping the length for 30min, releasing the stress born by the film, and testing the length after 12 hours to be L:
the products obtained in the above examples and comparative examples were subjected to the following performance tests:
note: in comparative example 5, after washing with water at 60 ℃ for 5 times, the degumming agent can be directly degummed and cannot be used.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. A process for preparing a TPU adhesive, characterized in that said process comprises:
step 1, adding polymer polyol containing organic polyisocyanate, with the number average molecular weight of 700-1000 g/mol and micromolecule diol with the number average molecular weight of 60-150 g/mol into the front section of a first-section continuous screw extrusion reactor, mixing, melting and reacting under the shearing action of a screw;
wherein the molar weight ratio of the organic polyisocyanate NCO groups to the OH groups of the polymer polyol and the small molecule diol is NCO: OH is 1.2-1.5;
step 2, continuously feeding the substance finally obtained in the step 1 into a second-section continuous screw extrusion reactor, adding a sealant into the front section of the second-section continuous screw extrusion reactor for continuous reaction, and adding micromolecule monohydric alcohol into the rear section of the second-section continuous screw extrusion reactor to obtain the molten TPU;
and 3, cutting the TPU in the molten state obtained in the step 2 into particles in an underwater cutting system, enabling the particles to pass through a cooling water circulation system, further forming the particles in the cooling process, fully washing off the sealing agent on the surfaces of the particles by cooling water, and finally drying the particles by cold air to obtain the TPU particles.
2. The process of claim 1, wherein the first continuous screw extrusion reactor is connected to the second continuous screw extrusion reactor; the temperature of the first stage continuous screw extrusion reactor is controlled above the melting temperature of the material and below the decomposition temperature thereof, and the temperature of the second stage continuous screw extrusion reactor of step 2 is controlled above the melting temperature of the material and below 100 ℃.
3. The process for preparing a TPU adhesive according to claim 1, wherein the reactions of step 1, step 2 and/or step 3 are carried out under an inert gas atmosphere which is unreactive with the starting materials; step 1 and/or step 2 are/is carried out in the presence of a catalyst; adding an additive during the step 1 and/or the step 2 and/or the step 3.
4. The preparation method of the TPU adhesive according to claim 1, wherein the temperature of the cooling water in the step 3 is controlled to be 0-10 ℃, the temperature of the cold air drying is controlled to be 8-15 ℃, and the moisture content of the dried TPU particles is controlled to be less than 100 ppm.
5. A method of making a TPU adhesive as set forth in claim 1 wherein said organic polyisocyanate comprises at least one aromatic polyisocyanate and/or at least one aliphatic polyisocyanate.
6. The method of claim 5, wherein the aromatic polyisocyanate contains at least 2 NCO groups and comprises at least one of toluene diisocyanate TDI, diphenylmethane diisocyanate MDI, naphthalene diisocyanate NDI, xylylene diisocyanate XDI, and isomers thereof; the aliphatic polyisocyanate at least contains 2 NCO groups and at least contains one of isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI) and isomers thereof.
7. The method of claim 1, wherein the polymer polyol comprises at least one of a polyester polyol or a polyether polyol.
8. The method of claim 7, wherein the polyester polyol is a branched polyester polyol and/or a linear polyester polyol;
the straight-chain polyester polyol is obtained by polycondensing at least one aliphatic dibasic acid and straight-chain aliphatic micromolecular diol, wherein the main molecular chain contains ester bond chain, the tail end of the ester bond chain is hydroxyl, the average hydroxyl functionality is 2, and the molecular chain is straight-chain polyester polyol;
the branched polyester polyol is prepared by polycondensing at least one aliphatic dibasic acid with at least one branched chain type aliphatic micromolecular dihydric alcohol and/or straight chain type aliphatic micromolecular aliphatic dihydric alcohol to obtain the polyester polyol with an ester bond chain end as a hydroxyl end, an average hydroxyl functionality of 2 and a branched chain as a molecular chain.
9. The method of claim 8, wherein the polyester polyol is a linear polyester polyol and a branched polyester polyol in a mass ratio of 12: 1 to 4.
10. The method of claim 7, wherein the polyether polyol is a polyether polyol having an average hydroxyl functionality of 2 obtained by polycondensation of a small molecule diol as an initiator with ethylene oxide and/or propylene oxide;
the micromolecular dihydric alcohol is straight-chain dihydric alcohol and comprises one or more than one of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol and 1, 8-octanediol.
11. The method of claim 1, wherein the blocking agent is one or more of potassium bisulfite and sodium bisulfite.
12. The method of claim 11, wherein the blocking agent reacts with NCO groups at a temperature below 90 ℃ and unblocks with NCO groups at a temperature above 90 ℃, and the molar ratio of the blocking agent to the residual NCO groups is 1.5-2.0: 1.
13. The method of claim 1, wherein the low molecular weight monohydric alcohol is a liquid at room temperature and is a straight or branched chain monohydric alcohol having a boiling point of 80-140 ℃.
14. Use of a TPU adhesive prepared by the process of claim 1 as a thermal adhesive for the bonding of fabrics, especially elastic fabrics; the film-like adhesive product formed by the dissolving and coating process in a solvent can be heat laminated to the fabric or can be laminated to the fabric by a casting machine process.
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