CN115109554A - Polyurethane adhesive and preparation method and application thereof - Google Patents
Polyurethane adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN115109554A CN115109554A CN202210943305.0A CN202210943305A CN115109554A CN 115109554 A CN115109554 A CN 115109554A CN 202210943305 A CN202210943305 A CN 202210943305A CN 115109554 A CN115109554 A CN 115109554A
- Authority
- CN
- China
- Prior art keywords
- polyurethane adhesive
- polyurethane resin
- chain extender
- polyurethane
- heat preservation
- 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
- 239000004814 polyurethane Substances 0.000 title claims abstract description 94
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 89
- 239000000853 adhesive Substances 0.000 title claims abstract description 87
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 73
- 239000004970 Chain extender Substances 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 19
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical group NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 125000003827 glycol group Chemical group 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 74
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
- -1 polybutylene adipate Polymers 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000004321 preservation Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 33
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 28
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 22
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 17
- 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 17
- 238000004821 distillation Methods 0.000 claims description 16
- 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 15
- 239000012298 atmosphere Substances 0.000 claims description 15
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 15
- 238000004945 emulsification Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 12
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 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 claims description 9
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 8
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 239000004359 castor oil Substances 0.000 claims description 8
- 235000019438 castor oil Nutrition 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 claims description 7
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 7
- 208000005156 Dehydration Diseases 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 6
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 150000003839 salts Chemical group 0.000 claims description 4
- 238000004383 yellowing Methods 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- WDWDWGRYHDPSDS-UHFFFAOYSA-N methanimine Chemical compound N=C WDWDWGRYHDPSDS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- 229940123208 Biguanide Drugs 0.000 description 21
- 229920003002 synthetic resin Polymers 0.000 description 14
- 239000000057 synthetic resin Substances 0.000 description 14
- 238000010276 construction Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- FYSJYVHOKOFOAP-UHFFFAOYSA-N hexanedioic acid;propane-1,3-diol Chemical compound OCCCO.OC(=O)CCCCC(O)=O FYSJYVHOKOFOAP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BTVWZWFKMIUSGS-UHFFFAOYSA-N 2-methylpropane-1,2-diol Chemical compound CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920005586 poly(adipic acid) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000921 polyethylene adipate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- BUOPYOGQBUMALK-UHFFFAOYSA-N 1,5-dioxacycloundecane-6,11-dione Chemical compound O=C1CCCCC(=O)OCCCO1 BUOPYOGQBUMALK-UHFFFAOYSA-N 0.000 description 1
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- RNQBCZCPNUHWLV-UHFFFAOYSA-N 1,8-dioxacyclotetradecane-2,7-dione Chemical compound O=C1CCCCC(=O)OCCCCCCO1 RNQBCZCPNUHWLV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 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
- 230000000295 complement effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- FZWBABZIGXEXES-UHFFFAOYSA-N ethane-1,2-diol;hexanedioic acid Chemical compound OCCO.OC(=O)CCCCC(O)=O FZWBABZIGXEXES-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- 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
-
- 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
- C09J11/08—Macromolecular additives
-
- 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
- C08G2170/00—Compositions for adhesives
Abstract
The invention relates to a polyurethane adhesive and a preparation method and application thereof, wherein the preparation raw materials of the polyurethane adhesive comprise polyurethane resin and a curing agent; the polyurethane resin comprises the following raw materials in percentage by weight: 22.0-28.5% of polyester polyol, 0.7-1.3% of guanidinium salt chain extender, 0.1-0.2% of glycol chain extender, 3.5-7.0% of diisocyanate, 0.02-0.1% of catalyst, 0.7-1.1% of polyethyleneimine, 35-40% of diluent and 100% of water. The polyurethane adhesive disclosed by the invention is a water-based polyurethane adhesive, has excellent hydrolysis resistance, chemical resistance and adhesion and is low in water absorption.
Description
Technical Field
The invention relates to the technical field of adhesives, and particularly relates to a polyurethane adhesive and a preparation method and application thereof.
Background
Polyurethane has been widely used in industries such as light textile, adhesive, printing and dyeing, leather processing, transportation, textile, civil construction, electronic components, shoemaking, packaging, paper making, foaming materials, coatings and the like at home and abroad due to the advantages of wide adjustable range of the softness of the molecular structure, low temperature resistance, good flexibility, strong adhesion, wear resistance, chemical resistance, aging resistance and the like.
The polyurethane adhesive is an adhesive containing urethane groups (-NHCOO-) in a molecular chain. Usually, the polyisocyanate is obtained by reacting polyisocyanate or an adduct thereof with a polyhydric alcohol having active hydrogen. Has the excellent performances of high reaction activity, strong cohesive force, normal temperature curing, impact resistance and the like. The solvent type polyurethane adhesive used in the industry at present adopts a large amount of organic solvent, which seriously pollutes the environment and increases the cost. Environmentally friendly aqueous polyurethanes with low VOC content, low or no pollution, using water as the dispersion medium, have become the direction of development and research of polyurethane resins in recent years. However, because the glue film has the defects of solvent resistance, chemical resistance, poor water resistance and the like, the single WPU emulsion does not meet the requirements of people in certain properties, and the property of the polyurethane adhesive can be improved by adding a substance with complementary properties in the process of synthesizing polyurethane, so that the glue film is more in line with the requirements of people.
CN114133533A discloses a waterborne polyurethane adhesive and a preparation method thereof, wherein the preparation method of the disclosed waterborne polyurethane adhesive comprises the following steps: under the protection of nitrogen, adding polyester polyol, polyether polyol, diisocyanate, an organic tin catalyst and dimethylolpropionic acid into a reaction kettle, and reacting at 80-90 ℃ for 1.5-2.5 h to obtain a polyurethane prepolymer; adding a hydrophilic chain extender into the polyurethane prepolymer, performing reflux reaction for 2-3h at 65-75 ℃ by taking acetone as a solvent, then adding an aqueous silane oligomer for reaction for 0.8-1.2 h, then adding a salt forming agent for neutralization, finally adding water for emulsification, and performing reduced pressure distillation to remove acetone to obtain an aqueous polyurethane adhesive; the aqueous silane oligomer is a mixture of an aminosilane oligomer and an epoxysilane oligomer. The waterborne polyurethane is modified by the waterborne silane oligomer, but the highest water resistance is only 72 hours.
CN113831883A discloses a yellowing-resistant waterborne polyurethane adhesive, a preparation method and an application thereof, wherein the disclosed waterborne polyurethane adhesive is prepared from the following raw materials in parts by weight: 50-80 parts of polyether polyol, 30-60 parts of sulfonate polyester polyol, 4-8 parts of micromolecular sulfonate diol, 40-60 parts of diisocyanate, 0.02-0.05 part of catalyst dibutyltin dilaurate, 100 parts of deionized water and 200 parts of rear chain extender sulfonate amine; the waterborne polyurethane adhesive with high solid content of 50-60%, high initial viscosity, drying time of 12-24h, high bonding strength and excellent yellowing resistance is prepared by matching polyether and polyester polyol, using 2000-5000 with high molecular weight as polyether polyol, using sulfonate polyester polyol with molecular weight of 1000-2000 as polyester polyol, using small molecular sulfonate glycol as chain extender and 450-550 with molecular weight of 450-550, adding water for dispersion after polymerization is completed by using HMDI or IPDI, and using amine of sulfonate as the chain extender. However, the formula of the polyurethane adhesive disclosed by the publication also comprises a hydrophilic chain extender, and both carboxyl and sulfonic group in the hydrophilic chain extender can accelerate hydrolysis of polyester, so that the hydrolysis resistance of the adhesive is influenced.
In view of the above, it is important to develop an aqueous polyurethane having excellent hydrolysis resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyurethane adhesive, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a polyurethane adhesive, wherein the polyurethane adhesive is prepared from raw materials including polyurethane resin and a curing agent;
the polyurethane resin comprises the following raw materials in percentage by weight:
in the polyurethane adhesive, polyethyleneimine in a specific proportion is matched with a curing agent during curing, and intramolecular micro-crosslinking is formed, so that the final tension and hydrolysis resistance of the waterborne polyurethane adhesive are greatly improved; compared with dimethylolpropionic acid in the prior art, the guanidino amine salt chain extender can avoid serious hydrolysis of polyester caused by carboxyl, greatly improves the storage stability and hydrolysis resistance of the waterborne polyurethane, and can also quickly crosslink carbonyl groups in a guanidino and waterborne polyurethane film through hydrogen bonds, so that the hydrophobicity of the film is increased, and the water absorption rate is reduced.
In the present invention, the weight percentage of the polyester polyol is 22.0% to 28.5%, such as 23%, 24%, 25%, 26%, 27%, 28%, etc.
The weight percentage of the guanidine-based salt chain extender is 0.7% -1.3%, such as 0.8%, 0.9%, 1%, 1.1%, 1.2% and the like.
The weight percentage of the glycol chain extender is 0.1% -0.2%, such as 0.12%, 0.14%, 0.16%, 0.18% and the like.
The weight percentage of the diisocyanate is 3.5% to 7.0%, such as 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, etc.
The weight percentage of the catalyst is 0.02-0.1%, such as 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09% and the like.
The weight percentage of the polyethyleneimine is 0.7% -1.1%, such as 0.8%, 0.9%, 1.0% and the like.
The weight percentage of the diluent is 35% -40%, such as 36%, 37%, 38%, 39%, etc.
The weight percentage of the water is up to 100%.
Preferably, the mass percentage of the curing agent is 2% to 3%, such as 2.2%, 2.4%, 2.6%, 2.8%, etc., based on 100% of the total mass of the polyurethane resin.
Preferably, the curing agent comprises a glycidyl ether curing agent.
In the invention, the curing agent is preferably a glycidyl ether curing agent, and can be better matched and used with polyethyleneimine to form a polyurethane adhesive with excellent performance.
Preferably, the curing agent comprises any one or a combination of at least two of trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil triglycidyl ether or sorbitol tetraglycidyl ether, wherein typical but non-limiting combinations include: a combination of trimethylolpropane triglycidyl ether and trimethylolethane triglycidyl ether, a combination of hydroxymethylethane triglycidyl ether, castor oil triglycidyl ether and sorbitol tetraglycidyl ether, a combination of trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil triglycidyl ether and sorbitol tetraglycidyl ether, and the like.
Preferably, the polyester polyol comprises any one or a combination of at least two of polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polybutylene adipate, or 1,3 propylene adipate, wherein typical but non-limiting combinations include: combinations of polyethylene glycol adipate and polybutylene adipate, combinations of 1,3 propylene glycol adipate and polybutylene adipate, and the like.
Preferably, the polyester polyol has a number average molecular weight of 1000-3000g/mol, such as 1200g/mol, 1400g/mol, 1600g/mol, 1800g/mol, 2000g/mol, 2200g/mol, 2400g/mol, 2600g/mol, and the like.
Preferably, the preparation raw materials of the guanidine-based salt chain extender comprise dimethylolpropionic acid and at least one guanidine-based compound.
Preferably, the guanidino compound comprises a primary methyleneamine in its structure.
Preferably, the guanidino compound comprises any one or at least two combinations of biguanidino hexylamine, biguanidino butylamine, or biguanidino n-octylamine, wherein typical but non-limiting combinations include: a combination of biguanidinohexamine and biguanidinobutylamine, a combination of biguanidinobutylamine and biguanidino-n-octylamine, a combination of biguanidinohexamine, biguanidinobutylamine and biguanidino-n-octylamine, and the like.
Preferably, the glycol chain extender comprises any one or a combination of at least two of 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol or 2-methylpropanediol, with typical but non-limiting combinations including: a combination of 1, 4-butanediol and 1, 6-hexanediol, a combination of neopentyl glycol and 2-methylpropanediol, and the like.
Preferably, the polyethyleneimine has a number average molecular weight of 3000-10000g/mol, such as 4000g/mol, 5000g/mol, 6000g/mol, 7000g/mol, 8000g/mol, 9000g/mol, and the like.
Preferably, the diisocyanate comprises a non-yellowing isocyanate.
Preferably, the diisocyanate comprises any one or a combination of at least two of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, or dicyclohexylmethane diisocyanate, wherein typical but non-limiting combinations include: combinations of isophorone diisocyanate and 1, 6-hexamethylene diisocyanate, combinations of 1, 6-hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, combinations of isophorone diisocyanate and dicyclohexylmethane diisocyanate, and the like.
Preferably, the catalyst comprises any one or a combination of at least two of dibutyltin dilaurate, stannous octoate, or organobismuth, wherein typical but non-limiting combinations include: combinations of dibutyltin dilaurate and stannous octoate, stannous octoate and organobismuth, dibutyltin dilaurate, stannous octoate and organobismuth, and the like.
Preferably, the diluent comprises acetone.
In a second aspect, the present invention provides a method for preparing the polyurethane adhesive according to the first aspect, wherein the method comprises the following steps:
(1) mixing polyester polyol, a guanidinium salt chain extender, a glycol chain extender, diisocyanate and a catalyst according to a formula amount, cooling after a first heat preservation reaction, adding a diluent and polyethyleneimine, performing a second heat preservation reaction, adding water, emulsifying and distilling to obtain polyurethane resin;
(2) and mixing polyurethane resin with a curing agent to obtain the polyurethane adhesive.
In the invention, the synthesis process of the polyurethane adhesive is extremely simple and convenient, only two steps are needed, the reaction time is short, the requirement on industrial production equipment is not high, the production period can be shortened, and the cost can be reduced.
Preferably, in step (1), the polyester polyol is subjected to dehydration treatment before mixing.
Preferably, the dehydration treatment comprises distillation under reduced pressure.
Preferably, the temperature of the reduced pressure distillation is 110-120 ℃, such as 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃ and the like.
Preferably, the time of the reduced pressure distillation is 1 to 3h, such as 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, 2.8h and the like.
Preferably, in step (1), the temperature of the mixing is 60 to 65 ℃, such as 61 ℃, 62 ℃, 63 ℃, 64 ℃ and the like.
Preferably, the temperature of the first incubation reaction is 70-85 deg.C, such as 72 deg.C, 74 deg.C, 76 deg.C, 78 deg.C, 80 deg.C, 82 deg.C, 84 deg.C, etc.
Preferably, the first incubation time is 2-3h, such as 2.1h, 2.2h, 2.4h, 2.6h, 2.8h, etc.
Preferably, the cooling temperature is 50-60 deg.C, such as 52 deg.C, 54 deg.C, 56 deg.C, 58 deg.C, etc.
Preferably, the diluent is added in a manner including dropwise addition.
Preferably, the rate of the dropwise addition is 20-60mL/min, such as 25mL/min, 30mL/min, 35mL/min, 40mL/min, 45mL/min, 50mL/min, 55mL/min, and the like.
Preferably, the temperature of the second incubation reaction is 30-45 deg.C, such as 32 deg.C, 34 deg.C, 36 deg.C, 38 deg.C, 40 deg.C, 42 deg.C, 44 deg.C, etc.
Preferably, the time of the second incubation reaction is 0.5 to 1h, such as 0.6h, 0.7h, 0.8h, 0.9h, and the like.
Preferably, the water addition further comprises stirring.
Preferably, the stirring rate is 2000-6000rpm, such as 2500rpm, 3000rpm, 3500rpm, 4000rpm, 4500rpm, 5000rpm, 5500rpm and the like.
Preferably, in step (2), the mixing means includes stirring.
Preferably, the stirring rate is 200-300rpm, such as 220rpm, 240rpm, 260rpm, 280rpm, and the like.
Preferably, the stirring time is 5-10min, such as 6min, 7min, 8min, 9min, and the like.
Preferably, said steps (1) and (2) are carried out under a protective atmosphere.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) carrying out reduced pressure distillation on the polyester polyol at the temperature of 110-120 ℃ for 1-3h to finish dehydration treatment;
under the protective atmosphere, mixing the dehydrated polyester polyol, the guanidinium salt chain extender, the glycol chain extender, the diisocyanate and the catalyst according to the formula amount at the temperature of 60-65 ℃, heating to 70-85 ℃, carrying out heat preservation reaction for 2-3h for the first time, cooling to 50-60 ℃, and dropwise adding the diluent at the rate of 20-60 mL/min;
then adding polyethyleneimine, carrying out a second heat preservation reaction for 0.5-1h at 30-45 ℃, adding water, stirring at 2000-6000rpm until complete emulsification, and carrying out reduced pressure distillation to obtain polyurethane resin;
(2) and stirring the polyurethane resin and the curing agent at the speed of 200-300rpm for 5-10min to obtain the polyurethane adhesive.
In a third aspect, the present invention provides a use of the polyurethane adhesive of the first aspect in rubber bonding.
Compared with the prior art, the invention has the following beneficial effects:
(1) the polyurethane adhesive disclosed by the invention has excellent chemical resistance, resistance to wet heat hydrolysis and adhesion, and the water absorption rate is kept at a low level.
(2) The tensile force of the polyurethane adhesive is more than 9.8Kgf/cm, the moisture and heat resistance hydrolysis is more than 128h, and the water absorption rate is less than 6.6%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides an aqueous polyurethane adhesive comprising a polyurethane resin and trimethylolpropane triglycidyl ether in an amount of 3% of the polyurethane resin.
The polyurethane resin comprises the following raw materials in percentage by weight of 100 percent:
24% of polybutylene adipate (molecular weight 2000g/mol, purchased from Zhejiang Huafeng synthetic resin and having a trademark of PE3020), 1.0% of biguanide-based hexamethylene amine salt chain extender, 0.13% of 1, 4-butanediol, 1.0% of isophorone diisocyanate, 4.0% of 1, 6-hexamethylene diisocyanate, 0.05% of dibutyltin dilaurate, 37% of acetone, 0.9% of polyethyleneimine (molecular weight 3000g/mol, purchased from Basff and having a trademark of polyethyleneimine FG) and 100% of deionized water.
The waterborne polyurethane adhesive is prepared by the following method, and the method comprises the following steps:
a. adding polybutylene adipate, biguanide-based hexane amine salt chain extender and 1, 4-butanediol into a four-neck flask provided with a condenser tube and a thermometer, carrying out reduced pressure distillation at 110 ℃ for 1.5h, and cooling to 60 ℃;
b. mixing dehydrated polybutylene adipate, biguanide hexylamine salt chain extender and 1, 4-butanediol with isophorone diisocyanate, 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate at 60 ℃ in a nitrogen protection atmosphere, heating to 75 ℃, and carrying out a first heat preservation reaction for 3 hours;
c. cooling to 55 ℃ for the first time, and dripping acetone at the rate of 40 mL/min;
d. adding polyethyleneimine, and carrying out a second heat preservation reaction at 40 ℃ for 30 min;
e. adding deionized water, stirring at 2000rpm until complete emulsification, and distilling under reduced pressure to remove acetone to obtain polyurethane resin (solid content 50%, average particle diameter 0.32 μm);
adding trimethylolpropane triglycidyl ether into polyurethane resin before application and construction, and stirring at 300rpm for 10min to obtain the polyurethane adhesive.
Example 2
This example provides an aqueous polyurethane adhesive comprising a polyurethane resin and trimethylolpropane triglycidyl ether in an amount of 3% of the polyurethane resin.
The polyurethane resin comprises the following raw materials in percentage by weight of 100 percent:
22% of polyethylene glycol adipate (molecular weight of 2000g/mol, purchased from Zhejiang Huafeng synthetic resin and having a mark of PE1020), 1.1% of biguanide-based hexylamine salt chain extender, 0.1% of 1, 6-hexanediol, 6.2% of 1, 6-hexamethylene diisocyanate, 0.05% of dibutyltin dilaurate, 40% of acetone, 1.1% of polyethyleneimine (molecular weight of 3000g/mol, purchased from Basff and having a mark of polyethyleneimine FG) and deionized water to 100%.
The waterborne polyurethane adhesive is prepared by the following method, and the method comprises the following steps:
a. adding polyethylene glycol adipate, biguanide-based hexane amine salt chain extender and 1, 6-hexanediol into a four-neck flask provided with a condenser pipe and a thermometer, distilling at 110 ℃ under reduced pressure for 1.5h, and cooling to 60 ℃;
b. mixing the dehydrated polyethylene glycol adipate, biguanide hexylamine salt chain extender and 1, 6-hexanediol with 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate at 60 ℃ in a nitrogen protection atmosphere, heating to 75 ℃, and carrying out a first heat preservation reaction for 3 hours;
c. cooling to 55 ℃, and dropwise adding acetone at the rate of 20 mL/min;
d. adding polyethyleneimine, and carrying out a second heat preservation reaction at 35 ℃ for 30 min;
e. adding deionized water, stirring at 2000rpm until complete emulsification, and distilling under reduced pressure to remove acetone to obtain the polyurethane resin (solid content is 50%, and average particle size is 0.35 μm);
before application and construction, trimethylolpropane triglycidyl ether is added into polyurethane resin, and the polyurethane resin is stirred for 10min at 300rpm to obtain the polyurethane adhesive.
Example 3
This example provides an aqueous polyurethane adhesive comprising a polyurethane resin and 2% trimethylolethane triglycidyl ether of the polyurethane resin.
The polyurethane resin comprises the following raw materials in percentage by weight of 100 percent:
16 percent of polyhexamethylene glycol adipate (with the molecular weight of 2000g/mol, which is purchased from Huafeng synthetic resin in Zhejiang river and has the brand number of PE5020), 6 percent of polybutanediol adipate (with the molecular weight of 2000g/mol, which is purchased from Huafeng synthetic resin and has the brand number of PE3020), 0.7 percent of biguanidino butylamine salt chain extender, 0.2 percent of neopentyl glycol, 0.5 percent of isophorone diisocyanate, 3.0 percent of 1, 6-hexamethylene diisocyanate, 0.02 percent of organic bismuth, 40 percent of acetone, 0.7 percent of polyethyleneimine (with the molecular weight of 4000g/mol, which is purchased from Basff and has the brand number of polyethyleneimine WF) and 100 percent of deionized water.
The waterborne polyurethane adhesive is prepared by the following method, and the method comprises the following steps:
a. adding poly (hexamethylene adipate), poly (butylene adipate), biguanide butylamine salt chain extender and neopentyl glycol into a four-neck flask provided with a condenser tube and a thermometer, distilling at 110 ℃ under reduced pressure for 1.5h, and cooling to 60 ℃;
b. mixing dehydrated polyhexamethylene adipate, polybutanediol adipate, biguanidino butylamine salt chain extender and neopentyl glycol with isophorone diisocyanate, 1, 6-hexamethylene diisocyanate and organic bismuth at 60 ℃ in a nitrogen protection atmosphere, heating to 75 ℃, and carrying out a first heat preservation reaction for 3 hours;
c. cooling to 55 ℃, and dripping acetone at the speed of 60 mL/min;
d. adding polyethyleneimine, and carrying out a second heat preservation reaction at 35 ℃ for 30 min;
e. adding deionized water, stirring at 2000rpm until complete emulsification, and distilling under reduced pressure to remove acetone to obtain the polyurethane resin (solid content is 50%, and average particle size is 0.3 μm);
before application and construction, the polyurethane adhesive is obtained by adding trimethylolethane triglycidyl ether into polyurethane resin and stirring at 300rpm for 10 min.
Example 4
This example provides an aqueous polyurethane adhesive comprising a polyurethane resin and 3% castor oil triglycidyl ether based on the polyurethane resin.
The polyurethane resin comprises the following raw materials in percentage by weight of 100 percent:
28.5 percent of poly butylene glycol adipate (molecular weight of 2000G/mol, purchased from Huafeng synthetic resin in Zhejiang province, and having the mark of PE1320), 1.3 percent of biguanidino n-octylamine salt chain extender, 0.1 percent of 2-methylpropanediol, 7.0 percent of dicyclohexyl methane diisocyanate, 0.1 percent of stannous octoate, 35 percent of acetone, 1.1 percent of polyethyleneimine (molecular weight of 10000G/mol, purchased from Basff, and having the mark of polyethyleneimine G100) and 100 percent of deionized water.
The waterborne polyurethane adhesive is prepared by the following method, and the method comprises the following steps:
a. adding poly (ethylene glycol adipate), bis (guanidino-n-octylamine) salt chain extender and 0.1% of 2-methylpropanediol into a four-neck flask provided with a condenser and a thermometer, distilling at 110 ℃ under reduced pressure for 1.5h, and cooling to 60 ℃;
b. in the atmosphere of nitrogen protection, mixing dehydrated polyethylene glycol adipate, biguanidino n-octylamine salt chain extender, 2-methylpropanediol, 7.0% dicyclohexylmethane diisocyanate and 0.1% stannous octoate at 60 ℃, heating to 75 ℃, and carrying out a first heat preservation reaction for 2.5 hours;
c. cooling to 55 ℃, and dripping acetone at the speed of 40 mL/min;
d. adding polyethyleneimine, and carrying out a second heat preservation reaction at 40 ℃ for 30 min;
e. adding deionized water, stirring at 2000rpm until complete emulsification, and distilling under reduced pressure to remove acetone to obtain the polyurethane resin (solid content is 50%, and average particle size is 0.28 μm);
before application and construction, adding the castor oil triglycidyl ether into the polyurethane resin, and stirring at 300rpm for 10min to obtain the polyurethane adhesive.
Example 5
This example provides an aqueous polyurethane adhesive comprising a polyurethane resin and 2% sorbitol tetraglycidyl ether of the polyurethane resin.
The polyurethane resin comprises the following raw materials in percentage by weight of 100 percent:
25% of poly 1, 3-propylene glycol adipate (molecular weight of 3000g/mol, purchased from Huafeng synthetic resin in Zhejiang province, and having the mark of PE8837), 0.8% of biguanidino n-octylamine salt chain extender, 0.15% of neopentyl glycol, 5.9% of dicyclohexyl methane diisocyanate, 0.04% of stannous octoate, 40% of acetone, 1.0% of polyethyleneimine (molecular weight of 4000g/mol, purchased from Bass, and having the mark of polyethyleneimine WF) and 100% of deionized water.
The waterborne polyurethane adhesive is prepared by the following method, and the method comprises the following steps:
a. adding poly (1, 3-propylene glycol adipate), biguanide n-octylamine salt chain extender and neopentyl glycol into a four-neck flask provided with a condenser tube and a thermometer, distilling at 110 ℃ under reduced pressure for 1.5h, and cooling to 60 ℃;
b. mixing dehydrated poly 1,3 propylene glycol adipate, bis-guanidino n-octylamine salt chain extender, neopentyl glycol, dicyclohexylmethane diisocyanate and stannous octoate at 60 ℃ in a nitrogen protection atmosphere, heating to 75 ℃, and carrying out a first heat preservation reaction for 3 hours;
c. cooling to 55 ℃, and dripping acetone at the speed of 40 mL/min;
d. adding polyethyleneimine, and carrying out a second heat preservation reaction at 40 ℃ for 30 min;
e. adding deionized water, stirring at 2000rpm until complete emulsification is achieved, and distilling under reduced pressure to remove acetone to obtain the polyurethane resin (solid content is 50%, and average particle size is 0.31 μm);
before application and construction, sorbitol tetraglycidyl ether is added into polyurethane resin, and stirring is carried out at 300rpm for 10min, so as to obtain the polyurethane adhesive.
Example 6
This example provides an aqueous polyurethane adhesive comprising a polyurethane resin and 2% sorbitol tetraglycidyl ether of the polyurethane resin.
The polyurethane resin comprises the following raw materials in percentage by weight of 100 percent:
8% of poly-1, 3-propylene glycol adipate (molecular weight of 3000g/mol, purchased from Huafeng synthetic resin in Zhejiang province, and having the brand number of PE8837), 17.6% of poly-butylene glycol adipate (molecular weight of 2000g/mol, purchased from Huafeng synthetic resin, and having the brand number of PE3020), 1.2% of biguanide-based hexamethylene amine salt chain extender, 0.17% of 1, 6-hexanediol, 1.0% of dicyclohexyl methane diisocyanate, 2.9% of 1, 6-hexamethylene diisocyanate, 0.07% of organic bismuth, 39% of acetone, 0.9% of polyethyleneimine (molecular weight of 4000g/mol, purchased from Basff, and having the brand number of polyethyleneimine WF) and 100% of deionized water.
The waterborne polyurethane adhesive is prepared by the following method, and the method comprises the following steps:
a. adding poly adipic acid 1,3 propylene glycol ester, poly adipic acid butanediol ester, biguanide group hexane amine salt chain extender and 1, 6-hexanediol into a four-neck flask provided with a condenser tube and a thermometer, distilling at 110 ℃ under reduced pressure for 1.5h, and cooling to 60 ℃;
b. mixing the dehydrated poly (1, 3-propylene glycol adipate), poly (butylene glycol adipate), biguanide-based hexamethylene amine salt chain extender and 1, 6-hexanediol with dicyclohexylmethane diisocyanate, 1, 6-hexamethylene diisocyanate and organic bismuth at 60 ℃ in a nitrogen protection atmosphere, heating to 75 ℃, and carrying out a first heat preservation reaction for 3 hours;
c. cooling to 55 ℃, and dripping acetone at the speed of 40 mL/min;
d. adding polyethyleneimine, and carrying out a second heat preservation reaction at 40 ℃;
e. adding deionized water, stirring at 2000rpm until complete emulsification, and distilling under reduced pressure to remove acetone to obtain the polyurethane resin (solid content is 50%, and average particle size is 0.3 μm);
before application and construction, sorbitol tetraglycidyl ether is added into polyurethane resin, and stirring is carried out at 300rpm for 10min, so as to obtain the polyurethane adhesive.
Example 7
This example provides an aqueous polyurethane adhesive comprising a polyurethane resin and trimethylolpropane triglycidyl ether in an amount of 2% of the polyurethane resin.
The polyurethane resin comprises the following raw materials in percentage by weight of 100 percent:
10% of polybutylene adipate (molecular weight 2000G/mol, purchased from Huafeng synthetic resin in Zhejiang province, and having the brand number of PE3020), 12.8% of polyethylene adipate (molecular weight 2000G/mol, purchased from Huafeng synthetic resin, and having the brand number of PE1020), 0.7% of biguanide butylamine salt chain extender, 0.12% of neopentyl glycol, 4.8% of 1, 6-hexamethylene diisocyanate, 0.04% of dibutyltin dilaurate, 37% of acetone, 1.0% of polyethyleneimine (molecular weight 10000G/mol, purchased from Basff, and having the brand number of polyethyleneimine G100), and 100% of deionized water.
The waterborne polyurethane adhesive is prepared by the following method, and the method comprises the following steps:
a. adding polybutylene adipate, polyethylene glycol adipate, biguanide butylamine salt chain extender and neopentyl glycol into a four-neck flask provided with a condenser tube and a thermometer, distilling at 110 ℃ under reduced pressure for 1.5h, and cooling to 60 ℃;
b. mixing dehydrated polybutylene adipate, polyethylene glycol adipate, biguanide butylamine salt chain extender and neopentyl glycol with 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate at 60 ℃ in a nitrogen protection atmosphere, heating to 75 ℃, and carrying out a first heat preservation reaction for 3 hours;
c. cooling to 55 ℃, and dripping acetone at the speed of 40 mL/min;
d. adding polyethyleneimine, and carrying out a second heat preservation reaction at 40 ℃ for 30 min;
e. adding deionized water, stirring at 2000rpm until complete emulsification is achieved, and distilling under reduced pressure to remove acetone to obtain the polyurethane resin (solid content is 50%, and average particle size is 0.3 um);
before application and construction, trimethylolpropane triglycidyl ether is added into polyurethane resin, and stirring is carried out at 300rpm for 10min, so as to obtain the polyurethane adhesive.
Example 8
This example provides an aqueous polyurethane adhesive comprising a polyurethane resin and trimethylolpropane triglycidyl ether in an amount of 2% of the polyurethane resin.
The polyurethane resin comprises the following raw materials in percentage by weight of 100 percent:
23.4 percent of polybutylene adipate (molecular weight of 2000g/mol, purchased from Zhejiang Huafeng synthetic resin and having the brand number of PE3020), 1.1 percent of biguanide hexylamine salt chain extender, 0.14 percent of 2-methylpropanediol, 2 percent of isophorone diisocyanate, 4.5 percent of 1, 6-hexamethylene diisocyanate, 0.09 percent of organic bismuth, 40 percent of acetone, 1.0 percent of polyethyleneimine (molecular weight of 4000g/mol, purchased from Basff and having the brand number of polyethyleneimine WF) and 100 percent of deionized water.
The waterborne polyurethane adhesive is prepared by the following method, and the method comprises the following steps:
a. adding polybutylene adipate, biguanide-based hexane amine salt chain extender and 2-methyl propylene glycol into a four-neck flask provided with a condenser tube and a thermometer, carrying out reduced pressure distillation at 110 ℃ for 1.5h, and cooling to 60 ℃;
b. mixing dehydrated polybutylene adipate, biguanide-based hexamethylene amine salt chain extender and 2-methyl propylene glycol with isophorone diisocyanate, 1, 6-hexamethylene diisocyanate and organic bismuth at 60 ℃ in a nitrogen protection atmosphere, heating to 75 ℃, and carrying out a first heat preservation reaction for 3 hours;
c. cooling to 55 ℃, and dripping acetone at the speed of 40 mL/min;
d. adding polyethyleneimine, and carrying out a second heat preservation reaction at 40 ℃ for 30 min;
e. adding deionized water, stirring at 2000rpm until complete emulsification is achieved, and distilling under reduced pressure to remove acetone to obtain the polyurethane resin (solid content is 50%, and average particle size is 0.35 um);
and adding trimethylolpropane triglycidyl ether into the waterborne polyurethane adhesive before application and construction, and stirring at 300rpm for 10min to obtain the polyurethane adhesive.
Example 9
This example provides an aqueous polyurethane adhesive comprising a polyurethane resin and 2% castor oil triglycidyl ether based on the polyurethane resin.
The polyurethane resin comprises the following raw materials in percentage by weight of 100 percent:
27% of polybutylene adipate (molecular weight of 2000g/mol, purchased from Huafeng synthetic resin in Zhejiang province, and having the brand number of PE3020), 0.7% of biguanidino n-octylamine salt chain extender, 0.12% of 1, 4-butanediol, 2% of isophorone diisocyanate, 5% of 1, 6-hexamethylene diisocyanate, 0.06% of organic bismuth, 38% of acetone, 0.9% of polyethyleneimine (molecular weight of 4000g/mol, purchased from Basv, and having the brand number of polyethyleneimine WF) and 100% of deionized water.
The waterborne polyurethane adhesive is prepared by the following method, and the method comprises the following steps:
a. adding polybutylene adipate, biguanide n-octylamine salt chain extender and 1, 4-butanediol into a four-neck flask provided with a condenser tube and a thermometer, carrying out reduced pressure distillation at 110 ℃ for 1.5h, and cooling to 60 ℃;
b. mixing dehydrated polybutylene adipate, biguanidino n-octylamine salt chain extender and 1, 4-butanediol with isophorone diisocyanate, 1, 6-hexamethylene diisocyanate and organic bismuth at 60 ℃ in a nitrogen protection atmosphere, heating to 75 ℃, and carrying out a first heat preservation reaction for 3 hours;
c. cooling to 55 ℃, and dripping acetone at the speed of 40 mL/min;
d. adding polyethyleneimine, and carrying out a second heat preservation reaction at 40 ℃ for 30 min;
e. adding deionized water, stirring at 2000rpm until complete emulsification, and distilling under reduced pressure to remove acetone to obtain the polyurethane resin (solid content is 50%, and average particle size is 0.4 μm);
before application and construction, adding the castor oil triglycidyl ether into the polyurethane resin, and stirring at 300rpm for 10min to obtain the polyurethane adhesive.
Comparative example 1
This comparative example provides an aqueous polyurethane adhesive comprising a polyurethane resin and trimethylolpropane triglycidyl ether accounting for 3% of the polyurethane resin.
The polyurethane resin comprises the following raw materials in percentage by weight of 100 percent:
24.3 percent of polybutylene adipate (with the molecular weight of 2000g/mol, which is purchased from Huafeng synthetic resin and has the brand number of PE3020), 1.1 percent of biguanide-based hexamethylene amine salt chain extender, 0.19 percent of 1, 4-butanediol, 1.0 percent of isophorone diisocyanate, 4.0 percent of 1, 6-hexamethylene diisocyanate, 0.05 percent of dibutyltin dilaurate, 38 percent of acetone, 0.2 percent of ethylenediamine and deionized water to 100 percent.
The waterborne polyurethane adhesive is prepared by the following method, and the method comprises the following steps:
a. adding polybutylene adipate, biguanide-based hexane amine salt chain extender and 1, 4-butanediol into a four-neck flask provided with a condenser tube and a thermometer, carrying out reduced pressure distillation at 110 ℃ for 1.5h, and cooling to 60 ℃;
b. mixing dehydrated polybutylene adipate, biguanide-based hexane amine salt chain extender and 1, 4-butanediol with isophorone diisocyanate, 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate at 60 ℃ in a nitrogen protection atmosphere, heating to 75 ℃, and carrying out a first heat preservation reaction for 3 hours;
c. cooling to 55 ℃, and dripping acetone at the speed of 40 mL/min;
d. adding ethylenediamine, and carrying out a second heat preservation reaction at 30 ℃ for 30 min;
e. adding deionized water, stirring at 2000rpm until complete emulsification, and distilling under reduced pressure to remove acetone to obtain the polyurethane resin (solid content is 50%, and average particle size is 0.32 μm);
before application and construction, trimethylolpropane triglycidyl ether is added into polyurethane resin, and the polyurethane resin is stirred for 10min at 300rpm to obtain the polyurethane adhesive.
Comparative example 2
This comparative example differs from example 1 in that the weight percent of polyethyleneimine is 1.5%, and the remainder is the same as in example 1.
Comparative example 3
This comparative example differs from example 1 in that the aqueous polyurethane adhesive does not include trimethylolpropane triglycidyl ether, and is otherwise the same as example 1.
Comparative example 4
This comparative example provides an aqueous polyurethane adhesive comprising a polyurethane resin and trimethylolpropane triglycidyl ether in an amount of 3% based on the polyurethane resin.
The polyurethane resin comprises the following raw materials in percentage by weight of 100 percent:
23.9% of polybutylene adipate (molecular weight 2000g/mol, available from Huafeng synthetic resin and having the brand number of PE3020), 1.0% of dimethylolpropionic acid, 0.13% of 1, 4-butanediol, 1.0% of isophorone diisocyanate, 4.0% of 1, 6-hexamethylene diisocyanate, 0.05% of dibutyltin dilaurate, 37% of acetone, 0.9% of polyethyleneimine (molecular weight 3000g/mol, available from Basff and having the brand number of polyethyleneimine FG), 0.21% of triethylamine and 100% of deionized water.
The waterborne polyurethane adhesive is prepared by the following method, and the method comprises the following steps:
a. adding polybutylene adipate, dimethylolpropionic acid and 1, 4-butanediol into a four-neck flask provided with a condenser tube and a thermometer, carrying out reduced pressure distillation at 110 ℃ for 1.5h, and cooling to 60 ℃;
b. mixing dehydrated polybutylene adipate, dimethylol propionic acid and 1, 4-butanediol with isophorone diisocyanate, 1, 6-hexamethylene diisocyanate and dibutyltin dilaurate at 60 ℃ in a nitrogen protection atmosphere, heating to 75 ℃, and carrying out a first heat preservation reaction for 3 hours;
c. cooling to 55 ℃, and dripping acetone at the speed of 40 mL/min;
d. adding polyethyleneimine, and carrying out a second heat preservation reaction at 40 ℃ for 30 min;
e. adding triethylamine, and continuing to perform a third heat preservation reaction for 25min, wherein the temperature is consistent with the second heat preservation temperature;
f. adding deionized water, stirring at 2000rpm until complete emulsification, and distilling under reduced pressure to remove acetone to obtain polyurethane resin (solid content 50%, average particle diameter 0.22 μm);
before application and construction, trimethylolpropane triglycidyl ether is added into polyurethane resin, and stirring is carried out at 300rpm for 10min, so as to obtain the polyurethane adhesive.
Comparative example 5
This comparative example differs from example 1 in that the weight percent of biguanide hexylamine salt chain extender is 1.4%, the weight percent of 1, 4-butanediol is 0.03%, and the remainder is the same as example 1.
Comparative example 6
The comparative example is different from example 1 in that trimethylolpropane triglycidyl ether is replaced by equal mass of carbodiimide curing agent (available from Shanghai Huafeng New Material research & development science Co., Ltd., under the designation Hustab-160), and the rest is the same as example 1.
Performance testing
The aqueous polyurethane adhesives described in examples 1-9 and comparative examples 1-6 were tested as follows:
(1) and (3) testing tension: the rubber is coated on two rubber strips which are subjected to surface polishing and pretreatment by a brush, the rubber strips are bonded by bonding and pressurizing after thermal activation, and the tensile force is tested according to the national standard GB/T2791-1995 after the rubber strips are placed for 2 days at room temperature.
(2) Testing of resistance to wet heat hydrolysis: coating the mixture on two rubber strips subjected to surface polishing and pretreatment by using a brush, and bonding by bonding and pressurizing after thermal activation; after being placed at room temperature for 2 days, the mixture is suspended in a constant temperature and humidity box, and the weight is 1Kg, and the humidity is 95 percent at 70 ℃. The time for complete peeling of the two rubber strips bonded together was monitored.
(3) Water absorption test of pure films: preparing a PU film with the dry film thickness of 60 mu m, placing the PU film in an oven for drying at 100 ℃ for 1 day, completely soaking the dried PU film in water for 24 hours, taking out the PU film, absorbing the water on the surface, calculating the mass difference before and after water absorption, and dividing the mass difference by the original mass to obtain the water absorption rate (%).
(4) Chemical resistance: preparing PU film with dry film thickness of 60 μm, drying in oven at 100 deg.C for 1 day, soaking in 50% ethanol solution for 12h, and observing whether the film is whitish, soft, sticky, and abnormal if it is whitish, soft, sticky.
The above tests were repeated three times and the mean value was taken.
The test results are summarized in table 1.
TABLE 1
| Numbering | Tension Kgf/cm | Resistance to wet heat hydrolysis | Water absorption rate | Resistance to chemical attack |
| Example 1 | 11.2 | 128h | 6.2％ | Is normal |
| Example 2 | 10.8 | 135h | 5.6％ | Is normal |
| Practice ofExample 3 | 11.6 | 142h | 6.6％ | Is normal |
| Example 4 | 11.8 | 132h | 6.3％ | Is normal |
| Example 5 | 12.1 | 148h | 5.9％ | Is normal |
| Example 6 | 11.2 | 130h | 4.9％ | Is normal |
| Example 7 | 10.6 | 141h | 5.2％ | Is normal |
| Example 8 | 11.7 | 143h | 5.6％ | Is normal |
| Example 9 | 10.3 | 128h | 6.4％ | Is normal |
| Comparative example 1 | 7.2 | 82h | 7.2％ | Whitening hair |
| Comparative example 2 | 5.2 | 100h | 8.1％ | Is normal |
| Comparative example 3 | 8.8 | 75h | 8.9％ | Whitening hair |
| Comparative example 4 | 7.5 | 54h | 14％ | Whitening hair |
| Comparative example 5 | 8.2 | 98h | 8.8％ | Is normal and normal |
| Comparative example 6 | 9.1 | 102h | 7.8％ | Whitening hair |
Analysis of the data in Table 1 shows that the polyurethane adhesive of the present invention has a tensile force of 9.8Kgf/cm or more, a resistance to wet heat hydrolysis of 128h or more, and a water absorption of 6.6% or less, and that the polyurethane adhesive of the present invention has excellent resistance to chemical, resistance to wet heat hydrolysis, and adhesion, and the water absorption is kept at a low level.
As can be seen from the analysis of comparative examples 1-2 and example 1, comparative examples 1-2 are inferior to example 1, and it is confirmed that the polyurethane adhesive formed by polyethyleneimine is more excellent in the range of 0.7% to 1.1%.
As can be seen from the analysis of comparative example 3 and example 1, comparative example 3 is inferior to example 1 in performance, and the setting of the curing agent, especially the glycidyl ether curing agent, in the polyurethane adhesive is proved to be better in performance.
As can be seen from the analysis of comparative examples 4-5 and example 1, comparative examples 4-5 are inferior to example 1 in performance, and the resulting polyurethane adhesive having a guanidinium salt chain extender in an amount ranging from 0.7% to 1.3% by weight has better performance.
As can be seen from the analysis of comparative example 6 and example 1, comparative example 6 is inferior to example 1 in performance, and the performance of the polyurethane adhesive formed by the preferred glycidyl ether curing agent of the present invention is better.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The polyurethane adhesive is characterized in that the preparation raw materials of the polyurethane adhesive comprise polyurethane resin and a curing agent;
the polyurethane resin comprises the following raw materials in percentage by weight:
2. the polyurethane adhesive according to claim 1, wherein the curing agent is present in an amount of 2 to 3% by mass based on 100% by mass of the polyurethane resin;
preferably, the curing agent comprises a glycidyl ether curing agent;
preferably, the curing agent comprises any one or a combination of at least two of trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil triglycidyl ether or sorbitol tetraglycidyl ether.
3. The polyurethane adhesive of claim 1 or 2, wherein the polyester polyol comprises any one or a combination of at least two of polyethylene glycol adipate, polybutylene adipate, polyhexamethylene adipate, polybutylene adipate, or polypropylene 1,3 adipate;
preferably, the number average molecular weight of the polyester polyol is 1000-3000 g/mol.
4. The polyurethane adhesive of any one of claims 1-3, wherein the guanidine-based salt chain extender is prepared from raw materials comprising dimethylolpropionic acid and at least one guanidine-based compound;
preferably, the guanidino compound comprises a primary methyleneamine in the structure;
preferably, the guanidino compound comprises any one or at least two of biguanidino hexylamine, biguanidino butylamine or biguanidino n-octylamine;
preferably, the glycol chain extender comprises any one or a combination of at least two of 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol or 2-methylpropanediol.
5. The polyurethane adhesive of any one of claims 1-4, wherein the polyethyleneimine has a number average molecular weight of 3000-10000 g/mol.
6. The polyurethane adhesive of any one of claims 1-5, wherein the diisocyanate comprises a non-yellowing isocyanate;
preferably, the diisocyanate comprises any one or at least two of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate or dicyclohexylmethane diisocyanate;
preferably, the catalyst comprises any one or at least two of dibutyltin dilaurate, stannous octoate or organic bismuth in combination;
preferably, the diluent comprises acetone.
7. A method for preparing the polyurethane adhesive of any one of claims 1-6, wherein the method comprises the steps of:
(1) mixing polyester polyol, a guanidinium salt chain extender, a glycol chain extender, diisocyanate and a catalyst according to a formula amount, cooling after a first heat preservation reaction, adding a diluent and polyethyleneimine, performing a second heat preservation reaction, adding water, emulsifying and distilling to obtain polyurethane resin;
(2) and mixing polyurethane resin with a curing agent to obtain the polyurethane adhesive.
8. The production method according to claim 7, wherein in the step (1), the polyester polyol is subjected to dehydration treatment before mixing;
preferably, the dehydration treatment comprises distillation under reduced pressure;
preferably, the temperature of the reduced pressure distillation is 110-120 ℃;
preferably, the time of the reduced pressure distillation is 1-3 h;
preferably, in the step (1), the temperature of the mixing is 60-65 ℃;
preferably, the temperature of the first heat preservation reaction is 70-85 ℃;
preferably, the time of the first heat preservation reaction is 2-3 h;
preferably, the temperature of the cooling is 50-60 ℃;
preferably, the addition mode of the diluent comprises dripping;
preferably, the dropping rate is 20-60 mL/min;
preferably, the temperature of the second heat preservation reaction is 30-45 ℃;
preferably, the time of the second heat preservation reaction is 0.5-1 h;
preferably, the water is added and then stirred;
preferably, the stirring rate is 2000-;
preferably, in step (2), the mixing manner includes stirring;
preferably, the stirring rate is 200-300 rpm;
preferably, the stirring time is 5-10 min;
preferably, said steps (1) and (2) are carried out under a protective atmosphere.
9. The method according to claim 7 or 8, characterized in that it comprises the steps of:
(1) carrying out reduced pressure distillation on the polyester polyol at the temperature of 110-120 ℃ for 1-3h to finish dehydration treatment;
under the protective atmosphere, mixing the dehydrated polyester polyol, the guanidinium salt chain extender, the glycol chain extender, the diisocyanate and the catalyst according to the formula amount at the temperature of 60-65 ℃, heating to 70-85 ℃, carrying out heat preservation reaction for 2-3h for the first time, cooling to 50-60 ℃, and dropwise adding the diluent at the rate of 20-60 mL/min;
then adding polyethyleneimine, carrying out a second heat preservation reaction for 0.5-1h at 30-45 ℃, adding water, stirring at 2000-6000rpm until complete emulsification, and carrying out reduced pressure distillation to obtain polyurethane resin;
(2) and stirring the polyurethane resin and the curing agent at the speed of 200-300rpm for 5-10min to obtain the polyurethane adhesive.
10. Use of the polyurethane adhesive of any one of claims 1-6 in rubber bonding.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH08311144A (en) * | 1995-05-16 | 1996-11-26 | Dainippon Ink & Chem Inc | Aqueous dispersion of crosslinked polyurethane resin particle |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08311144A (en) * | 1995-05-16 | 1996-11-26 | Dainippon Ink & Chem Inc | Aqueous dispersion of crosslinked polyurethane resin particle |
Non-Patent Citations (2)
| Title |
|---|
| B. ZHAO 等: "Design and synthesis of antibacterial waterborne fluorinated polyurethane", 《J. APPL. POLYM. SCI》, vol. 136, no. 2, pages 46923 - 46923 * |
| 张孜文 等: "聚六亚甲基胍盐酸盐改性非离子型抗菌水性聚氨酯脲分散体的制备与性能", 《高分子材料科学与工程》, vol. 36, no. 6, pages 110 - 117 * |
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