CN117050710A - Polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth and preparation method and application thereof - Google Patents
Polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth and preparation method and application thereof Download PDFInfo
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- CN117050710A CN117050710A CN202311115143.2A CN202311115143A CN117050710A CN 117050710 A CN117050710 A CN 117050710A CN 202311115143 A CN202311115143 A CN 202311115143A CN 117050710 A CN117050710 A CN 117050710A
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- main agent
- polyurethane adhesive
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 88
- 239000000853 adhesive Substances 0.000 title claims abstract description 87
- 239000004744 fabric Substances 0.000 title claims abstract description 74
- 238000005406 washing Methods 0.000 title claims abstract description 68
- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 114
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 41
- 150000002009 diols Chemical class 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 230000007062 hydrolysis Effects 0.000 claims abstract description 27
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 27
- 239000004970 Chain extender Substances 0.000 claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 239000012948 isocyanate Substances 0.000 claims abstract description 22
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 22
- 239000011324 bead Substances 0.000 claims abstract description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 18
- 239000004417 polycarbonate Substances 0.000 claims abstract description 18
- 230000001737 promoting effect Effects 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 9
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 41
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 39
- 238000005886 esterification reaction Methods 0.000 claims description 38
- 230000032050 esterification Effects 0.000 claims description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 24
- 238000006297 dehydration reaction Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 125000004427 diamine group Chemical group 0.000 claims description 8
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 8
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 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 6
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 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 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 4
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 4
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000012795 verification Methods 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 21
- 239000002585 base Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- -1 carrier Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 230000036626 alertness Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C08G18/3237—Polyamines aromatic
- C08G18/324—Polyamines aromatic containing only one aromatic ring
-
- 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth, a preparation method and application thereof, wherein the adhesive is a solvent polyurethane system, and comprises a main agent, a curing agent, an adhesion promoting auxiliary agent and a solvent, wherein the mass of the curing agent is 4-10% of the mass of the main agent, and the mass of the adhesion promoting auxiliary agent is 1% of the mass of the main agent3% of the total weight of the composition. The main agent adopts hydroxyl-terminated prepolymer prepared from polyester polyol, polycarbonate diol, isocyanate, chain extender, anti-hydrolysis agent, catalyst, silane coupling agent and ethyl acetate; the chain extender is prepared from micromolecular dihydric alcohol and diamine. The polyurethane adhesive disclosed by the invention is a high-end product for the reflective material industry, can be used for compounding a high-end bright silver bead membrane and a cloth base, and the compounded reflective cloth has excellent flexibility, high temperature resistance and hydrolysis resistance, and can meet the ENISO6330-2012 international industrial washing standard: retroreflective index after 50 times of washing (alkali addition) at 90 DEG C >150cd/(lx·m 2 ) And the cost is low, and compared with the products of the same type at home and abroad, the method has obvious price advantage.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth, and a preparation method and application thereof.
Background
The manufacturing principle of the reflective cloth is that glass beads with high refractive index are adhered to the surface of a cloth base by a coating or film laminating process, so that the common cloth can reflect incident light irradiated on the common cloth according to the direction of an original light source, and the visibility of the common cloth is improved, and therefore the common cloth is manufactured into clothing or other articles. The bright color of the light source can play an obvious warning role in daytime, and the bright light reflecting effect can effectively enhance the recognition capability of people at night or under the condition of insufficient light, so that the target can be seen clearly, the alertness is caused, the accident occurrence is avoided, the casualties are reduced, the economic loss is reduced, and the light source has obvious social benefit.
The reflective adhesive is an adhesive applied to the field of reflective materials such as reflective cloth and the like, and can realize firm bonding of glass beads and cloth base. The composite structure of the high-end bright silver bead membrane is generally as follows: bright silver bead planting film (surface glass bead// transparent resin// metal reflective coating)// adhesive// cloth base. In the using process of the reflective cloth material, daily washing and airing are needed, so that the adhesive and the used material have high requirements on the adhesive property. The adhesive is required to have good bonding strength on each composite layer, and higher flexibility, heat resistance, hydrolysis resistance and the like.
At present, the adhesive for the middle-high-end reflective cloth is usually a double-component polyurethane adhesive, the technology is mostly a huge monopoly of foreign adhesives, the strength of domestic adhesive manufacturers in the aspect of compounding high-end reflective materials is still relatively weak, most of commercial products are medium-low-end water washing, and the adhesive can be applied to a few industrial washing adhesive products with a high-end bright silver bead planting film and cloth base in compound adhesion. The conventional polyurethane adhesive produced at home often has the problem that the heat resistance and the water-resistant washing resistance are not perfectly coordinated, for example, the washing times at 90 ℃ are lower than 10 times, the glass beads are seriously fallen off, the actual use requirement cannot be met, and the price of a high-end product is still very expensive.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth, and a preparation method and application thereof, wherein the polyurethane adhesive is applied to compounding of a high-end bright silver bead-implanted film and a cloth base, and the compounded reflective cloth has excellent flexibility, high temperature resistance and hydrolysis resistance, and can meet the ENISO6330-2012 international industrial washing standard: retroreflective index after 50 times of washing (alkali addition) at 90 DEG C>150cd/(lx·m 2 ) And further solves the technical problems existing in the prior art.
The invention aims at realizing the following technical scheme:
the embodiment of the invention provides a polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth, which consists of a main agent, a curing agent, an adhesion promoting auxiliary agent and a solvent, wherein the mass of the curing agent is 4-10% of that of the main agent, and the mass of the adhesion promoting auxiliary agent is 1-3% of that of the main agent;
the main agent adopts hydroxyl-terminated prepolymer prepared from polyester polyol, polycarbonate diol, isocyanate, chain extender, silane coupling agent, anti-hydrolysis agent, catalyst and ethyl acetate; the solid content of the hydroxyl-terminated prepolymer is 45 to 60 weight percent, and the rotational viscosity at 25 ℃ is 5000 to 12000 mPa.s;
the curing agent is an ethyl acetate solution of isocyanate prepolymer, the NCO content is 10-15 wt% and the solid content is 70-77%;
the adhesion promoting auxiliary agent is at least one of (3-aminopropyl) trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidol ether oxypropyl trimethoxysilane, gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane;
the solvent adopts ethyl acetate which has the moisture content of less than or equal to 300ppm and does not contain alcohols and active hydroxyl solvents.
Preferably, in the adhesive, the main agent comprises the following components in parts by mass:
29 to 43 parts by mass of polyester polyol,
3 to 6 parts by mass of polycarbonate diol,
4.7 to 6.1 parts by mass of isocyanate,
0.9 to 1.6 parts by mass of chain extender,
0.28 to 0.32 mass portion of silane coupling agent,
0.5 to 2 parts by mass of hydrolysis resistance agent,
0.01 to 0.05 mass portion of catalyst,
46-65 parts by mass of ethyl acetate.
Preferably, in the adhesive, the average molecular weight of the polyester polyol in the main agent is 1500-2600, and the hydroxyl value is 43-78 mgKOH/g; the polyester polyol is synthesized from dihydric alcohol, dibasic acid, an antioxidant and an esterification catalyst.
Preferably, in the above adhesive, in the polyester polyol of the main agent, the dihydric alcohol adopts at least two of ethylene glycol, diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, methyl propylene glycol and neopentyl glycol, and the side chain group dihydric alcohol accounts for 31-43% of the total mass of the dihydric alcohol;
the dibasic acid in the polyester polyol of the main agent adopts aromatic dibasic acid and aliphatic dibasic acid, and the aromatic dibasic acid accounts for 38-62% of the total mass of the dibasic acid; wherein, the aromatic dibasic acid adopts at least two of isophthalic acid, terephthalic acid and phthalic anhydride; the aliphatic dibasic acid adopts at least one of adipic acid, succinic acid, sebacic acid and azelaic acid;
The antioxidant is triphenyl phosphite;
the esterification catalyst is tetra-n-butyl titanate.
Preferably, in the above adhesive, the average molecular weight of the polycarbonate diol in the main agent is 2000;
the isocyanate in the main agent is at least one of 2, 4-toluene diisocyanate, 2,4' -diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
Preferably, in the above adhesive, the chain extender in the main agent is small molecular diol and diamine.
Preferably, in the chain extender of the adhesive, the small molecular dihydric alcohol adopts at least one of ethylene glycol, diethylene glycol, 1, 6-hexanediol and 1, 4-butanediol;
the diamine adopts diethyl toluenediamine.
Preferably, in the above adhesive, the hydrolysis inhibitor in the main agent is hydrolysis inhibitor 1010.
The embodiment of the invention also provides a preparation method of the polyurethane adhesive for the 90 ℃ industrial washing-resistant reflective cloth, which comprises the following steps:
preparing a main agent:
adding 29-43 parts by mass of polyester polyol, 3-6 parts by mass of polycarbonate diol, 0.6-1 part by mass of micromolecular diol and 0.5-2 parts by mass of hydrolysis resistance agent into a reaction kettle, uniformly mixing, sequentially adding 0.01-0.05 part by mass of catalyst and 4.7-6.1 parts by mass of isocyanate, heating to 80-85 ℃ for reacting for 2-3 hours, adding 0.3-0.6 part by mass of diamine chain extender for continuous reaction for 1-2 hours, then reducing the system temperature to 60 ℃, and adding 0.28-0.32 part by mass of silane coupling agent and 46-65 parts by mass of solvent to prepare a main agent with the solid content of 45-60 wt% and the rotational viscosity of 5000-12000 mPa.s at 25 ℃;
Preparing an adhesive:
uniformly mixing a main agent, a curing agent, an auxiliary agent and a solvent according to the mass ratio of 100:4-10:1-3:15-44 to obtain the polyurethane adhesive for the 90 ℃ resistant industrial washing reflective cloth according to any one of claims 1-8.
Preferably, in the above method, the polyester polyol in the main agent is prepared in the following manner, comprising:
esterification reaction: adding dihydric alcohol, dibasic acid, antioxidant and esterification catalyst into a reaction kettle, stirring, heating to 150-170 ℃ to start dehydration, and then gradually heating to 220-240 ℃; the temperature of the distiller is controlled at 95-105 ℃; after esterification and dehydration for 8-12 hours, detecting the acid value of the system to be less than or equal to 10mgKOH/g;
polycondensation reaction: after the esterification dehydration reaction is finished, vacuumizing the reaction kettle, controlling the temperature to be 220-240 ℃, performing dealcoholization reaction, gradually increasing negative pressure by vacuumizing according to-0.02 MPA, -0.04MPA, -0.06MPA and-0.08 MPA, vacuumizing each section for 0.5-1 hour, performing long vacuumizing operation, wherein the vacuum degree reaches 0.1MPA, and the long vacuumizing time is 0.5-3 hours until the acid value of a product is less than or equal to 1.0mgKOH/g and the hydroxyl value of the product reaches 43-78 mgKOH/g, thus obtaining the polyester polyol; wherein the molar ratio of hydroxyl contained in the dihydric alcohol to carboxyl contained in the dibasic acid is 1.23-1.39:1, and the aromatic dibasic acid accounts for 38-62% of the total mass of the dibasic acid.
The embodiment of the invention further provides an application mode of the polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth, which comprises the following steps:
(1) Coating: the coating thickness is controlled to be 12-20 filaments by using a coating tool, and the polyurethane adhesive for the 90 ℃ industrial washing-resistant reflective cloth is uniformly coated on a bright silver bead-planting film;
(2) Predrying: placing the coated bright silver bead membrane in an oven, and adjusting the temperature rising rate of the oven to gradually rise from 25 ℃ to 90 ℃ for 5-10 min;
(3) Thermal compounding: placing the cloth substrate and the bright silver bead membrane on a composite press roll to carry out hot press at the hot press temperature of 80-100 ℃ and the pressure of 0.3-0.6 MPA;
(4) Curing: curing the composite film after hot pressing in the environment of 60-80 ℃ for 48-72 hours, placing a weight of 2kg on the film to help pressing curing, peeling off the PE waste film after curing, naturally placing and curing for 24-48 hours, and then carrying out water washing verification and comparison results.
Compared with the prior art, the polyurethane adhesive for the 90 ℃ resistant industrial washing reflective cloth, and the preparation method and the application thereof, provided by the invention, have the beneficial effects that:
because the main agent is hydroxyl-terminated polyester polyol prepared from aromatic dibasic acid, aliphatic dibasic acid and dihydric alcohol in a specific proportion, wherein the aromatic dibasic acid containing a benzene ring structure can provide better heat resistance for the polyester polyol, and the long-chain aliphatic dibasic acid and the straight-chain dihydric alcohol can meet enough softness of the polyester polyol, and the side chain dihydric alcohol can increase the crosslinking density of the system so as to further enhance the hydrolysis resistance. Therefore, the invention reasonably selects and designs the proportion of the dibasic acid and the dibasic alcohol with different structures from the synthesis angle of the polyester polyol, and achieves perfect coordination of the high temperature resistance, the hydrolysis resistance and the softness of the adhesive layer of the polyester polyol; and secondly, part of polycarbonate diol is doped in the synthesis of the main agent, so that compared with the conventional polyester polyol, the polyurethane can effectively improve the durability, hydrolysis resistance and chemical resistance of polyurethane, improve the softness of a glue layer and meet the application requirements of reflective materials such as reflective cloth and the like. In the application process of the composite reflective cloth, the adhesive force promoting auxiliary agent is additionally added when the adhesive working solution is prepared so as to further improve the bonding performance of the adhesive to the base material. The main agent, the curing agent, the auxiliary agent and the solvent are mixed according to a certain proportion and then are used for compounding the high-end bright silver bead planting film and the cloth base, and the compounded reflective cloth has excellent flexibility, high temperature resistance and hydrolysis resistance and can meet the ENISO6330-2012 international industrial washing standard: retroreflective index after 50 times of washing (alkali addition) at 90 DEG C >150cd/(lx·m 2 ) And the cost is low, and compared with the corresponding products at home and abroad, the method has obvious price advantage.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below in combination with the specific content of the invention; it will be apparent that the described embodiments are only some embodiments of the invention, but not all embodiments, which do not constitute limitations of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The terms that may be used herein will first be described as follows:
the term "and/or" is intended to mean that either or both may be implemented, e.g., X and/or Y are intended to include both the cases of "X" or "Y" and the cases of "X and Y".
The terms "comprises," "comprising," "includes," "including," "has," "having" or other similar referents are to be construed to cover a non-exclusive inclusion. For example: including a particular feature (e.g., a starting material, component, ingredient, carrier, formulation, material, dimension, part, means, mechanism, apparatus, step, procedure, method, reaction condition, processing condition, parameter, algorithm, signal, data, product or article of manufacture, etc.), should be construed as including not only a particular feature but also other features known in the art that are not explicitly recited.
The term "consisting of … …" is meant to exclude any technical feature element not explicitly listed. If such term is used in a claim, the term will cause the claim to be closed, such that it does not include technical features other than those specifically listed, except for conventional impurities associated therewith. If the term is intended to appear in only a clause of a claim, it is intended to limit only the elements explicitly recited in that clause, and the elements recited in other clauses are not excluded from the overall claim.
The term "parts by mass" means a mass ratio relationship between a plurality of components, for example: if the X component is described as X parts by mass and the Y component is described as Y parts by mass, the mass ratio of the X component to the Y component is expressed as x:y;1 part by mass may represent any mass, for example: 1 part by mass may be expressed as 1kg or 3.1415926 kg. The sum of the mass parts of all the components is not necessarily 100 parts, and may be more than 100 parts, less than 100 parts, or 100 parts or equal. The parts, proportions and percentages described herein are by mass unless otherwise indicated.
When concentrations, temperatures, pressures, dimensions, or other parameters are expressed as a range of values, the range is to be understood as specifically disclosing all ranges formed from any pair of upper and lower values within the range of values, regardless of whether ranges are explicitly recited; for example, if a numerical range of "2 to 8" is recited, that numerical range should be interpreted to include the ranges of "2 to 7", "2 to 6", "5 to 7", "3 to 4 and 6 to 7", "3 to 5 and 7", "2 and 5 to 7", and the like. Unless otherwise indicated, numerical ranges recited herein include both their endpoints and all integers and fractions within the numerical range.
The polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth, and the preparation method and application thereof provided by the invention are described in detail below. What is not described in detail in the embodiments of the present invention belongs to the prior art known to those skilled in the art. The specific conditions are not noted in the examples of the present invention and are carried out according to the conditions conventional in the art or suggested by the manufacturer. The reagents or apparatus used in the examples of the present invention were conventional products commercially available without the manufacturer's knowledge.
Preferably, in the polyester polyol of the main agent, at least two of ethylene glycol, diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, methyl propylene glycol and neopentyl glycol are adopted as the dihydric alcohol.
Preferably, in the polyester polyol of the main agent, the dibasic acid adopts aromatic dibasic acid and aliphatic dibasic acid, and the aromatic dibasic acid accounts for 38-62% of the total mass of the dibasic acid. Preferably, the aromatic dibasic acid is at least two of isophthalic acid, terephthalic acid and phthalic anhydride. The aliphatic dibasic acid adopts at least one of adipic acid, succinic acid, sebacic acid and azelaic acid.
Preferably, in the polyester polyol of the main agent, the antioxidant is triphenyl phosphite.
Preferably, in the polyester polyol of the main agent, the esterification catalyst is tetra-n-butyl titanate.
Preferably, in the main agent, the isocyanate is at least one of 2, 4-toluene diisocyanate, 2,4' -diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
Preferably, in the main agent, the adhesion promoting auxiliary agent is one of (3-aminopropyl) trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidol ether oxypropyl trimethoxysilane, gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane.
Preferably, the chain extender in the main agent is small molecular dihydric alcohol and diamine. The small molecular dihydric alcohol preferably adopts at least one of ethylene glycol, diethylene glycol, 1, 6-hexanediol and 1, 4-butanediol; the diamine adopts diethyl toluenediamine.
The embodiment of the invention provides a preparation method of the polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth, which comprises the following steps:
Preparing a main agent:
adding 29-43 parts by mass of polyester polyol, 3-6 parts by mass of polycarbonate diol, 0.6-1 part by mass of micromolecular diol and 0.5-2 parts by mass of hydrolysis resistance agent into a reaction kettle, uniformly mixing, sequentially adding 0.01-0.05 part by mass of catalyst and 4.7-6.1 parts by mass of isocyanate, heating to 80-85 ℃ for reacting for 2-3 hours, adding 0.3-0.6 part by mass of diamine chain extender for continuous reaction for 1-2 hours, then reducing the system temperature to 60 ℃, and adding 0.28-0.32 part by mass of silane coupling agent and 46-65 parts by mass of ethyl acetate to prepare a main agent with the solid content of 45-60 wt% and the rotational viscosity of 5000-12000 mPa.s at 25 ℃;
the curing agent is an ethyl acetate solution of isocyanate prepolymer, the NCO content of the curing agent is 10-15 wt% and the solid content of the curing agent is 70-77%;
and uniformly mixing the main agent, the curing agent, the adhesion promoting auxiliary agent and the solvent according to the mass ratio of 100:4-10:1-3:15-44, thus obtaining the polyurethane adhesive for the 90 ℃ industrial washing-resistant reflective cloth.
Preferably, in the above method, the polyester polyol used as the main agent has an average molecular weight of 1500 to 2600 and a hydroxyl value of 43 to 78mgKOH/g, is synthesized from a diol, a dibasic acid, an antioxidant and an esterification catalyst, and has a molar ratio of hydroxyl groups contained in the diol to carboxyl groups contained in the dibasic acid of 1.23 to 1.39:1; in the dihydric alcohol, the side chain group dihydric alcohol accounts for 31-43% of the total mass of the dihydric alcohol.
The average molecular weight of the polycarbonate diol is 2000. Commercially available YC-2565, preferably of the metary chemistry, can be used.
The solvent adopts ethyl acetate, the moisture content is less than or equal to 300ppm, and the solvent does not contain alcohols and active hydroxyl solvents.
Preferably, the polyester polyol used in the above main agent is prepared in the following manner, comprising:
esterification reaction: adding dihydric alcohol, dibasic acid, antioxidant and esterification catalyst into a reaction kettle, stirring, heating to 150-170 ℃ to start dehydration, and then gradually heating to 220-240 ℃; the temperature of the distiller is controlled between 95 ℃ and 105 ℃; after esterification and dehydration for 8-12 hours, detecting the acid value of the system to be less than or equal to 10mgKOH/g;
polycondensation reaction: after the esterification dehydration reaction is finished, vacuumizing the reaction kettle, controlling the temperature to be 220-240 ℃, performing dealcoholization reaction, gradually increasing negative pressure by vacuumizing according to-0.02 MPA, -0.04MPA, -0.06MPA and-0.08 MPA, vacuumizing each section for 0.5-1 hour, performing long vacuumizing operation, wherein the vacuum degree reaches 0.1MPA, and the long vacuumizing time is 0.5-3 hours until the acid value of a product is less than or equal to 1.0mgKOH/g and the hydroxyl value of the product reaches 43-78 mgKOH/g, thus obtaining the polyester polyol;
In the polyester polyol, the molar ratio of hydroxyl groups contained in the dihydric alcohol to carboxyl groups contained in the dibasic acid is 1.23-1.39:1; in the dihydric alcohol, the side chain group dihydric alcohol accounts for 31-43% of the total mass of the dihydric alcohol.
The polyurethane adhesive for the 90 ℃ industrial washing-resistant reflective cloth is used for bonding and compositing a high-end bright silver bead-implanted film and a cloth base.
The embodiment of the invention provides a polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth, which consists of a main agent, a curing agent, an adhesion promoting auxiliary agent and a solvent, wherein the mass of the curing agent is 4-10% of that of the main agent, and the mass of the adhesion promoting auxiliary agent is 1-3% of that of the main agent;
wherein, the polyurethane adhesive for the 90 ℃ resistant industrial washing reflective cloth can comprise the following embodiments:
(1) The main agent is a hydroxyl-terminated prepolymer prepared from 29 to 43 parts by mass of polyester polyol, 3 to 6 parts by mass of polycarbonate diol, 0.6 to 1 part by mass of micromolecular diol, 0.5 to 2 parts by mass of hydrolysis inhibitor, 0.01 to 0.05 part by mass of catalyst, 4.7 to 6.1 parts by mass of isocyanate, 0.3 to 0.6 part by mass of diamine chain extender, 0.28 to 0.32 part by mass of silane coupling agent and 46 to 65 parts by mass of ethyl acetate, wherein the solid content of the hydroxyl-terminated prepolymer is 45 to 60wt%, and the rotational viscosity at 25 ℃ is 5000 to 12000 mPa.s.
Wherein the average molecular weight of the polyester polyol is 1500-2600 and the hydroxyl value is 43-78 mgKOH/g.
The average molecular weight of the polycarbonate diol is 2000. Commercially available YC-2565, which is preferably of Yuan Li chemical, may be used.
(2) The curing agent is ethyl acetate solution of isocyanate prepolymer, the NCO content is 10-15 wt% and the solid content is 70-77%; commercially available curing agents, preferably the German ColorChemicals L-75 curing agent, can be used.
(3) The adhesion promoting auxiliary agent is at least one of (3-aminopropyl) trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidol ether oxypropyl trimethoxysilane, gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane. The adhesive force promoting auxiliary agent is selected during the preparation and application of the adhesive, so that the bonding capability of the polyurethane adhesive to glass beads and cloth base can be further improved.
(4) The solvent adopts ethyl acetate, the moisture content is less than or equal to 300ppm, and the solvent does not contain alcohols and active hydroxyl solvents.
Specifically, the main agent in the polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth can adopt the following embodiments:
(11) The polyester polyol is synthesized from dihydric alcohol, dibasic acid, an antioxidant and an esterification catalyst, and the molar ratio of hydroxyl contained in the dihydric alcohol to carboxyl contained in the dibasic acid is 1.23-1.39:1; in the dihydric alcohol, the side chain group dihydric alcohol accounts for 31-43% of the total mass of the dihydric alcohol.
(1) In the preparation of the polyester polyol, the dihydric alcohol adopts at least two of ethylene glycol, diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, methyl propylene glycol and neopentyl glycol.
(2) In the preparation of the raw materials of the polyester polyol, the dibasic acid adopts aromatic dibasic acid and aliphatic dibasic acid, and the aromatic dibasic acid accounts for 38-62% of the total mass of the dibasic acid; the aromatic dibasic acid adopts at least two of isophthalic acid, terephthalic acid and phthalic anhydride; the aliphatic dibasic acid adopts at least one of adipic acid, succinic acid, sebacic acid and azelaic acid.
In the preparation of the raw materials of the polyester polyol, the antioxidant is triphenyl phosphite; the esterification catalyst adopts tetrabutyl titanate.
Specifically, the polyester polyol is prepared by taking 5 to 15 parts by weight of isophthalic acid, 8 to 20 parts by weight of terephthalic acid, 15 to 32 parts by weight of adipic acid, 18 to 35 parts by weight of diethylene glycol, 5 to 8 parts by weight of neopentyl glycol and 3 to 7 parts by weight of 1, 4-butanediol as raw materials, adding 0.01 to 0.03 part by weight of antioxidant and adding 0.01 to 0.03 part by weight of esterification catalyst, and carrying out esterification reaction and polycondensation reaction.
(4) In the preparation of the raw materials of the polyester polyol, the ethyl acetate is used as a solvent, the moisture content is less than or equal to 300ppm, and the active hydroxyl solvent is not contained.
(12) The isocyanate adopts at least one of 2, 4-Toluene Diisocyanate (TDI), 2,4' -diphenylmethane diisocyanate (MDI), hexamethylene Diisocyanate (HDI), dimethylene benzene diisocyanate (XDI), hexamethylene diisocyanate and isophorone diisocyanate; preferably at least one of 2, 4-toluene diisocyanate, 2,4' -diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate.
(13) The chain extender consists of micromolecular dihydric alcohol and diamine, wherein the micromolecular dihydric alcohol adopts at least one of ethylene glycol, diethylene glycol, 1, 6-hexanediol and 1, 4-butanediol. The doping amount is 0.6% -1%, preferably 1%;
the diamine adopts diethyl toluenediamine. The blending amount is 0.3-0.6% of the total mass of the formula, and the preferable dosage is 0.6% of the total mass of the formula.
The diethyl toluenediamine is selected as an amine chain extender, and compared with the amine chain extender commonly used in polyurethane laminating adhesives, the reaction speed of the diethyl toluenediamine containing a benzene ring structure and a polyurethane prepolymer is high, but the reaction process is relatively mild, the control is easy, and the gel and the bursting phenomenon can not occur. Branching and crosslinking are generated through the reaction of the adhesive and isocyanate groups, so that the adhesive strength, heat resistance, hydrolysis resistance and other performances of the adhesive on cloth groups and glass beads are improved.
(14) The hydrolysis inhibitor is hydrolysis inhibitor 1010, the adding amount is 0.5-2%, and the preferable dosage is 1%.
(15) The catalyst is organic bismuth, the doping amount is 0.01% -0.05%, and the preferable dosage is 0.03%.
(16) The ethyl acetate is a solvent, the moisture content is less than or equal to 300ppm, and the ethyl acetate does not contain an active hydroxyl solvent.
Further, the preparation method of the polyurethane adhesive for the 90 ℃ resistant industrial washing reflective cloth can comprise the following steps:
(1) Preparation of polyester polyol:
esterification reaction: adding dihydric alcohol, dibasic acid, antioxidant and esterification catalyst into a reaction kettle, stirring, heating to 150-170 ℃ to start dehydration, and then gradually heating to 220-240 ℃; the temperature of the distiller is controlled between 95 ℃ and 105 ℃; after esterification and dehydration for 8-12 hours, detecting the acid value of the system to be less than or equal to 10mgKOH/g;
polycondensation reaction: after the esterification dehydration reaction is finished, vacuumizing the reaction kettle, controlling the temperature to be 220-240 ℃, performing dealcoholization reaction, gradually increasing negative pressure by vacuumizing according to-0.02 MPA, -0.04MPA, -0.06MPA and-0.08 MPA, vacuumizing each section for 0.5-1 hour, performing long vacuumizing operation, wherein the vacuum degree reaches 0.1MPA, and the long vacuumizing time is 0.5-3 hours until the acid value of a product is less than or equal to 1.0mgKOH/g and the hydroxyl value of the product reaches 43-78 mgKOH/g, thereby preparing the polyester polyol;
Wherein the mol ratio of the hydroxyl contained in the dihydric alcohol to the carboxyl contained in the dibasic acid is 1.23-1.39:1; in the dihydric alcohol, side chain group dihydric alcohol accounts for 28-45% of the total mass of the dihydric alcohol, and aromatic dibasic acid accounts for 38-62% of the total mass of the dibasic acid.
(2) Preparing a main agent: adding 29-43 parts by mass of polyester polyol, 3-6 parts by mass of polycarbonate diol, 0.6-1 part by mass of micromolecular diol and 0.5-2 parts by mass of hydrolysis resistance agent into a reaction kettle, uniformly mixing, sequentially adding 0.01-0.05 part by mass of catalyst and 4.7-6.1 parts by mass of isocyanate, heating to 80-85 ℃ for reacting for 2-3 hours, adding 0.3-0.6 part by mass of diamine chain extender for continuous reaction for 1-2 hours, then reducing the system temperature to 60 ℃, and adding 0.28-0.32 part by mass of silane coupling agent and 46-65 parts by mass of ethyl acetate to prepare a main agent with the solid content of 45-60 wt% and the rotational viscosity of 5000-12000 mPa.s at 25 ℃;
(3) And (3) selecting a curing agent: the curing agent adopts isocyanate addition product, the NCO content is 10-15 wt% and the solid content is 70-77%; commercially available L-75 curing agents, preferably from Colorum Germany, can be used.
(4) Preparation of the adhesive: the main agent, the curing agent, the auxiliary agent and the solvent are uniformly mixed according to the mass ratio of 100:4-10:1-3:15-44, so that the polyurethane adhesive for the 90 ℃ resistant industrial washing reflective cloth is obtained.
The embodiment of the invention further provides an application of the polyurethane adhesive for the 90 ℃ industrial washing-resistant reflective cloth, which comprises the following steps:
(1) Coating: using a coating tool to control the coating thickness to be 12-20 filaments, and uniformly coating the polyurethane adhesive for the 90 ℃ resistant industrial washing reflective cloth according to any one of claims 1-7 on a bright silver bead-planting film;
(2) Predrying: placing the coated bright silver bead membrane in an oven, and adjusting the temperature rising rate of the oven to gradually rise from 25 ℃ to 90 ℃ for 5-10 min; in the step, according to experience, the dried rubber surface is optimally provided with fingerprints but not rubber by hand pressure;
(3) Thermal compounding: placing the cloth substrate and the bright silver bead membrane on a composite press roll to carry out hot press at the hot press temperature of 80-100 ℃ and the pressure of 0.3-0.6 MPA;
(4) Curing: curing the composite film after hot pressing in the environment of 60-80 ℃ for 48-72 hours, placing a weight of 2kg on the film to help pressing curing, peeling off the PE waste film after curing, naturally placing and curing for 24-48 hours, and then carrying out water washing verification and comparison results.
The polyurethane adhesive for the 90 ℃ industrial washing resistant reflective cloth provided by the invention can be used for compounding a high-end bright silver bead membrane and a cloth base, and the compounded reflective cloth has excellent flexibility, high temperature resistance and hydrolysis resistance, and can meet the ENISO6330-2012 international industrial washing standard: retroreflective index after 50 times of washing (alkali addition) at 90 DEG C>150cd/(lx·m 2 ) And the cost is low, and compared with the corresponding products at home and abroad, the method has obvious price advantage.
In summary, the embodiment of the invention has excellent bonding strength, flexibility, heat resistance and hydrolysis resistance, meets the 90 ℃ industrial water washing resistance standard specified in the ENISO6330-2012 international industrial washing standard, and can provide a solution for the high-temperature industrial washing requirement.
In order to clearly show the technical scheme and the technical effects, the polyurethane adhesive for the 90 ℃ industrial washing resistant reflective cloth and the preparation method thereof are described in detail in the following by using specific embodiments.
Example 1
The embodiment provides a polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth, and the preparation method thereof can comprise the following steps:
(1) Polyester polyol for preparing main agent:
(1) esterification and dehydration reaction: in a nitrogen atmosphere, adding isophthalic acid, terephthalic acid, adipic acid, diethylene glycol, neopentyl glycol and 1, 4-butanediol into a reaction kettle according to the mass ratio of 12:12:30:32:8:6, after all, adding 0.03 weight part of triphenyl phosphite and 0.03 weight part of tetra-n-butyl titanate, and heating to 150-170 ℃, wherein the reaction system starts to dehydrate; then gradually heating to 220-240 ℃; the temperature of the distiller is controlled between 95 ℃ and 105 ℃; after the esterification and dehydration are carried out for 8 hours, the esterification and dehydration reaction is completed, the water yield accounts for 12.6% of the total mass of the raw materials, and the acid value of a detection system is 7.9mgKOH/g;
(2) Polycondensation reaction: after the esterification dehydration reaction is finished, vacuumizing the reaction kettle, controlling the temperature to be 220-240 ℃, performing dealcoholization reaction, gradually increasing negative pressure by vacuumizing under the control of-0.02 MPA, -0.04MPA, -0.06MPA and-0.08 MPA, vacuumizing each section for 0.5 hour, and performing long vacuumizing operation until the vacuum degree reaches 0.1MPA and the long vacuumizing time is 1 hour until the hydroxyl value of the product reaches 56.39mgKOH/g and the acid value of the product is 0.24mgKOH/g, thereby preparing the polyester polyol;
(2) Preparing a main agent: adding 34 parts by mass of the prepared polyester polyol, 5 parts by mass of polycarbonate diol, 0.8 part by mass of micromolecular diol and 1 part by mass of hydrolysis inhibitor into a reaction kettle, uniformly mixing, sequentially adding 0.03 part by mass of catalyst and 5.2 parts by mass of isocyanate, heating to 85 ℃ for reacting for 2.5 hours, adding 0.5 part by mass of diamine chain extender, continuously reacting for 1 hour, then reducing the system temperature to 60 ℃, and adding 0.32 part by mass of silane coupling agent and 50 parts by mass of ethyl acetate to prepare the main agent with the solid content of 48.37wt% and the rotational viscosity of 6200 mPa.s at 25 ℃.
(3) And (3) selecting a curing agent: the curing agent is L-75 curing agent of German Kogyo.
(4) Selecting a solvent: the solvent adopts ethyl acetate, the moisture content is less than or equal to 300ppm, and the solvent does not contain alcohols and active hydroxyl solvents.
(5) Preparing an adhesive: the main agent, the curing agent, the adhesion promoting auxiliary agent and the solvent are uniformly mixed according to the mass ratio of 100:4:3:28.5, so that the polyurethane adhesive for the 90 ℃ resistant industrial washing reflective cloth is obtained.
Example 2
The embodiment provides a polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth, and the preparation method thereof can comprise the following steps:
(1) Polyester polyol for preparing main agent:
(1) esterification and dehydration reaction: in a nitrogen atmosphere, adding isophthalic acid, terephthalic acid, adipic acid, diethylene glycol, neopentyl glycol and 1, 4-butanediol into a reaction kettle according to the mass ratio of 12:10:30:34:7, after all, adding 0.03 weight part of triphenyl phosphite and 0.03 weight part of tetra-n-butyl titanate, and heating to 150-170 ℃, wherein the reaction system starts to dehydrate; then gradually heating to 220-240 ℃; the temperature of the distiller is controlled between 95 ℃ and 105 ℃; after the esterification and dehydration are carried out for 8 hours, the esterification and dehydration reaction is completed, the water yield accounts for 12.2% of the total mass of the raw materials, and the acid value of a detection system is 8.8mgKOH/g;
(2) polycondensation reaction: after the esterification dehydration reaction is finished, vacuumizing the reaction kettle, controlling the temperature to be 220-240 ℃, performing dealcoholization reaction, gradually increasing negative pressure by vacuumizing under the control of-0.02 MPA, -0.04MPA, -0.06MPA and-0.08 MPA, vacuumizing each section for 0.5 hour, and performing long vacuumizing operation until the vacuum degree reaches 0.1MPA and the long vacuumizing time is 1.5 hours until the hydroxyl value of a product reaches 44mgKOH/g and the acid value of the product is 0.17mgKOH/g, thereby preparing the polyester polyol;
(2) Preparing a main agent: adding 33 parts by mass of polyester polyol, 3 parts by mass of polycarbonate diol, 0.6 part by mass of micromolecular diol and 1 part by mass of hydrolysis inhibitor into a reaction kettle, uniformly mixing, sequentially adding 0.03 part by mass of catalyst and 5.1 parts by mass of isocyanate, heating to 85 ℃ for reacting for 2.5 hours, adding 0.6 part by mass of diamine chain extender for continuous reaction for 1 hour, then reducing the system temperature to 60 ℃, and adding 0.32 part by mass of silane coupling agent and 43 parts by mass of ethyl acetate to prepare the main agent with the solid content of 50.4wt% and the rotational viscosity of 5700 mPa.s at 25 ℃.
(3) And (3) selecting a curing agent: the curing agent is L-75 curing agent of German Kogyo.
(4) Selecting a solvent: the solvent adopts ethyl acetate, the moisture content is less than or equal to 300ppm, and the solvent does not contain alcohols and active hydroxyl solvents.
(5) Preparing an adhesive: the main agent, the curing agent, the adhesion promoting auxiliary agent and the solvent are uniformly mixed according to the mass ratio of 100:6:3:30.5, so that the polyurethane adhesive for the 90 ℃ resistant industrial washing reflective cloth is obtained.
Example 3
The embodiment provides a polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth, and the preparation method thereof can comprise the following steps:
(1) Preparation of polyester polyol:
(1) Esterification and dehydration reaction: in a nitrogen atmosphere, adding isophthalic acid, terephthalic acid, adipic acid, diethylene glycol, neopentyl glycol and 1, 4-butanediol into a reaction kettle according to the mass ratio of 12:14:28:33:7:6, after all, adding 0.03 weight part of triphenyl phosphite and 0.03 weight part of tetra-n-butyl titanate, and heating to 150-170 ℃, wherein the reaction system starts to dehydrate; then gradually heating to 220-240 ℃; the temperature of the distiller is controlled between 95 ℃ and 105 ℃; after the esterification and dehydration are carried out for 8 hours, the esterification and dehydration reaction is completed, the water yield accounts for 12.5% of the total mass of the raw materials, and the acid value of a detection system is 8.3mgKOH/g;
(2) polycondensation reaction: after the esterification dehydration reaction is finished, vacuumizing the reaction kettle, controlling the temperature to be 220-240 ℃, performing dealcoholization reaction, gradually increasing negative pressure by vacuumizing under the control of-0.02 MPA, -0.04MPA, -0.06MPA and-0.08 MPA, vacuumizing each section for 0.5 hour, and performing long vacuumizing operation until the vacuum degree reaches 0.1MPA and the long vacuumizing time is 0.5 hour until the acid value of a product is 0.14mgKOH/g and the hydroxyl value of the product reaches 65mgKOH/g, thereby preparing the polyester polyol;
(2) Preparing a main agent: adding 33 parts by mass of polyester polyol, 6 parts by mass of polycarbonate diol, 0.8 part by mass of micromolecular diol and 1.5 parts by mass of hydrolysis inhibitor into a reaction kettle, uniformly mixing, sequentially adding 0.03 part by mass of catalyst and 4.9 parts by mass of isocyanate, heating to 85 ℃ for reaction for 3 hours, adding 0.6 part by mass of diamine chain extender for continuous reaction for 1 hour, then reducing the system temperature to 60 ℃, and adding 0.3 part by mass of silane coupling agent and 38 parts by mass of ethyl acetate to prepare the main agent with the solid content of 55wt% and the rotational viscosity of 8600 mPa.s at 25 ℃.
(3) And (3) selecting a curing agent: the curing agent is L-75 curing agent of German Kogyo.
(4) Selecting a solvent: the solvent adopts ethyl acetate, the moisture content is less than or equal to 300ppm, and the solvent does not contain alcohols and active hydroxyl solvents.
(5) Preparing an adhesive: the main agent, the curing agent, the adhesion promoting auxiliary agent and the solvent are uniformly mixed according to the mass ratio of 100:10:2:34, so that the polyurethane adhesive for the 90 ℃ industrial washing-resistant reflective cloth is obtained.
And (3) performance detection:
the application and performance test methods of the polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth provided in the embodiment 1, the embodiment 2 and the embodiment 3 of the invention are as follows:
working solution concentration: 35 to 40 percent
Curing conditions: 60-80 ℃ for 48-72 h
Sizing thickness: 12-20 filaments
Composite structure: bright silver bead-planting film (surface glass bead// transparent resin// metal reflective coating)// adhesive// cloth base
Washing conditions: according to ENISO6330-2012 standard
Retroreflective coefficient determinator: roadvista 932
The results of 90 ℃ industry standard washing of the polyurethane adhesives (comparative example 1) for 90 ℃ industry washing reflective cloths of the same type as those sold in the market abroad in the examples 1, 2 and 3 of the present invention and the product of me (comparative example 2) with patent number CN100338165C are shown in table 1:
Table 1:
it can be seen from the summary that the embodiment of the invention is a reflective material prepared by compounding the high-end bright silver bead membrane and the cloth baseThe cloth had a retroreflective index comparable to that of comparative examples 1 and 2 before and after washing with water, and had a retroreflective index after washing with water (alkali addition) at 90℃for 50 times>150cd/(lx·m 2 ) The ENISO6330-2012 international industrial washing standard can be satisfied. The reflective cloth compounded by the embodiment of the invention has excellent softness, high temperature resistance and hydrolysis resistance, and has no appearance crack and no adhesive layer falling phenomenon after being washed for 50 times at 90 ℃. The cost of the adhesive of each embodiment of the invention is smaller than that of the adhesive of the comparative example 1 and the adhesive of the comparative example 2 by accounting the cost, and the adhesive has obvious price advantage on the premise of meeting the same performance.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims. The information disclosed in the background section herein is only for enhancement of understanding of the general background of the invention and is not to be taken as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Claims (10)
1. The polyurethane adhesive for the 90 ℃ industrial washing-resistant reflective cloth is characterized by comprising a main agent, a curing agent, an adhesion promoting auxiliary agent and a solvent, wherein the mass of the curing agent is 4-10% of that of the main agent, and the mass of the adhesion promoting auxiliary agent is 1-3% of that of the main agent;
the main agent adopts hydroxyl-terminated prepolymer prepared from polyester polyol, polycarbonate diol, isocyanate, chain extender, silane coupling agent, anti-hydrolysis agent, catalyst and ethyl acetate; the solid content of the hydroxyl-terminated prepolymer is 45 to 60 weight percent, and the rotational viscosity at 25 ℃ is 5000 to 12000 mPa.s;
the curing agent is an ethyl acetate solution of isocyanate prepolymer, the NCO content is 10-15 wt% and the solid content is 70-77%;
the auxiliary agent is at least one of (3-aminopropyl) trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidol ether oxypropyl trimethoxysilane, gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane;
the solvent adopts ethyl acetate which has the moisture content of less than or equal to 300ppm and does not contain alcohols and active hydroxyl solvents.
2. The polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth according to claim 1, wherein the main agent comprises the following components in parts by mass:
29 to 43 parts by mass of polyester polyol,
3 to 6 parts by mass of polycarbonate diol,
4.7 to 6.1 parts by mass of isocyanate,
0.9 to 1.6 parts by mass of chain extender,
0.28 to 0.32 mass portion of silane coupling agent,
0.5 to 2 parts by mass of hydrolysis resistance agent,
0.01 to 0.05 mass portion of catalyst,
46-65 parts by mass of ethyl acetate.
3. The polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth according to claim 1 or 2, wherein the average molecular weight of the polyester polyol in the main agent is 1500-2600, and the hydroxyl value is 43-78 mgKOH/g; the polyester polyol is synthesized from dihydric alcohol, dibasic acid, an antioxidant and an esterification catalyst.
4. The polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth according to claim 3, wherein in the polyester polyol of the main agent, at least two of ethylene glycol, diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, methyl propylene glycol and neopentyl glycol are adopted as the dihydric alcohol, and the dihydric alcohol with side chain groups accounts for 31-43% of the total mass of the dihydric alcohol;
The dibasic acid in the polyester polyol of the main agent adopts aromatic dibasic acid and aliphatic dibasic acid, and the aromatic dibasic acid accounts for 38-62% of the total mass of the dibasic acid; wherein, the aromatic dibasic acid adopts at least two of isophthalic acid, terephthalic acid and phthalic anhydride; the aliphatic dibasic acid adopts at least one of adipic acid, succinic acid, sebacic acid and azelaic acid;
the antioxidant is triphenyl phosphite;
the esterification catalyst is tetra-n-butyl titanate.
5. The polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth according to claim 1 or 2, wherein the average molecular weight of the polycarbonate diol in the main agent is 2000;
the isocyanate in the main agent is at least one of 2, 4-toluene diisocyanate, 2,4' -diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
6. The polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth according to claim 1 or 2, wherein the chain extender in the main agent is small molecular diol and diamine;
the hydrolysis inhibitor in the main agent is hydrolysis inhibitor 1010.
7. The polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth according to claim 6, wherein the chain extender is at least one of ethylene glycol, diethylene glycol, 1, 6-hexanediol and 1, 4-butanediol;
the diamine adopts diethyl toluenediamine.
8. A method for preparing the polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth according to any one of claims 1 to 7, which is characterized by comprising the following steps:
preparing a main agent:
adding 29-43 parts by mass of polyester polyol, 3-6 parts by mass of polycarbonate diol, 0.6-1 part by mass of micromolecular diol and 0.5-2 parts by mass of hydrolysis resistance agent into a reaction kettle, uniformly mixing, sequentially adding 0.01-0.05 part by mass of catalyst and 4.7-6.1 parts by mass of isocyanate, heating to 80-85 ℃ for reacting for 2-3 hours, adding 0.3-0.6 part by mass of diamine chain extender for continuous reaction for 1-2 hours, then reducing the system temperature to 60 ℃, and adding 0.28-0.32 part by mass of silane coupling agent and 46-65 parts by mass of solvent to prepare a main agent with the solid content of 45-60 wt% and the rotational viscosity of 5000-12000 mPa.s at 25 ℃;
preparing an adhesive:
uniformly mixing a main agent, a curing agent, an auxiliary agent and a solvent according to the mass ratio of 100:4-10:1-3:15-44 to obtain the polyurethane adhesive for the 90 ℃ resistant industrial washing reflective cloth according to any one of claims 1-7.
9. The method for preparing the polyurethane adhesive for the 90 ℃ industrial washing-resistant reflective cloth according to claim 8, wherein the polyester polyol in the main agent is prepared in the following manner, and comprises the following steps:
esterification reaction: adding dihydric alcohol, dibasic acid, antioxidant and esterification catalyst into a reaction kettle, stirring, heating to 150-170 ℃ to start dehydration, and then gradually heating to 220-240 ℃; the temperature of the distiller is controlled at 95-105 ℃; after esterification and dehydration for 8-12 hours, detecting the acid value of the system to be less than or equal to 10mgKOH/g;
polycondensation reaction: after the esterification dehydration reaction is finished, vacuumizing the reaction kettle, controlling the temperature to be 220-240 ℃, performing dealcoholization reaction, gradually increasing negative pressure by vacuumizing according to-0.02 MPA, -0.04MPA, -0.06MPA and-0.08 MPA, vacuumizing each section for 0.5-1 hour, performing long vacuumizing operation, wherein the vacuum degree reaches 0.1MPA, and the long vacuumizing time is 0.5-3 hours until the acid value of a product is less than or equal to 1.0mgKOH/g and the hydroxyl value of the product reaches 43-78 mgKOH/g, thus obtaining the polyester polyol; wherein the molar ratio of hydroxyl contained in the dihydric alcohol to carboxyl contained in the dibasic acid is 1.23-1.39:1, and the aromatic dibasic acid accounts for 38-62% of the total mass of the dibasic acid.
10. Use of the polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloths as claimed in any one of claims 1 to 7, characterized by comprising:
(1) Coating: using a coating tool to control the coating thickness to be 12-20 filaments, and uniformly coating the polyurethane adhesive for the 90 ℃ resistant industrial washing reflective cloth according to any one of claims 1-7 on a bright silver bead-planting film;
(2) Predrying: placing the coated bright silver bead membrane in an oven, and adjusting the temperature rising rate of the oven to gradually rise from 25 ℃ to 90 ℃ for 5-10 min;
(3) Thermal compounding: placing the cloth substrate and the bright silver bead membrane on a composite press roll to carry out hot press at the hot press temperature of 80-100 ℃ and the pressure of 0.3-0.6 MPA;
(4) Curing: curing the composite film after hot pressing in the environment of 60-80 ℃ for 48-72 hours, placing a weight of 2kg on the film to help pressing curing, peeling off the PE waste film after curing, naturally placing and curing for 24-48 hours, and then carrying out water washing verification and comparison results.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311115143.2A CN117050710A (en) | 2023-08-31 | 2023-08-31 | Polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311115143.2A CN117050710A (en) | 2023-08-31 | 2023-08-31 | Polyurethane adhesive for 90 ℃ resistant industrial washing reflective cloth and preparation method and application thereof |
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| CN117050710A true CN117050710A (en) | 2023-11-14 |
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| CN (1) | CN117050710A (en) |
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