CN116162434A - Epoxy modified low-VOC (volatile organic compound) double-component polyurethane adhesive and preparation method thereof - Google Patents
Epoxy modified low-VOC (volatile organic compound) double-component polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN116162434A CN116162434A CN202211699024.1A CN202211699024A CN116162434A CN 116162434 A CN116162434 A CN 116162434A CN 202211699024 A CN202211699024 A CN 202211699024A CN 116162434 A CN116162434 A CN 116162434A
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- epoxy modified
- polyurethane prepolymer
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- diisocyanate
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 64
- 239000000853 adhesive Substances 0.000 title claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 28
- 239000004814 polyurethane Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000012855 volatile organic compound Substances 0.000 title abstract description 16
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 59
- 229920005862 polyol Polymers 0.000 claims abstract description 17
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 10
- 229920003232 aliphatic polyester Polymers 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 43
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 33
- 229920000570 polyether Polymers 0.000 claims description 33
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 125000005442 diisocyanate group Chemical group 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920003054 adipate polyester Polymers 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- -1 polyoxypropylene Polymers 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 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 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000007789 sealing Methods 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 3
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000002318 adhesion promoter Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-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
- C09J175/08—Polyurethanes from polyethers
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of adhesives, and particularly relates to an epoxy modified low-VOC (volatile organic compound) double-component polyurethane adhesive and a preparation method thereof. The adhesive comprises the following components in parts by weight: (1) A component: 40-46 parts of epoxy modified polyurethane prepolymer A; 40-46 parts of low-viscosity polyurethane prepolymer B; 8-20 parts of a non-reactive plasticizer; (2) component B: 80-90 parts of aliphatic polyester polyol; 10-20 parts of a non-polyester polyol; 0.05-0.5 part of catalyst, wherein the volume ratio of the component A to the component B is 1:1. The polyurethane adhesive prepared by the invention contains no solvent, is suitable for adhering a polymer film to a substrate, has excellent mechanical properties, and can maintain good bonding and sealing effects after long-term use.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to an epoxy modified low-VOC (volatile organic compound) double-component polyurethane adhesive and a preparation method thereof.
Background
Polymeric roofing membranes are often used with adhesion to roofing substrates and can be made from a variety of polymeric materials such as ethylene propylene diene monomer rubber, thermoplastic olefins, polyvinyl chloride, and the like. Roofing membranes are typically made in wide sheets that are bonded together at seams to form a continuous membrane that is impermeable to water.
While roof membranes often require adhesion to the roof deck substrate by a variety of different adhesives. Most of these adhesives contain a large amount of solvents, which are not in compliance with environmental regulations, and thus, reduction of Volatile Organic Compounds (VOC) is very important.
At present, various adhesion promoters are often contained in adhesive compositions for adhering roof membranes, the adhesion promoters are relatively high in cost, and in particular, adhesives containing the halogenated adhesion promoters are unfavorable for greening and environmental protection requirements, and chemical resistance, mechanical properties and adhesion sealing performance of the adhesives are required to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an epoxy modified low-VOC bi-component polyurethane adhesive and a preparation method thereof. The epoxy modified low VOC two-component polyurethane adhesive is suitable for adhering polymeric roofing membranes to roofing substrates.
In order to achieve the above purpose, the technical scheme adopted is as follows:
one of the purposes of the invention is to provide an epoxy modified low-VOC two-component polyurethane adhesive, which comprises the following components in parts by weight:
(1) And (3) a component A: 40-46 parts of epoxy modified polyurethane prepolymer A; 40-46 parts of low-viscosity polyurethane prepolymer B; 8-20 parts of a non-reactive plasticizer;
(2) And the component B comprises the following components: 80-90 parts of aliphatic polyester polyol; 10-20 parts of a non-polyester polyol; 0.05-0.5 part of catalyst.
Further, the epoxy modified polyurethane prepolymer A is a polymer containing NCO ends prepared by the reaction of the following raw materials in percentage by weight: 15-40% of polyether triol, 20-45% of epoxy modified polyether triol and 20-40% of diisocyanate; the molar ratio of isocyanate groups to hydroxyl groups of the epoxy modified polyurethane prepolymer A is 2.0-3.0:1.
further, the polyether triol is polyoxypropylene triol with the average molecular weight of 2000-6000; the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate and p-phenylene diisocyanate.
The beneficial effects of adopting the further technical scheme are that: the main chain of the polyoxypropylene triol contains ether bond (-R-O-R-), and the terminal group or the side group contains three hydroxyl groups (-OH), so that diisocyanate can be catalyzed, the crosslinking reaction of polyurethane prepolymer can be promoted, and the excellent water resistance, impact resistance and low temperature property can be provided; the epoxy modified polyurethane prepolymer A with a stable network structure is formed by adopting the diisocyanate with high activity and high-efficiency crosslinking with polyether triol and epoxy modified polyether triol.
Further, the epoxy modified polyether triol is an end OH compound prepared by reacting trifunctional glycidyl epoxy resin with polyethylene glycol, wherein the molar ratio of epoxy groups to hydroxyl groups is 1:1.5-2.5; the trifunctional glycidyl epoxy resin is glycidyl ether epoxy resin or glycidyl amine epoxy resin; the molecular weight of the polyethylene glycol is 500-3000.
The beneficial effects of adopting the further technical scheme are that: the epoxy modified polyether triol has the advantages of high functionality, high activity, high crosslinking density, high corrosion resistance and excellent mechanical strength, and the epoxy modified polyether triol has better rigidity characteristic and high corrosion resistance by reacting with polyethylene glycol.
Still further, the glycidyl ether epoxy resin is triglycidyl isocyanurate.
Further, the low-viscosity polyurethane prepolymer B is a polymer containing NCO ends prepared by the reaction of the following raw materials in percentage by weight: 40-80% of polyether glycol and 20-60% of diisocyanate; the molar ratio of isocyanate groups to hydroxyl groups of the low-viscosity polyurethane prepolymer B is 2.5-3.0:1, a step of; the viscosity of the low-viscosity polyurethane prepolymer B is 1000-2000 mPa.s.
The beneficial effects of adopting the further technical scheme are that: the relative molecular weight distribution of the prepared low-viscosity polyurethane prepolymer B is narrower and the viscosity is lower (1000-3000 mPa.s) by adopting polyether glycol and diisocyanate to crosslink and polymerize and strictly controlling the dosage of each material and the molar ratio of groups.
Further, the polyether glycol is polyoxypropylene glycol with the average molecular weight of 500-2000; the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
The beneficial effects of adopting the further technical scheme are that: the main chain of the adopted polyoxypropylene glycol contains ether bond (-R-O-R-), and the terminal group or the side group contains two hydroxyl groups (-OH), so that the polymerization reaction of diisocyanate can be catalyzed, the crosslinking effect of polyurethane prepolymer is promoted, and the low-viscosity polyurethane prepolymer B with stable network structure is formed.
Further, the non-polyester polyol is selected from at least one of ethylene glycol, 1, 4-butanediol and 1, 3-butanediol;
still further, the non-polyester polyol has a low molecular weight, for example a molecular weight of about 400g/mol or less, and an OH number in the range of about 280 to 1830, and a functionality of less than 3;
further, the aliphatic polyester polyol is an adipate polyester polyol.
Further, the aliphatic polyester polyol has a hydroxyl number of 150 to 300mg KOH/g and an average hydroxyl functionality of 1.8 to 2.2; the acid value is less than 2.
Further, the non-reactive plasticizer includes at least one of propylene carbonate, triethyl phosphate, tris-isopropyl chloride (TCPP) and other non-reactive phosphate esters, preferably propylene carbonate.
Further, the catalyst comprises at least one of urethane, triethylenediamine, heterocyclic tertiary amine triethylenediamine.
The second object of the invention is to provide a preparation method of the epoxy modified low-VOC bi-component polyurethane adhesive, which comprises the following steps:
d1, preparing epoxy modified polyether triol: 150g of polyethylene glycol with relative molecular weight of 500 and 29.7g of glycidyl ether epoxy resin are added into a dry 1L four-mouth bottle, the temperature is raised to 80 ℃, 0.9g of boron trifluoride serving as a catalyst is added, the reaction is carried out for 4 hours at constant temperature, after infrared detection, the reaction is stopped after the peak of an epoxy group is completely disappeared, and the temperature is reduced and the material is discharged, so that the epoxy modified polyether triol is prepared;
d2, preparing an epoxy modified polyurethane prepolymer A: according to weight percentage, mixing polyether triol and epoxy modified polyether triol, heating to 100-110 ℃, vacuumizing to remove water, cooling to 80-85 ℃, adding diisocyanate, reacting under the protection of nitrogen until NCO value is unchanged, and cooling to room temperature to obtain epoxy modified polyurethane prepolymer A;
d3, preparing a low-viscosity polyurethane prepolymer B: according to weight percentage, heating polyether glycol to 100-110 ℃, vacuumizing to remove water, cooling to room temperature, slowly and uniformly dripping the water into diisocyanate for 0.8-1.2h, reacting for 4-6h under the protection of nitrogen with the temperature of 80-85 ℃ until NCO value is unchanged, and cooling to room temperature to obtain low-viscosity polyurethane prepolymer B;
d4, 40-46 parts of epoxy modified polyurethane prepolymer A and 40-46 parts of low-viscosity polyurethane prepolymer B; 8-20 parts of non-reactive plasticizer is put into a stirring kettle, vacuumized and stirred for 1-2 hours, the mixing temperature is less than or equal to 50 ℃, and the vacuum degree is-0.08-0.09 MPA, so that a component A is obtained;
d5, 80-90 parts of aliphatic polyester polyol and 10-20 parts of non-polyester polyol; and (3) adding 0.05-0.5 part of catalyst into a stirring kettle, vacuumizing and stirring for 1-2 hours, wherein the mixing temperature is less than or equal to 60 ℃, and the vacuum degree is-0.08-0.09 MPA to obtain the component B.
Compared with the prior art, the invention has the beneficial effects that:
the epoxy modified low VOC two-component polyurethane adhesive prepared by the invention comprises A, B component, wherein the overall viscosity of the component B is less than 2000cps at 25 ℃; the a component has an overall viscosity of less than 3000cps (using a Brookfield viscometer with a #14 spindle) at 25 c, and the low viscosity imparts good fluidity to facilitate mixed sizing. The adhesive composition is prepared by combining the component A and the component B in a volume ratio of 1:1, is suitable for adhering the polymer film to a roof substrate, has better chemical corrosion resistance and excellent mechanical property, and can maintain good bonding and sealing effects in a long-term use process.
The adhesive composition prepared by the invention without an adhesion promoter has the advantages of lower cost, easiness in preparation and the like, does not contain a halogenated adhesion promoter, and is environment-friendly. The use of solvent-free, epoxy-modified low VOC adhesives, more readily mixed sizing, can provide a controlled cure rate, and can provide good adhesive strength.
Detailed Description
The principles and features of the present invention are described below in connection with examples, which are set forth only to illustrate the present invention and not to limit the scope of the invention.
Example 1
1. Preparation of modified body
S1, preparing epoxy modified polyether triol: 150g of polyethylene glycol with relative molecular weight of 500 and 29.7g of glycidyl ether epoxy resin are added into a dry 1L four-mouth bottle, the temperature is raised to 80 ℃, 0.9g of boron trifluoride serving as a catalyst is added, the reaction is carried out for 4 hours at constant temperature, after infrared detection, the reaction is stopped after the peak of an epoxy group is completely disappeared, and the temperature is reduced and the material is discharged, so that the epoxy modified polyether triol is prepared;
s2, preparing an epoxy modified polyurethane prepolymer A: sequentially adding 360g of epoxy modified polyether triol and 480g of polyether triol (with relative molecular weight of 5000) into a dried 2L four-port bottle, heating to 100 ℃ for vacuum dehydration for 2h, cooling to 80 ℃ after detecting that the moisture content of liquid material is less than or equal to 100ppm, adding 280g of diphenylmethane diisocyanate, reacting for 5h under the protection of nitrogen in a heat-preserving manner, cooling to room temperature when the NCO value is unchanged, discharging to obtain an epoxy modified polyurethane prepolymer A, and placing the epoxy modified polyurethane prepolymer A into a dried nitrogen closed container for standby;
s3, preparing a low-viscosity polyurethane prepolymer B: 800g of polyether glycol is placed in a single-mouth bottle, the temperature is raised to 100 ℃, the vacuum dehydration is carried out, the temperature is reduced to room temperature after the moisture content is less than 100ppm, the mixture is transferred to a separating funnel, the mixture is dropwise added into a four-mouth flask containing 240g of isophorone diisocyanate and 2g of catalyst stannous octoate at a constant speed, the dropping speed is controlled to be 1h, the constant temperature reaction is carried out for 6h under the protection of nitrogen with the temperature of 80 ℃, the temperature is reduced to the room temperature when the NCO value is unchanged, the material is discharged, and the low-viscosity polyurethane prepolymer B is prepared and is placed in a dry nitrogen closed container for standby.
2. Preparation of two-component polyurethane adhesives
D1, 44g of epoxy modified polyurethane prepolymer A and 44g of low-viscosity polyurethane prepolymer B; 12g of propylene carbonate is put into a stirring kettle, and is vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 50 ℃, and the vacuum degree is-0.08-0.09 MPA, so that a well mixed component A is obtained;
d2, 90g of adipate polyester polyol and 10g of ethylene glycol; 0.16g of carbamate is put into a stirring kettle, vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 60 ℃, and the vacuum degree is-0.08-0.09 MPA, so that the mixed component B is obtained.
Example 2
1. The preparation of the modified product was the same as in example 1.
2. Preparation of two-component polyurethane adhesives
D1, 40g of epoxy modified polyurethane prepolymer A and 40g of low-viscosity polyurethane prepolymer B; 20g of propylene carbonate is put into a stirring kettle, and is vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 50 ℃, and the vacuum degree is-0.08-0.09 MPA, so that a well mixed component A is obtained;
d2, 90g of adipate polyester polyol and 10g of ethylene glycol; 0.16g of carbamate is put into a stirring kettle, vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 60 ℃, and the vacuum degree is-0.08-0.09 MPA. The well mixed component B is obtained.
Example 3
1. The preparation of the modified body is as in example 1;
2. preparation of two-component polyurethane adhesives
D1, 46g of epoxy modified polyurethane prepolymer A and 46g of low-viscosity polyurethane prepolymer B; 8g of propylene carbonate is put into a stirring kettle, and is vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 50 ℃, and the vacuum degree is-0.08-0.09 MPA, so that a well mixed component A is obtained;
d2, 80g of adipic acid ester polyester polyol and 20g of ethylene glycol; 0.16g of carbamate is put into a stirring kettle, vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 60 ℃, and the vacuum degree is-0.08-0.09 MPA. The well mixed component B is obtained.
Comparative example 1
1. The preparation of the modified body was the same as in example 1;
2. preparation of two-component polyurethane adhesives
D1, 39g of epoxy modified polyurethane prepolymer A and 39g of low-viscosity polyurethane prepolymer B; 22g of propylene carbonate is put into a stirring kettle, and is vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 50 ℃, and the vacuum degree is-0.08-0.09 MPA, so that a well mixed component A is obtained;
d2, 91g of adipate polyester polyol and 9g of ethylene glycol; 0.16g of carbamate is put into a stirring kettle, vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 60 ℃, and the vacuum degree is-0.08-0.09 MPA. The well mixed component B is obtained.
Comparative example 2
1. The preparation of the modified body is as in example 1;
2. preparation of two-component polyurethane adhesives
D1, 47g of epoxy modified polyurethane prepolymer A and 47g of low-viscosity polyurethane prepolymer B; 6g of propylene carbonate is put into a stirring kettle, and is vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 50 ℃, and the vacuum degree is-0.08-0.09 MPA, so that a well mixed component A is obtained;
d2, 78g of adipate polyester polyol and 22g of ethylene glycol; adding 0.16g of carbamate into a stirring kettle, vacuumizing and stirring for 1.5 hours, wherein the mixing temperature is less than or equal to 60 ℃, and the vacuum degree is-0.08-0.09 MPA to obtain a mixed component B;
comparative example 3
1. Preparation of modified body
Preparation of epoxy modified polyurethane prepolymer a and epoxy modified polyether triol as in example 1;
preparing a low-viscosity polyurethane prepolymer D: 800g of polypropylene glycol is placed in a single-mouth bottle, the temperature is raised to 100 ℃, the vacuum dehydration is carried out, after the moisture content is less than 100ppm, the temperature is reduced to room temperature, the mixture is transferred to a separating funnel, the mixture is added into a four-mouth flask containing 240g of isophorone diisocyanate and 2g of catalyst stannous octoate at a constant speed, the dropping speed is controlled to be 1h, the constant temperature reaction is carried out for 6h under the protection of nitrogen with the temperature of 80 ℃, when the NCO value is unchanged, the temperature is reduced to the room temperature, the material is discharged, and the low-viscosity polyurethane prepolymer D is prepared and is placed in a dry nitrogen closed container for standby.
2. Preparation of two-component polyurethane adhesives
D1, 44g of epoxy modified polyurethane prepolymer A and 44g of low-viscosity polyurethane prepolymer D; 12g of propylene carbonate is put into a stirring kettle, and is vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 50 ℃, and the vacuum degree is-0.08-0.09 MPA, so that a well mixed component A is obtained;
d2, 78g of adipate polyester polyol and 22g of ethylene glycol; 0.16g of carbamate is put into a stirring kettle, vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 60 ℃, and the vacuum degree is-0.08-0.09 MPA, so that the mixed component B is obtained.
Comparative example 4
1. Preparation of modified body
Preparation of low viscosity polyurethane prepolymer B was as in example 1;
preparing an epoxy modified polyurethane prepolymer C: sequentially adding 840g of polyoxypropylene triol into a dry 2L four-mouth bottle, heating to 100 ℃ for vacuum dehydration for 2 hours, cooling to 80 ℃ after detecting that the moisture content of liquid is less than or equal to 100ppm, adding 280g of diphenylmethane diisocyanate, carrying out heat preservation reaction for 5 hours under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged during the reaction, discharging to obtain an epoxy modified polyurethane prepolymer C, and placing the epoxy modified polyurethane prepolymer C in a dry nitrogen closed container for standby;
2. preparation of two-component polyurethane adhesives
D1, 44g of epoxy modified polyurethane prepolymer C; 44g of low-viscosity polyurethane prepolymer B; 12g of propylene carbonate is put into a stirring kettle, and is vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 50 ℃, and the vacuum degree is-0.08-0.09 MPA, so that a well mixed component A is obtained;
d2, 78g of adipate polyester polyol and 22g of ethylene glycol; 0.16g of carbamate is put into a stirring kettle, vacuumized and stirred for 1.5 hours, the mixing temperature is less than or equal to 60 ℃, and the vacuum degree is-0.08-0.09 MPA, so that the mixed component B is obtained.
Testing
The following performance tests were conducted on the adhesives prepared in examples 1 to 3 and comparative examples 1 to 4, and the results obtained are shown in Table 1.
1. Mechanical testing
Measuring the tensile shear strength of GB/T7124-2008 adhesive;
measurement of the elongation at break of GB/T2567-2008 adhesive.
2. Wind pressure resistance test
Standard test standard for wind-lift-resistant bearing capacity of coiled material roofing system under dynamic wind load of CSA A123.21.
3. Peel test
GB/T 2792-2014。
TABLE 1 comparison of the adhesive test data for examples 1-3 and comparative examples 1-4
As can be seen from the test results in Table 1, the two-component polyurethane adhesive in the examples of the present invention has excellent mechanical properties and can maintain good adhesion and sealing effects even in long-term use.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. An epoxy modified low-VOC two-component polyurethane adhesive is characterized by comprising the following components in parts by weight:
(1) And (3) a component A: 40-46 parts of epoxy modified polyurethane prepolymer A; 40-46 parts of low-viscosity polyurethane prepolymer B; 8-20 parts of a non-reactive plasticizer;
(2) And the component B comprises the following components: 80-90 parts of aliphatic polyester polyol; 10-20 parts of a non-polyester polyol; 0.05-0.5 part of catalyst.
2. The epoxy modified low VOC two-component polyurethane adhesive of claim 1 wherein the epoxy modified polyurethane prepolymer a is a polymer comprising terminal NCO produced by the reaction of the following raw materials in weight percent: 15-40% of polyether triol, 20-45% of epoxy modified polyether triol and 20-40% of diisocyanate; the molar ratio of isocyanate groups to hydroxyl groups of the epoxy modified polyurethane prepolymer A is 2.0-3.0:1.
3. the epoxy modified low VOC two-component polyurethane adhesive of claim 2 wherein the polyether triol is a polyoxypropylene triol having an average molecular weight of 2000-6000; the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate and p-phenylene diisocyanate.
4. The epoxy modified low VOC two-component polyurethane adhesive of claim 2, wherein the epoxy modified polyether triol is a terminal OH compound prepared by reacting a trifunctional glycidyl epoxy resin with polyethylene glycol, wherein the molar ratio of epoxy groups to hydroxyl groups is 1:1.5-2.5; the trifunctional glycidyl epoxy resin is glycidyl ether epoxy resin or glycidyl amine epoxy resin; the molecular weight of the polyethylene glycol is 500-3000.
5. The epoxy modified low VOC two-component polyurethane adhesive of claim 1 wherein the low viscosity polyurethane prepolymer B is a polymer comprising terminal NCO produced by the reaction of the following raw materials in weight percent: 40-80% of polyether glycol and 20-60% of diisocyanate; the molar ratio of isocyanate groups to hydroxyl groups of the low-viscosity polyurethane prepolymer B is 2.5-3.0:1, a step of; the viscosity of the low-viscosity polyurethane prepolymer B is 1000-2000 mPa.s.
6. The epoxy modified low VOC two-component polyurethane adhesive of claim 5 wherein the polyether glycol is a polyoxypropylene glycol having an average molecular weight of 500-2000; the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
7. The epoxy modified low VOC two-component polyurethane adhesive of claim 1, wherein the non-polyester polyol is selected from at least one of ethylene glycol, 1, 4-butanediol, 1, 3-butanediol; the functionality of the non-polyester polyol is less than 3; the aliphatic polyester polyol is an adipate polyester polyol.
8. The epoxy modified low VOC two-component polyurethane adhesive of claim 1 wherein the aliphatic polyester polyol has a hydroxyl number of 150-300mg KOH/g and an average hydroxyl functionality of 1.8-2.2; the acid value is less than 2.
9. The epoxy modified low VOC two-component polyurethane adhesive of claim 1, wherein the non-reactive plasticizer comprises propylene carbonate.
10. A method of preparing the epoxy modified low VOC two component polyurethane adhesive of any one of claims 1 to 9 comprising the steps of:
d1, preparing epoxy modified polyether triol: 150g of polyethylene glycol with relative molecular weight of 500 and 29.7g of glycidyl ether epoxy resin are added into a dry 1L four-mouth bottle, the temperature is raised to 80 ℃, 0.9g of boron trifluoride serving as a catalyst is added, the reaction is carried out for 4 hours at constant temperature, after infrared detection, the reaction is stopped after the peak of an epoxy group is completely disappeared, and the temperature is reduced and the material is discharged, so that the epoxy modified polyether triol is prepared;
d2, preparing an epoxy modified polyurethane prepolymer A: according to weight percentage, mixing polyether triol and epoxy modified polyether triol, heating to 100-110 ℃, vacuumizing to remove water, cooling to 80-85 ℃, adding diisocyanate, reacting under the protection of nitrogen until NCO value is unchanged, and cooling to room temperature to obtain epoxy modified polyurethane prepolymer A;
d3, preparing a low-viscosity polyurethane prepolymer B: according to weight percentage, heating polyether glycol to 100-110 ℃, vacuumizing to remove water, cooling to room temperature, slowly and uniformly dripping the water into diisocyanate for 0.8-1.2h, reacting for 4-6h under the protection of nitrogen with the temperature of 80-85 ℃ until NCO value is unchanged, and cooling to room temperature to obtain low-viscosity polyurethane prepolymer B;
d4, 40-46 parts of epoxy modified polyurethane prepolymer A and 40-46 parts of low-viscosity polyurethane prepolymer B; 8-20 parts of non-reactive plasticizer is put into a stirring kettle, vacuumized and stirred for 1-2 hours, the mixing temperature is less than or equal to 50 ℃, and the vacuum degree is-0.08-0.09 MPA, so that a component A is obtained;
d5, 80-90 parts of aliphatic polyester polyol and 10-20 parts of non-polyester polyol; and (3) adding 0.05-0.5 part of catalyst into a stirring kettle, vacuumizing and stirring for 1-2 hours, wherein the mixing temperature is less than or equal to 60 ℃, and the vacuum degree is-0.08-0.09 MPA to obtain the component B.
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