CN107353863B - Modified polyurethane adhesive for dry-cleaning-resistant reflective material - Google Patents
Modified polyurethane adhesive for dry-cleaning-resistant reflective material Download PDFInfo
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- CN107353863B CN107353863B CN201710671553.3A CN201710671553A CN107353863B CN 107353863 B CN107353863 B CN 107353863B CN 201710671553 A CN201710671553 A CN 201710671553A CN 107353863 B CN107353863 B CN 107353863B
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- 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
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- 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
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- 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
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- 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
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C08K5/00—Use of organic ingredients
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- C08K5/00—Use of organic ingredients
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- C08K5/544—Silicon-containing compounds containing nitrogen
Abstract
The invention discloses a modified polyurethane adhesive for a dry-cleaning resistant reflective material, which is prepared from the following components in percentage by weight: 10-20% of polyester polyol, 5-10% of hydroxyl organosilicon, 5-20% of epoxy resin, 5-8.2% of isocyanate, 1-2% of micromolecule dihydric alcohol, 3-5% of chain extender, 50-59% of solvent and auxiliary agent, wherein the auxiliary agent comprises 0.1-1% of antioxidant, 0.5-1% of catalyst and 0.1-1% of silane coupling agent, and the sum of the antioxidant, the catalyst and the silane coupling agent is 1-2%. The invention has excellent adhesiveness, temperature resistance, acid resistance, alkali resistance and tetrachloroethylene washing resistance.
Description
Technical Field
The invention relates to the technical field of reflective material production, in particular to a modified polyurethane adhesive for a dry-cleaning resistant reflective material.
Background
The reflecting material is also called as a retroreflective material and a retro-reflective material, is widely applied to various road traffic safety facilities such as traffic sign marks, raised road signs, contour marks, traffic cones, anti-collision barrels and the like, and automobile license plates, clothes, shoes and hats, fire fighting, railways, water transportation, mining areas and the like, and can be divided into a traffic sign reflecting material, a road mark reflecting material, a raised road sign, a contour mark, a reflecting material for clothes and the like. The industrial work and outfit of the reflective material used in the heavy industry pollution field of petroleum, coal and the like has special requirements on the aspect of washing, and needs acid resistance, alkali resistance, washing resistance, repeated use and high temperature washing resistance. In order to clean, tetrachloroethylene is often used as a cleaning agent for dry cleaning in industry, and the cleaning capacity is strong, so that very special requirements are provided for the adhesive for the reflective material. The adhesion of the reflective material to the substrate is critical and whether the reflective material can withstand dry cleaning is completely dependent on the adhesive itself.
Disclosure of Invention
The invention aims to provide a modified polyurethane adhesive for a dry-cleaning resistant reflective material, which has excellent adhesion, temperature resistance, acid resistance, alkali resistance and tetrachloroethylene washing resistance.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a modified polyurethane adhesive for dry-cleaning resistant reflective materials is prepared from the following components in percentage by weight: 10-20% of polyester polyol, 5-10% of hydroxyl organosilicon, 5-20% of epoxy resin, 5-8.2% of isocyanate, 1-2% of micromolecule dihydric alcohol, 3-5% of chain extender, 50-59% of solvent and auxiliary agent, wherein the auxiliary agent comprises 0.1-1% of antioxidant, 0.5-1% of catalyst and 0.1-1% of silane coupling agent, and the sum of the antioxidant, the catalyst and the silane coupling agent is 1-2%.
The invention is characterized in that a polyurethane end-capping reagent is obtained by polymerization reaction of isocyanate, hydroxyl organosilicon and epoxy resin, a polyurethane initiator is generated by chain extension reaction of micromolecular dihydric alcohol, polyester polyol and isocyanate, and finally a novel polyurethane resin adhesive is synthesized by the polyurethane initiator, the chain extender and the polyurethane end-capping reagent. The reflective material product prepared by the adhesive has good dry cleaning resistance, and especially has good tetrachloroethylene washing resistance.
Preferably, the polyester polyol is one or more selected from the group consisting of poly (m-phthalic acid-adipic acid-3-methyl-1, 5-pentanediol) diol, poly (phthalic acid-3-methyl-1, 5-pentanediol) diol, and poly (m-phthalic acid-3-methyl-1, 5-pentanediol) diol, and the number average molecular weight of the polyester polyol is 2000-4000 g/mol.
Preferably, the hydroxyl organosilicon is one or more of RNS-0808, RNS-0806, RNS-0804 and RNS-0805 of Dow Corning, and the hydroxyl organosilicon is hydroxyl organosilicon with hydroxyl groups at two ends of a molecular chain and silicon content higher than 50%.
Preferably, the epoxy resin is one or more of bisphenol A type, bisphenol F type and phenolic aldehyde type. Preferably, the isocyanate is one or more of trimethylethane diisocyanate, 1, 4-cyclohexane diisocyanate, tetramethyl m-xylylene diisocyanate and cyclohexane dimethylene diisocyanate.
Preferably, the small-molecule diol is one or more selected from 2-methyl-1, 3-propanediol with symmetrical pendant group structure, 2, 4-diethyl-1, 5-pentanediol, hydroxypivalic acid neopentyl glycol monoester and 3-methyl-1, 5-pentanediol. The 2-methyl-1, 3-propylene glycol with symmetrical lateral group structure can carry lateral groups on the whole molecular chain after carrying the lateral groups, the mutual attraction between the components can be generated between every two lateral groups, and a conjugated electron layer is formed outside the molecular chain, so that the molecular chain is not easy to damage, the peeling strength is increased, and the dry cleaning resistance is also increased.
Preferably, the chain extender is one or more of 4,4 '-diamino-3, 3' -dichlorodiphenylmethane, dimethylthiotoluenediamine and diethyltoluenediamine.
Preferably, the solvent is one or more selected from toluene, xylene, ethyl acetate, butyl acetate and butanone.
Preferably, the silane coupling agent is selected from one or more of gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane; the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the catalyst is a mixture of an organic zinc catalyst and an organic bismuth catalyst according to a weight ratio of 3: 5. The silane coupling agent can improve the bonding capability of the polyurethane adhesive, effectively reduce the surface tension, and effectively permeate into the surface of each substrate from better wetting performance of the reflective material and the substrate, thereby enhancing the bonding capability.
Preferably, the preparation method comprises the following steps:
firstly, preparing a polyurethane initiator:
(1) carrying out vacuum dehydration on polyester polyol at the temperature of 105-115 ℃ to ensure that the water content is less than 0.03%; the purpose of controlling the water content of the polyester polyol to be less than 0.03% in the step is to prevent the moisture in the polyester polyol from reacting with isocyanate to generate other substances, so that the bonding capability of the adhesive is influenced.
(2) Putting 35-45wt% of polyester polyol, micromolecular dihydric alcohol, solvent and 50wt% of antioxidant into a reaction kettle, controlling the temperature to be 40-60 ℃, and stirring and mixing uniformly; the temperature is controlled to be 40-60 ℃, so that the polyester polyol is melted, fully stirred and uniformly mixed with the solvent, the antioxidant and the like, and the phenomenon that the reaction speed is too high when the isocyanate is added in the next step is avoided.
(3) Then 70wt% of isocyanate and 70wt% of catalyst are put into the reaction kettle, and the mixture is condensed and refluxed for reaction for 4 to 6 hours at the temperature of 105-115 ℃ to synthesize a polyurethane initiator;
secondly, preparing a polyurethane end-capping agent:
(4) vacuum dehydrating the epoxy resin at 90-100 ℃ to ensure that the water content is less than 0.03%; the purpose of controlling the water content of the epoxy resin to be less than 0.03% in the step is to prevent the moisture in the epoxy resin from reacting with isocyanate to generate other substances and influence the bonding capability of the adhesive.
(5) Putting hydroxyl organic silicon, epoxy resin, residual isocyanate, residual catalyst and residual antioxidant into a reaction kettle, reacting for 3-4 hours at 85-95 ℃, detecting whether a-NCO reaction group remains, and continuing to react for 1 hour if the-NCO reaction group remains, so as to synthesize a polyurethane end-capping reagent; the purpose of detecting the existence of NCO is to ensure that the hydroxyl organosilicon and the epoxy resin completely react with isocyanate and ensure that two ends of the whole molecular chain are blocked by hydroxyl.
Thirdly, synthesizing a product:
(6) heating the polyurethane initiator to 80-90 ℃; this step is intended to have sufficient subsequent reaction activation energy to react with the chain extender.
(7) Slowly dripping the chain extender dissolved with the solvent, and reacting for 1 hour after the chain extender is dripped within 1 hour; the aim of the step is to control the reaction speed, control the molecular weight distribution not too wide, control the molecular weight narrow resin crystallization performance good, the cohesive force is strong. The molecular weight is too large, the cohesive energy is high, and the cohesive force is reduced.
(8) Adding the rest solvent, adding the polyurethane end-capping reagent, and reacting at 100-110 ℃ for 2-3 hours; in the step, the polyurethane end-capping reagent is added so that the molecular chain of the whole adhesive contains silicon groups and epoxy groups. The resistance of the adhesive to tetrachloroethylene and polar substances can be improved, and the bonding performance of the adhesive to base cloth and a reflective material is improved.
(9) Cooling to 40 ℃, adding the silane coupling agent, stirring for 1 hour, metering and packaging to obtain the product. The silane coupling agent is added in the step to further increase the surface wetting of the base cloth and the reflective material so as to improve the bonding strength, the temperature is controlled to be 30-40 ℃ so as to ensure that the stirring is more sufficient, and the temperature is prevented from exceeding 40 ℃ so that the silane coupling agent can generate side reaction with the polyurethane adhesive to influence the bonding effect.
One of the creation points of the invention lies in the design of the whole molecular chain, polyurethane molecules are taken as the core, then the chain is extended by an amino chain extender, amino resin structures at two ends of the middle polyurethane are formed, the two structures have mutual excitation function, and finally the two structures are coated by silicon and epoxy resin; most of molecular chains are linear molecular chains containing methyl lateral groups, and each methyl group can generate intermolecular attraction to generate a conjugation effect, so that the dry cleaning resistance effect is greatly improved.
The second creation point of the invention is that the synthetic process of dripping the chain extender dissolved by the solvent is adopted, the whole reaction degree, the molecular weight and the molecular weight distribution of the polyurethane resin can be perfectly controlled, and the bonding capability to the reflective material is controlled.
The third creation point of the invention is that the isocyanate of the polyurethane initiator and the polyurethane end-capping agent can be interchanged by adopting the adhesive synthesized by the process.
The invention has the beneficial effects that:
1. the adhesive can resist acid, alkali, corrosion, high temperature and tetrachloroethylene washing, and has strong adhesive force to the reflective material and the base cloth.
2. The reflective adhesive film prepared by the product has good dry-cleaning resistance, can improve the utilization rate of the work clothes of a heavy industry enterprise, and saves the cost.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
a modified polyurethane adhesive for dry-cleaning resistant reflective materials is prepared from the following components in percentage by weight: 10% of polyester polyol, 5% of hydroxyl organic silicon, 20% of epoxy resin, 5% of isocyanate, 2% of micromolecular dihydric alcohol, 5% of chain extender, 51.5% of solvent, 0.5% of antioxidant, 0.6% of catalyst and 0.4% of silane coupling agent.
In the embodiment, the polyester polyol is poly phthalic acid-adipic acid-3-methyl-1, 5-pentanediol glycol, and the number average molecular weight is 2000-4000 g/mol. One or more of poly (3-methyl-1, 5-pentanediol isophthalate-adipate), poly (3-methyl-1, 5-pentanediol phthalate) and poly (3-methyl-1, 5-pentanediol isophthalate) may be used in place of poly (3-methyl-1, 5-pentanediol isophthalate) according to the actual circumstances.
In the embodiment, the hydroxyl organosilicon (commercially available) is RNS-0805 of Dow Corning, and one or more of RNS-0808, RNS-0806 and RNS-0804 can be used for replacing RNS-0805 according to actual conditions.
In the present embodiment, the epoxy resin (commercially available) is bisphenol a type, and may be replaced by one or more of bisphenol F type and phenol type depending on the actual situation.
In this embodiment, the isocyanate (commercially available) is trimethylethane diisocyanate, and may be replaced by one or more of 1, 4-cyclohexane diisocyanate, tetramethylm-xylylene diisocyanate, and cyclohexanedimethylene diisocyanate according to actual conditions.
In the embodiment, the small molecule dihydric alcohol (commercially available) is 2-methyl-1, 3-propanediol with symmetrical pendant group structure, and can be replaced by one or more of 2, 4-diethyl-1, 5-pentanediol, hydroxypivalic acid neopentyl glycol monoester and 3-methyl-1, 5-pentanediol according to actual conditions.
In this embodiment, the chain extender is 4,4 '-diamino-3, 3' -dichlorodiphenylmethane, and may be replaced by one or more of dimethylthiotoluenediamine and diethyltoluenediamine according to actual conditions.
In this embodiment, the solvent is toluene, and may be replaced by one or more of xylene, ethyl acetate, butyl acetate, and butanone according to actual conditions.
In this embodiment, the silane coupling agent is gamma-aminopropyltriethoxysilane, which can be replaced by one or more of gamma- (2, 3-glycidoxy) propyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, and gamma-methacryloxypropyltrimethoxysilane according to actual conditions.
The antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the catalyst is a mixture of an organic zinc catalyst (available from ZB1001, a leading environmental protection material Co., Ltd., Dongguan) and an organic bismuth catalyst (available from Bi2010, a leading environmental protection material Co., Ltd., Dongguan) according to a weight ratio of 3: 5.
Example 2:
a modified polyurethane adhesive for dry-cleaning resistant reflective materials is prepared from the following components in percentage by weight: 20% of polyester polyol, 10% of hydroxyl organosilicon, 5% of epoxy resin, 8.2% of isocyanate, 1% of micromolecular dihydric alcohol, 3% of chain extender, 50.3% of solvent, 0.6% of antioxidant, 0.8% of catalyst and 0.6% of silane coupling agent.
In this example, the polyester polyol is a mixture of poly (isophthalic acid) -adipic acid-3-methyl-1, 5-pentanediol ester diol and poly (phthalic acid) -3-methyl-1, 5-pentanediol ester diol in a weight ratio of 1: 1.
The hydroxyl silicone (commercially available) in this example was a mixture of RNS-0808 and RNS-0806 from Dow Corning in a weight ratio of 1: 1.
In this example, the epoxy resin (commercially available) is a mixture of bisphenol a epoxy resin and phenol epoxy resin at a weight ratio of 1: 1.
The isocyanate described in this example (commercially available) is a 3:1 weight ratio mixture of 1.4-cyclohexane diisocyanate and tetramethyl-m-xylylene diisocyanate.
The small molecule diol (commercially available) in this example is a mixture of 2, 4-diethyl-1, 5-pentanediol and hydroxypivalic acid neopentyl glycol monoester in a weight ratio of 1: 1.
In this embodiment, the chain extender is a mixture of dimethylthiotoluenediamine and diethyltoluenediamine at a weight ratio of 1: 1.
In this embodiment, the solvent is a mixture of ethyl acetate and butyl acetate in a weight ratio of 2: 1.
In this embodiment, the silane coupling agent is a mixture of γ -aminopropyltriethoxysilane and γ - (2, 3-glycidoxy) propyltrimethoxysilane at a weight ratio of 2: 1.
The antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the catalyst is a mixture of an organic zinc catalyst (available from ZB1001, a leading environmental protection material Co., Ltd., Dongguan) and an organic bismuth catalyst (available from Bi2010, a leading environmental protection material Co., Ltd., Dongguan) according to a weight ratio of 3: 5.
Example 3:
a modified polyurethane adhesive for dry-cleaning resistant reflective materials is prepared from the following components in percentage by weight: 13% of polyester polyol, 6.7% of hydroxyl organosilicon, 8.5% of epoxy resin, 6% of isocyanate, 1.5% of small molecular dihydric alcohol, 4% of chain extender, 59% of solvent, 0.4% of antioxidant, 0.6% of catalyst and 0.3% of silane coupling agent.
In the embodiment, the polyester polyol is poly (isophthalic acid) -adipic acid-3-methyl-1, 5-pentanediol ester diol, and the number average molecular weight is 2000-4000 g/mol.
The hydroxyl silicone (commercially available) described in this example was RNS-0804 from Dow Corning.
The epoxy resin (commercially available) described in this example was bisphenol F.
The isocyanate (commercially available) described in this example was cyclohexanedimethylene diisocyanate.
The small molecule diol (commercially available) in this example was 3-methyl-1, 5-pentanediol.
In this embodiment, the chain extender is dimethylthiotoluenediamine.
In this example, the solvent was methyl ethyl ketone.
In this example, the silane coupling agent is N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane.
The antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the catalyst is a mixture of an organic zinc catalyst (available from ZB1001, a leading environmental protection material Co., Ltd., Dongguan) and an organic bismuth catalyst (available from Bi2010, a leading environmental protection material Co., Ltd., Dongguan) according to a weight ratio of 3: 5.
The preparation method of the product comprises the following steps:
firstly, preparing a polyurethane initiator:
(1) carrying out vacuum dehydration on polyester polyol at the temperature of 105-115 ℃ to ensure that the water content is less than 0.03%;
(2) putting 35-45wt% of polyester polyol, micromolecular dihydric alcohol, solvent and 50wt% of antioxidant into a reaction kettle, controlling the temperature to be 40-60 ℃, and stirring and mixing uniformly;
(3) then 50-70wt% of isocyanate and 50-70wt% of catalyst are put into the reaction kettle, and the mixture is condensed and refluxed for reaction for 4-6 hours at the temperature of 105-115 ℃ to synthesize a polyurethane initiator;
secondly, preparing a polyurethane end-capping agent:
(4) vacuum dehydrating the epoxy resin at 90-100 ℃ to ensure that the water content is less than 0.03%;
(5) putting hydroxyl organic silicon, epoxy resin, residual isocyanate, residual catalyst and residual antioxidant into a reaction kettle, reacting for 3-4 hours at 85-95 ℃, detecting whether a-NCO reaction group remains, and continuing to react for 1 hour if the-NCO reaction group remains, so as to synthesize a polyurethane end-capping reagent;
thirdly, synthesizing a product:
(6) heating the polyurethane initiator to 80-90 ℃;
(7) slowly dripping the chain extender dissolved with the solvent, and reacting for 1 hour after the chain extender is dripped within 1 hour;
(8) adding the rest solvent, adding the polyurethane end-capping reagent, and reacting at 100-110 ℃ for 2-3 hours;
(9) cooling to 40 ℃, adding the silane coupling agent, stirring for 1 hour, metering and packaging to obtain the product.
The product of the invention can resist acid (the surface of the product is not changed at all after being soaked in 10% HCL solution for 240 h), resist alkali (the surface of the product is not changed at all after being soaked in 10% NaOH solution for 240 h), resist corrosion (the salt spray resistance is over 1000 h), resist high temperature (the luminosity retention ratio of the reflective material is over 10% of the industrial standard after being washed by 90-degree EN ISO6330 water for 50 times), and resist tetrachloroethylene washing.
The reflective adhesive film prepared by the product has good dry-cleaning resistance, can improve the utilization rate of the work clothes of a heavy industry enterprise, and saves the cost.
The washing test is carried out according to EN ISO3175 standard, and the product can resist over 50 times of dry cleaning.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (7)
1. The modified polyurethane adhesive for the dry-cleaning-resistant reflective material is characterized by comprising the following components in parts by weight: the paint is prepared from the following components in percentage by weight: 10-20% of polyester polyol, 5-10% of hydroxyl organosilicon, 5-20% of epoxy resin, 5-8.2% of isocyanate, 1-2% of micromolecular dihydric alcohol, 3-5% of chain extender, 50-59% of solvent and auxiliary agent, wherein the auxiliary agent comprises 0.1-1% of antioxidant, 0.5-1% of catalyst and 0.1-1% of silane coupling agent, and the sum of the antioxidant, the catalyst and the silane coupling agent is 1-2%;
the hydroxyl organic silicon is one or more of RNS-0808, RNS-0806, RNS-0804 and RNS-0805 of Dow Corning, the hydroxyl organic silicon is hydroxyl organic silicon with hydroxyl groups at two ends of a molecular chain, and the silicon content is higher than 50%;
the micromolecular dihydric alcohol is selected from one or more of 2-methyl-1, 3-propanediol with symmetrical side group structure, 2, 4-diethyl-1, 5-pentanediol, neopentyl glycol hydroxypivalate monoester and 3-methyl-1, 5-pentanediol;
the chain extender is one or more of 4,4 '-diamino-3, 3' -dichlorodiphenylmethane, dimethylthiotoluenediamine and diethyltoluenediamine.
2. The modified polyurethane adhesive for dry-cleaning resistant reflective material according to claim 1, wherein: the polyester polyol is selected from one or more of poly (m-phthalic acid) -adipic acid-3-methyl-1, 5-pentanediol ester diol, poly (phthalic acid) -3-methyl-1, 5-pentanediol ester diol, and poly (m-phthalic acid) -3-methyl-1, 5-pentanediol ester diol, and the number average molecular mass of the polyester polyol is 2000-4000 g/mol.
3. The modified polyurethane adhesive for dry-cleaning resistant retroreflective material as claimed in claim 1 or 2, wherein: the epoxy resin is one or more of bisphenol A type, bisphenol F type and phenolic aldehyde type.
4. The modified polyurethane adhesive for dry-cleaning resistant retroreflective material as claimed in claim 1 or 2, wherein: the isocyanate is one or more of trimethylethane diisocyanate, 1, 4-cyclohexane diisocyanate, tetramethyl m-xylylene diisocyanate and cyclohexane dimethylene diisocyanate.
5. The modified polyurethane adhesive for dry-cleaning resistant retroreflective material as claimed in claim 1 or 2, wherein: the solvent is selected from one or more of toluene, xylene, ethyl acetate, butyl acetate and butanone.
6. The modified polyurethane adhesive for dry-cleaning resistant retroreflective material as claimed in claim 1 or 2, wherein: the silane coupling agent is selected from one or more of gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane; the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the catalyst is a mixture of an organic zinc catalyst and an organic bismuth catalyst according to a weight ratio of 3: 5.
7. The modified polyurethane adhesive for dry-cleaning resistant reflective material according to claim 1 or 2, wherein the preparation method comprises the steps of:
firstly, preparing a polyurethane initiator:
(1) carrying out vacuum dehydration on polyester polyol at the temperature of 105-115 ℃ to ensure that the water content is less than 0.03%;
(2) putting 35-45wt% of polyester polyol, micromolecular dihydric alcohol, solvent and 50wt% of antioxidant into a reaction kettle, controlling the temperature to be 40-60 ℃, and stirring and mixing uniformly;
(3) then 50-70wt% of isocyanate and 50-70wt% of catalyst are put into the reaction kettle, and the mixture is condensed and refluxed for reaction for 4-6 hours at the temperature of 105-115 ℃ to synthesize a polyurethane initiator;
secondly, preparing a polyurethane end-capping agent:
(4) vacuum dehydrating the epoxy resin at 90-100 ℃ to ensure that the water content is less than 0.03%;
(5) putting hydroxyl organic silicon, epoxy resin, residual isocyanate, residual catalyst and residual antioxidant into a reaction kettle, reacting for 3-4 hours at 85-95 ℃, detecting whether a-NCO reaction group remains, and continuing to react for 1 hour if the-NCO reaction group remains, so as to synthesize a polyurethane end-capping reagent;
thirdly, synthesizing a product:
(6) heating the polyurethane initiator to 80-90 ℃;
(7) slowly dripping the chain extender dissolved with the solvent, and reacting for 1 hour after the chain extender is dripped within 1 hour;
(8) adding the rest solvent, adding the polyurethane end-capping reagent, and reacting at 100-110 ℃ for 2-3 hours;
(9) cooling to 40 ℃, adding the silane coupling agent, stirring for 1 hour, metering and packaging to obtain the product.
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| CN110452629B (en) * | 2019-08-12 | 2022-01-07 | 浙江夜光明光电科技股份有限公司 | Vulcanized reflective cloth for bicycle tire |
| CN112358842A (en) * | 2020-09-29 | 2021-02-12 | 无锡市佳盛高新改性材料有限公司 | Preparation method of organic silicon polyurethane adhesive |
| CN115820195A (en) * | 2022-08-15 | 2023-03-21 | 杭州星华反光材料股份有限公司 | Polyurethane glue for high-brightness reflective material and application thereof |
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| CN104178077A (en) * | 2013-05-28 | 2014-12-03 | 福建省奥翔体育塑胶有限公司 | Polyurethane adhesive used for durable and environmentally friendly plastic runway |
| CN106281199A (en) * | 2016-08-08 | 2017-01-04 | 贵阳时代沃顿科技有限公司 | A kind of chemical-resistant stability monocomponent polyurethane adhesive and preparation method thereof |
| CN106479425A (en) * | 2016-08-26 | 2017-03-08 | 杭州星华反光材料股份有限公司 | A kind of adhesive of resistance to industrial washing and preparation method and application |
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