CN112143436B - Preparation method of high-temperature and high-humidity resistant polyurethane adhesive - Google Patents
Preparation method of high-temperature and high-humidity resistant polyurethane adhesive Download PDFInfo
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses a preparation method of a high-temperature and high-humidity resistant polyurethane adhesive, which comprises the following specific preparation processes: weighing a certain amount of antibacterial cross-linking agent, an antibacterial polymer and an ethanol solution, simultaneously adding the antibacterial cross-linking agent, the antibacterial polymer and the ethanol solution into a reaction kettle, stirring and dissolving, heating for reaction for 2 hours, then adding triethylamine into the reaction kettle, cooling and discharging after the reaction, removing the solvent, adding the solid substance into ethanol, and stirring to prepare the polyurethane adhesive. One end of the antibacterial cross-linking agent prepared by the invention is connected with one side of the carbonyl of the-NH-COO-mesoester group in the antioxidant-assisted polymer, and the other end is connected with one end of the hydroxyl of the mesoester group in the antioxidant-assisted polymer, so that when the adhesive is hydrolyzed in high-temperature water, polymer chains are still connected through the antibacterial cross-linking agent and still can be tightly compounded on the surface of a test piece, and the reduction of the adhesive strength caused by hydrolysis is avoided.
Description
Technical Field
The invention belongs to the field of adhesive preparation, and relates to a preparation method of a high-temperature and high-humidity resistant polyurethane adhesive.
Background
The polyurethane adhesive can be used for self or mutual adhesion of metal, rubber, plastic, fabric, leather, rubber and plastic materials, wood, ceramic, glass and the like, even has certain adhesion strength for polyethylene and polypropylene which are difficult to adhere, but the polyurethane adhesive has poor heat resistance, the adhesive is easy to hydrolyze under high temperature and high humidity to reduce the bonding strength, in order to improve the heat resistance of the adhesive, in the prior art, a hydrophobic oxysilane bond is usually introduced into a polymer, so that the high temperature resistance is realized, at the same time, the polyurethane can be hydrophobic, but because the prepared polyurethane contains-NHCOO-group, and weak hydrogen bonds are easily formed between the amino groups and the adjacent polymer carbonyl groups, and under the action of high temperature and high humidity, the ester group in the polymer can still be hydrolyzed, and hydrogen bonds can be broken, so that polymer chains are broken, the polymerization degree is reduced, and the adhesive strength is reduced.
Food sterilization is carried out on packaging bag packaging food under high-temperature steam of 121-.
Disclosure of Invention
The invention aims to provide a preparation method of a high-temperature and high-humidity resistant polyurethane adhesive, wherein a prepared auxiliary antioxidant polymer chain contains-NH-COO-bonds, can be subjected to a cross-linking reaction with one end of an antibacterial cross-linking agent, and is grafted with a branched chain on the auxiliary antibacterial polymer chain
The group can react with the other end of the antibacterial cross-linking agent, so that one end of the antibacterial cross-linking agent is connected with one side of a carbonyl group of an-NH-COO-middle ester group, and the other end of the antibacterial cross-linking agent is connected with one end of a hydroxyl group of the ester group, so that when the adhesive is hydrolyzed in a high-temperature and high-humidity environment, polymer chains are still connected through the antibacterial cross-linking agent and can still be tightly compounded on the surface of a test piece, the reduction of the adhesive strength of the test piece due to hydrolysis is avoided, meanwhile, because amino in the adhesive directly acts with the antibacterial cross-linking agent at high temperature, hydrogen bonds in the adhesive are converted into chain connection and cannot break under the action of high temperature and high humidity, and the problem that the adhesive property of.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a high-temperature and high-humidity resistant polyurethane adhesive comprises the following specific preparation processes:
firstly, adding a dihydroxyvinyl acetate-based silanized monomer into a reaction kettle, decompressing, heating to 120 ℃ for dehydration, then adding isophorone diisocyanate and dibutyltin dilaurate, heating to 80-85 ℃, stirring for reaction for 2-3h, then cooling to 60 ℃, adding 1, 4-butanediol, stirring at constant temperature for reaction for 40-50min, and obtaining a polymer glue solution; the weight parts of the added raw materials are as follows: 78-85 parts of dihydroxyvinyl acetate-based silanized monomer, 13-15 parts of isophorone diisocyanate, 0.15-0.16 part of dibutyltin dilaurate and 0.4-0.6 part of 1, 4-butanediol;
secondly, adding polymer colloid into a reaction kettle, cooling to 5 ℃, adding methyl bromide, stirring for 30min, heating and pressurizing to 0.7-0.8MPa, stopping heating, recovering excessive methyl bromide after stirring and reacting for 7-8h, adding absolute ethyl alcohol and activated carbon, heating to dissolve, driving up methyl bromide, heating to 90 ℃, recovering ethyl alcohol, adding acetone, stirring for 10min, filtering while hot, naturally cooling filtrate, evaporating off acetone, and drying the obtained solid product to obtain the antibacterial polymer; wherein 213-219g of methyl bromide is added per kilogram of polymer colloid; the polymer colloid contains tertiary amino, and can react with methyl bromide to generate ammonium chloride;
thirdly, weighing a certain amount of antibacterial cross-linking agent, an antibacterial polymer and an ethanol solution, adding the antibacterial cross-linking agent, the antibacterial polymer and the ethanol solution into a reaction kettle, stirring and dissolving, heating to 110-115 ℃, reacting for 2 hours, adding triethylamine into the reaction kettle, cooling to 75-80 ℃, reacting for 6-7 hours, cooling and discharging, performing rotary evaporation on the obtained product, removing the solvent and the micromolecule substances in the product to obtain a solid substance, adding the solid substance into ethanol, stirring and preparing into glue solution with the viscosity of 6000-6500mPa.s, namely the polyurethane glue solution; wherein 169g of the antibacterial cross-linking agent 163-169g is added in each kilogram of the antibacterial polymer; because the auxiliary anti-oxygen polymer chain contains-NH-COO-bonds, weak hydrogen bond action is destroyed at high temperature, amino in the auxiliary anti-oxygen polymer chain can carry out ring-opening reaction with epoxy groups in the antibacterial cross-linking agent, so that one end of the antibacterial cross-linking agent is fixed on the auxiliary antibacterial polymer chain in a cross-linking way, and simultaneously, because the auxiliary antibacterial polymer chain is grafted with branched chains
The methylene between two carbonyl groups has high activity under the alkaline condition of adding triethylamine, can generate carbanions, and simultaneously one end of the antibacterial cross-linking agent contains alphaBeta unsaturated carbonyl can perform addition reaction, so that the other end of the antibacterial cross-linking agent is connected to the adjacent antibacterial polymer chains, the antibacterial polymer chains are connected through the antibacterial cross-linking agent to form a compact net structure, the cross-linking structural formula is shown in figure 1, the adhesive can be tightly attached to the surface of a test piece in the using process of the adhesive to realize high adhesion performance, meanwhile, one end of the antibacterial cross-linking agent is connected with one side of carbonyl of an-NH-COO-middle ester group, the other end of the antibacterial cross-linking agent is connected with one end of hydroxyl of the ester group, so that when the adhesive is hydrolyzed in high-temperature water, the polymer chains are still connected through the antibacterial cross-linking agent, and the hydrogen bond action is connected through chemical action and cannot be broken, so that the adhesive cannot be reduced in adhesion strength due to hydrolysis;
because the ammonium chloride group on the polymer main chain in the polyurethane adhesive net structure and the isothiazolinone group on the antibacterial cross-linking agent are adjacent, the ammonium chloride group is positively charged, the cell membrane of the microorganism is negatively charged, the antibacterial polymer can be adsorbed on the cell membrane of the bacterium through electrostatic action, further the surface charge number of the bacterium is changed to a great extent to generate bacterial dissolution, and the high-efficiency sterilization performance is realized, meanwhile, the isothiazolinone group contained in the antibacterial cross-linking agent directly destroys the DNA molecules in the bacterial cells to inactivate the bacterium, further the antibacterial polymer adsorbs the bacterium through the ammonium chloride group, and the external cell walls of the bacterium are destroyed on the surface of the bacterium, the isothiazolinone group on the polymer directly destroys the DNA molecules in the bacterium after the cell walls are destroyed, further, the effects that the polymer firstly destroys the cell walls and then destroys the DNA molecules in the bacterium are realized, the synergistic effect of the ammonium chloride and the isothiazolinone can realize high-efficiency bactericidal action, and the ammonium chloride and the isothiazolinone are uniformly distributed in the net structure, so that the polymer has uniform and high-efficiency bactericidal performance;
in order to realize high antibacterial performance of the adhesive, a water-absorbing group quaternary ammonium group is introduced to an antibacterial cross-linking agent chain to cause the adhesive to absorb water, but the antibacterial cross-linking agent is directly connected to a branched chain
The groups are connected with polydimethylsiloxane, and the polydimethylsiloxane has higher hydrophobic property, so that the water absorption of quaternary ammonium groups is compensated by the polydimethylsiloxane, and the large amount of absorption of water vapor is reduced;
the polyurethane adhesive is prepared by cross-linking an auxiliary antibacterial polymer, wherein the auxiliary antibacterial polymer is formed by polymerizing a dihydroxyvinylacetate-based silanized monomer, the dihydroxyvinylacetate-based silanized monomer is formed by polymerizing dihydroxyacetoacetoxyethyl polydimethylsiloxane and polyether dihydric alcohol, so that a large number of oxysilane bonds and acetoacetoxyethyl bonds are uniformly distributed on the prepared polymer face, the high-temperature resistance of the polymer is improved by uniformly introducing the oxysilane bonds, and meanwhile, the introduction of the acetoacetoxyethyl bonds provides an action site for the subsequent reaction;
the specific preparation process of the dihydroxyvinyl acetate-based silanized monomer is as follows:
step 1: adding 4-methyl chloroacetoacetate into a reaction kettle, stirring and cooling to 0-5 ℃, dropwise adding a methylamine ethanol solution with the mass concentration of 33%, dropwise adding a liquid alkali solution with the mass concentration of 40% after dropwise adding for 5min, controlling the dropwise adding of the methylamine ethanol solution to be complete within 1h, controlling the dropwise adding of the 40% liquid alkali solution and the methylamine ethanol solution to be complete simultaneously, controlling the reaction temperature to be 10-15 ℃ in the dropwise adding process, heating to 70-75 ℃ after the dropwise adding is complete, reacting for 3-4h, separating an oil layer after standing, and performing rotary evaporation to recover methylamine to obtain 4-methyl aminoacetoacetate; wherein 750-770mL of methylamine ethanol solution with the mass concentration of 33 percent is added into each kilogram of 4-chloroacetoacetic acid methyl ester;
step 2: adding 4-methyl amino methyl acetoacetate and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into a reaction kettle at the same time, heating to 80-85 ℃, stirring for reaction for 5-6h, and then performing rotary evaporation to collect unreacted 4-methyl amino methyl acetoacetate to obtain siloxane-based methyl acetoacetate; wherein 4-methyl aminoacetoacetate and gamma- (2, 3-glycidoxy) propyl trimethoxy silane are added according to the mass ratio of 1: 0.94-0.96;
and step 3: adding alpha, omega-dihydroxy polydimethylsiloxane into a reaction kettle, stirring and heating to 80-85 ℃, then adding siloxane-based methyl acetoacetate and 25% tetramethyl ammonium hydroxide aqueous solution, stirring and reacting for 2h, heating to 140-150 ℃, then carrying out reflux reaction for 6-7h, adding the product into ethyl acetate, stirring and layering, taking an upper oil layer, and then carrying out rotary evaporation to remove ethyl acetate, thus obtaining the dihydroxy-acetoacetate ethyl-ester-based polydimethylsiloxane; wherein, 155-163g of siloxane-based methyl acetoacetate and 36-38g of tetramethylammonium hydroxide aqueous solution with the mass concentration of 25 percent are added into each kilogram of alpha, omega-dihydroxy polydimethylsiloxane;
and 4, step 4: installing an HCl absorption device in a reaction kettle, then simultaneously adding polyether glycol and diethyl ether into the reaction kettle, then dropwise adding dimethyldichlorosilane into the reaction kettle at the temperature of 5-10 ℃, controlling the dropwise adding to be complete within 2h, then stirring for reacting for 8-10h, then adding dihydroxyacetoacetic acid ethyl ester-based polydimethylsiloxane, then heating to 90-95 ℃ for reflux reaction for 10-12h, and removing the solvent by reduced pressure distillation to obtain a dihydroxyacetic acid vinyl ester-based silanized monomer; wherein 278 and 281g of dimethyldichlorosilane is added into each kilogram of polyether glycol, and 1.63 to 1.64kg of dihydroxyacetoacetic acid ethyl ester-based polydimethylsiloxane is added; two alcoholic hydroxyl groups in the polyether diol can react with two silicon-chlorine bonds in the dimethyldichlorosilane, so that silicon-chlorine bonds are introduced into two sides of the polyether diol, and the silicon-chlorine bonds can react with hydroxyl groups in the dihydroxyacetoacetic acid ethyl ester-based polydimethylsiloxane, so that the polyether diol and the dihydroxyacetoacetic acid ethyl ester-based polydimethylsiloxane formed in the prepared dihydroxyacetoacetic acid vinyl ester-based silanization monomer are subjected to a crosslinking reaction through the dimethyldichlorosilane;
the specific preparation process of the antibacterial cross-linking agent is as follows:
(1) adding 3-mercaptopropionic acid methyl ester and 25 mass percent ammonia water into a reaction kettle at the temperature of 0-5 ℃, stirring for reaction for 2 hours, slowly heating to 50-60 ℃, preserving heat for reaction for 4-5 hours, and then evaporating unreacted ammonia water to obtain 3-mercaptopropionamide; wherein, 140-150mL of ammonia water with the mass concentration of 25% is added into each mole of the 3-mercaptopropionic acid methyl ester;
(2) adding 3-mercaptopropionamide and dichloromethane into a reaction kettle at the same time, heating to 40-45 ℃, dropwise adding sulfonyl chloride, controlling the dropwise adding to be complete within 1h, then carrying out heat preservation reaction for 7-8h, carrying out rotary evaporation, recovering a solvent, and then recrystallizing the obtained product with petroleum ether to obtain 5-chloroisothiazolinone; wherein 3-mercaptopropionamide and sulfonyl chloride are added according to the mass ratio of 1:3, and 100mL of dichloromethane is added into each mole of 3-mercaptopropionamide;
(3) simultaneously adding 5-chloroisothiazolinone, 3-butene-2-one, paraformaldehyde, ethanol and concentrated hydrochloric acid into a reaction tank, stirring and heating to 80-85 ℃, carrying out reflux reaction for 8-9h, removing ethanol by rotary evaporation, adding the obtained solid into water, washing to be neutral, and then drying to obtain 5-chloro-ketene-isothiazolinone; wherein, 5-chloroisothiazolinone and 3-butene-2-ketone are mixed according to the mass ratio of 1:1.1, 58-61g of paraformaldehyde, 400mL of ethanol and 450mL of concentrated hydrochloric acid are added into each mole of 5-chloroisothiazolinone at the same time;
(4) simultaneously adding resorcinol, 5-chloro-ketene-isothiazolinone, potassium carbonate and potassium iodide into a reaction kettle, then adding an acetone solution into the reaction kettle, stirring and dissolving, heating to 95 ℃ under the protection of nitrogen, carrying out reflux reaction for 10-12h, standing overnight, filtering, adding water into filtrate for diluting, extracting with benzene, washing an extracting solution with water for 3 times, drying, and removing a solvent by rotary evaporation to obtain the phenolic ketene isothiazolinone; wherein resorcinol and 5-chloro-ketene-isothiazolinone are mixed according to the mass ratio of 1:1.01-1.02, 150-154g potassium carbonate and 173-175g potassium iodide are added into each mol of resorcinol;
(5) adding phenolic ketene isothiazolinone, liquid alkali with the mass concentration of 40% and ethanol into a reaction kettle at the same time, stirring and dissolving, heating to 90 ℃, dropwise adding epoxy chloropropane between 1-1.5h for reaction, controlling the dropwise adding completely within 30min, keeping the temperature for reaction for 8-9h after the dropwise adding is finished, heating to 100-105 ℃, evaporating azeotrope of epoxy chloropropane and ethanol, washing the obtained solid to neutrality, and drying to obtain the antibacterial cross-linking agent, wherein 2.3-2.4mol of epoxy chloropropane is added into each mol of the phenolic ketene isothiazolinone, 52-58g of sodium hydroxide solution is added, and 400mL of ethanol 380-containing organic solvent is added.
The invention has the beneficial effects that:
1. the auxiliary antioxidant polymer chain prepared by the invention contains-NH-COO-bond, can carry out ring-opening reaction with epoxy group in the antibacterial cross-linking agent at high temperature, so that one end of the antibacterial cross-linking agent is fixed on the auxiliary antibacterial polymer chain in a cross-linking way, and meanwhile, a branched chain is grafted on the auxiliary antibacterial polymer chain
The group and methylene between two carbonyls have higher activity under the alkaline condition of adding triethylamine, can generate carbanions, simultaneously one end of the antibacterial cross-linking agent contains alpha and beta unsaturated carbonyl groups, and can perform addition reaction, so that the other end of the antibacterial cross-linking agent is connected to adjacent auxiliary antibacterial polymer chains, the auxiliary antibacterial polymer chains are connected through the antibacterial cross-linking agent, a compact network structure is formed, the antibacterial cross-linking agent can be tightly attached to the surface of a test piece in the using process of the adhesive, and high adhesion performance is realized.
2. One end of the antibacterial cross-linking agent prepared by the invention is connected with one side of the carbonyl of the-NH-COO-mesoester group in the antioxidant-assisted polymer, and the other end is connected with one end of the hydroxyl of the mesoester group in the antioxidant-assisted polymer, so that when the adhesive is hydrolyzed in high-temperature water, polymer chains are still connected through the antibacterial cross-linking agent, and the adhesive cannot be reduced in adhesive strength due to hydrolysis.
3. In order to realize high antibacterial performance of the adhesive, the water-absorbing group quaternary ammonium group is introduced into the antibacterial cross-linking agent chain to cause the adhesive to absorb water, so that the adhesive is easy to hydrolyze, but the antibacterial cross-linking agent is directly connected to the branched chain
The groups are connected with polydimethylsiloxane, and the polydimethylsiloxane has higher hydrophobic property, so that the water absorption of quaternary ammonium groups is compensated by the polydimethylsiloxane, and the large amount of absorption of water vapor is reduced.
4. In the prepared polyurethane adhesive mesh structure, ammonium chloride groups on a polymer main chain are adjacent to isothiazolinone groups on an antibacterial cross-linking agent, ammonium chloride destroys external cell walls of bacteria on the surface of the bacteria, the isothiazolinone groups on the polymer directly destroy DNA molecules in the bacteria after the cell walls are destroyed, and then the effects that the polymer destroys the cell walls and then destroys the DNA molecules in the bacteria are achieved.
5. The polyurethane adhesive is prepared by crosslinking an assistant antibacterial polymer, wherein the assistant antibacterial polymer is polymerized by a dihydroxyvinylacetate-based silanized monomer, and the dihydroxyvinylacetate-based silanized monomer is polymerized by dihydroxyacetoacetoxyethyl-polydimethyl siloxane and polyether diol, so that a large number of oxysilane bonds and acetoacetoxyethyl bonds are uniformly distributed on the prepared polymer face, and the high-temperature resistance of the polymer is improved by uniformly introducing the oxysilane bonds.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
FIG. 1 is a cross-linking structural diagram of the polyurethane adhesive of the present invention.
Detailed Description
Referring to fig. 1, the following embodiments are described in detail:
example 1:
the specific preparation process of the antibacterial cross-linking agent is as follows:
(1) adding 2mol of 3-mercaptopropionic acid methyl ester and 300mL of ammonia water with the mass concentration of 25% into a reaction kettle at the temperature of 5 ℃, stirring for reacting for 2 hours, slowly heating to 60 ℃, preserving the temperature for reacting for 4 hours, and then evaporating unreacted ammonia water to obtain 3-mercaptopropionamide; the infrared analysis of the product showed that the concentration was 3189cm-1And 3366cm-1A double peak of amino groups appears;
(2) 2mol of 3-mercaptopropionamide and 100mL of dichloromethaneAdding alkane into a reaction kettle at the same time, heating to 45 ℃, dropwise adding 3mol of sulfonyl chloride, controlling the dropwise adding to be complete within 1h, then carrying out heat preservation reaction for 7h, carrying out rotary evaporation, recovering a solvent, and then recrystallizing the obtained product with petroleum ether to obtain 5-chloroisothiazolinone; the infrared analysis of the product showed that the concentration was 1608cm-1An infrared absorption peak of olefin appeared, and the double peak of amino group became 3300cm-1A single peak of (a);
(3) adding 2mol of 5-chloroisothiazolinone, 2.2mol of 3-butene-2-one, 120g of paraformaldehyde, 850mL of ethanol and 8.8mL of concentrated hydrochloric acid into a reaction tank at the same time, stirring and heating to 85 ℃, carrying out reflux reaction for 8h, carrying out rotary evaporation to remove ethanol, adding the obtained solid into water, washing to neutrality, and then drying to obtain the 5-chloro-ketene-isothiazolinone, wherein the reaction structural formula is shown in the specification, and 3300cm of infrared analysis is carried out on the product-1The infrared absorption peak of the secondary amino group disappears;
(4) simultaneously adding 2mol of resorcinol, 2.03mol of 5-chloro-ketene-isothiazolinone, 304g of potassium carbonate and 348g of potassium iodide into a reaction kettle, then adding 800mL of acetone solution into the reaction kettle, stirring and dissolving the acetone solution, heating the mixture to 95 ℃ under the protection of nitrogen for reflux reaction for 11 hours, standing the mixture overnight, filtering the mixture, adding water into filtrate for dilution, then extracting the filtrate by using benzene, washing an extracting solution by using water for 3 times, drying the extracting solution, and removing the solvent by rotary evaporation to obtain the phenol ketene-isothiazolinone, wherein the reaction structural formula is shown in the specification, and the infrared analysis of the product is 3350cm-1An infrared absorption peak of the phenolic hydroxyl appears;
(5) simultaneously adding 1mol of phenolic ketene isothiazolinone, 55g of liquid alkali with the mass concentration of 40% and 400mL of ethanol into a reaction kettle, stirring and dissolving, heating to 90 ℃, dropwise adding 2.35mol of epoxy chloropropane during the reaction for 1-1.5h, and controlling the dropwise addition to be complete within 30minAfter the reaction is finished, the temperature is kept for reaction for 9 hours, then the temperature is raised to 100 ℃, azeotrope of epichlorohydrin and ethanol is evaporated, the obtained solid is washed to be neutral and dried, the antibacterial cross-linking agent is obtained, the reaction structural formula is shown in the specification, and infrared analysis is carried out on the product, wherein the infrared analysis shows that 906cm is obtained-1An infrared absorption peak of an epoxy group appears;
example 2:
the specific preparation process of the cross-linking agent is as follows:
(1) adding a mixed solvent of 200mL of ethanol and 100mL of water, 80g of paraformaldehyde and 226(2mol) g of N-isopropylacrylamide into a reaction tank, stirring to dissolve, heating to 65 ℃, adding 396g (2.1mol) of p-nitrophenol, stirring to react for 7 hours, evaporating the solvent to separate out crystals, recrystallizing the obtained crystals with ethanol to obtain acrylamide nitrophenol, wherein the reaction structural formula is shown in the specification, and infrared analysis on the product shows that 1613cm of the product is 1613cm-1Shows an infrared absorption peak of the conjugated olefin of 3350cm-1An infrared absorption peak of the phenolic hydroxyl appears, meanwhile, carbon atoms in the ortho-position and the meta-position of the phenolic hydroxyl contain active hydrogen, aminomethylation reaction can be carried out, and one of the ortho-positions of the hydroxyl in the p-nitrophenol is reacted by controlling the addition amount of the N-isopropylacrylamide;
(2) adding 2mol of acrylamide nitrophenol, 55g of liquid caustic soda with the mass concentration of 40% and 400mL of ethanol into a reaction kettle at the same time, stirring and dissolving, heating to 90 ℃, dropwise adding 4.1mol of epoxy chloropropane between 1 and 1.5 hours of reaction, controlling the dropwise adding within 30min to be complete, keeping the temperature and reacting for 9 hours after the dropwise adding is finished, heating to 100 ℃, evaporating an azeotrope of the epoxy chloropropane and the ethanol, washing the obtained solid to be neutral, drying to obtain a cross-linking agent, carrying out infrared analysis on the product, and carrying out 906cm of ethanol-1An infrared absorption peak of the epoxy group appears.
Example 3:
the specific preparation process of the cross-linking agent is as follows:
adding a mixed solvent of 200mL of ethanol and 100mL of water, 80g of paraformaldehyde and 113g (1mol) of gN-isopropylacrylamide into a reaction tank, stirring for dissolving, heating to 65 ℃, adding 396g (2.1mol) of p-nitrophenol, stirring for reacting for 7 hours, evaporating the solvent to separate out crystals, and recrystallizing the obtained crystals with ethanol to obtain acrylamide nitrophenol; the reaction structure formula is as follows, and the infrared analysis of the product can show that 1613cm-1Shows an infrared absorption peak of the conjugated olefin of 3350cm-1The infrared absorption peak of the phenolic hydroxyl is absent, meanwhile, carbon atoms in the ortho-position and the meta-position of the phenolic hydroxyl contain active hydrogen, aminomethylation reaction can be carried out, and one of the ortho-positions of the hydroxyl in the p-nitrophenol is reacted by controlling the addition amount of the N-isopropylacrylamide;
example 4:
the specific preparation process of the cross-linking agent is as follows:
adding 1mol of resorcinol, 55g of liquid caustic soda with the mass concentration of 40% and 400mL of ethanol into a reaction kettle at the same time, stirring and dissolving, heating to 90 ℃, dropwise adding 4.1mol of epoxy chloropropane between 1 and 1.5 hours of reaction, controlling the dropwise adding completely within 30min, keeping the temperature after completing the dropwise adding, reacting for 9 hours, heating to 100 ℃, evaporating an azeotrope of the epoxy chloropropane and the ethanol, washing the obtained solid to be neutral, drying to obtain a cross-linking agent, wherein the reaction structural formula is as follows, performing infrared analysis on the product, and analyzing 906cm of the product-1An infrared absorption peak of an epoxy group appears at the same time of 3350cm-1The infrared absorption peak of the phenolic hydroxyl disappears;
example 5:
the specific preparation process of the dihydroxyvinyl acetate-based silanized monomer is as follows:
step 1: adding 1kg of 4-methyl chloroacetoacetate into a reaction kettle, stirring and cooling to 5 ℃, dropwise adding 760mL of 33 mass percent methylamine ethanol solution, dropwise adding 120mL of 40 mass percent liquid alkali solution for 5min, controlling the methylamine ethanol solution to be completely dropwise added within 1h, controlling the 40 percent liquid alkali solution and the methylamine ethanol solution to be completely dropwise added simultaneously, controlling the reaction temperature to be 15 ℃ in the dropwise adding process, heating to 75 ℃ after completely dropwise adding, reacting for 4h, standing, separating an oil layer, and performing rotary evaporation to recover methylamine to obtain the methyl 4-methylaminoacetoacetate, wherein the reaction structural formula is as follows, performing infrared analysis on the product, and performing infrared analysis at 772cm-1The absorption peak at C-Cl disappeared at 3281cm-1The absorption peak of secondary amine appears;
step 2: simultaneously adding 4-methyl amino methyl acetoacetate and 0.95mol gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into a reaction kettle, heating to 85 ℃, stirring for reaction for 6 hours, and then carrying out rotary evaporation to collect unreacted 4-methyl amino methyl acetoacetate to obtain siloxane methyl acetoacetate; the product was analyzed by infrared at 3281cm-1The absorption peak at the secondary amine disappeared at the same time at 1100cm-1Shows an infrared absorption peak of a silicon-oxygen bond at 1744cm-1Infrared absorption peak of carbonyl appears;
and step 3: adding 1kg of alpha, omega-dihydroxy polydimethylsiloxane into a reaction kettle, stirring and heating to 85 ℃, then adding 160g of siloxane-based methyl acetoacetate and 37g of 25% tetramethyl ammonium hydroxide aqueous solution, stirring and reacting for 2h, heating to 150 ℃, then carrying out reflux reaction for 6h, adding the product into ethyl acetate, stirring and layering, taking an upper oil layer, and then carrying out rotary evaporation to remove ethyl acetate, thus obtaining the dihydroxyacetoacetic acid ethyl ester-based polydimethylsiloxane;
and 4, step 4: installing an HCl absorption device in a reaction kettle, then simultaneously adding 1kg of polyether diol and 1.5L of diethyl ether into the reaction kettle, controlling the temperature to be 10 ℃ and dropwise adding 280g of dimethyldichlorosilane into the reaction kettle, controlling the dropwise adding to be complete within 2h, then stirring and reacting for 10h, taking a certain amount of reaction liquid, carrying out infrared analysis to know that an infrared absorption peak of a silicon-chlorine bond appears and an infrared absorption peak of hydroxyl disappears, thus knowing that two polyether diols are completely reacted, carrying out infrared analysis during the reaction process when 275g of dimethyldichlorosilane is dropwise added, still having a hydroxyl peak, thus knowing that the reaction is incomplete when 275g of dimethyldichlorosilane is added, then adding 1.63kg of dihydroxyacetoacetic acid ethyl ester-based polydimethylsiloxane into the reaction liquid, then heating to 95 ℃ and carrying out reflux reaction for 10h, carrying out reduced pressure distillation to remove a solvent to obtain the dihydroxyacetic acid vinyl ester-based silanized monomer, it was found that there was no infrared absorption peak of silicon-chlorine bond by the infrared analysis of the product, and when 1.62kg of bishydroxyacetoacetato-based polydimethylsiloxane was controlled to be added, the product was subjected to the infrared analysis for the presence of silicon-chlorine bond, whereby it was found that when 280g of dimethyldichlorosilane and 1.63kg of bishydroxyacetoacetato-based polydimethylsiloxane were added in this example, both ends of the prepared polymer were terminated by the bishydroxyacetoacetato-based polydimethylsiloxane.
Example 6:
a preparation method of a high-temperature and high-humidity resistant polyurethane adhesive comprises the following specific preparation processes:
firstly, adding 800g of the bishydroxyvinyl acetate based silanized monomer prepared in the example 5 into a reaction kettle, decompressing, heating to 120 ℃ for dehydration treatment, then adding 140g of isophorone diisocyanate and 1.5g of dibutyltin dilaurate, heating to 85 ℃, stirring for reaction for 3 hours, then cooling to 60 ℃, adding 5g of 1, 4-butanediol, stirring for reaction for 50 minutes at constant temperature, and obtaining a polymer glue solution; performing infrared analysis on the polymer glue solution at 1540cm-1The infrared absorption peak of the amino ester is appeared at 2270cm-1An infrared absorption peak having no isocyanate group;
secondly, adding 1kg of polymer colloid into a reaction kettle, cooling to 5 ℃, adding 215g of methyl bromide, stirring for 30min, heating and pressurizing to 0.7-0.8MPa, stopping heating, recovering excessive methyl bromide after stirring and reacting for 8h, adding absolute ethyl alcohol and activated carbon, heating to dissolve, driving off the methyl bromide, heating to 90 ℃, recovering ethanol, adding acetone, stirring for 10min, filtering while hot, naturally cooling filtrate, evaporating the acetone, and drying the obtained solid product to obtain the antibacterial assisting polymer;
step three, 165g of the antibacterial cross-linking agent prepared in the example 1, 1kg of the antibacterial polymer and 5L of ethanol solution are weighed and added into a reaction kettle at the same time, stirred and dissolved, the temperature is raised to 110 ℃ for reaction for 2 hours, 800g of triethylamine is added into the reaction kettle, the reaction temperature is reduced to 75 ℃ for reaction for 7 hours, then the reaction product is cooled and discharged, the obtained product is subjected to rotary evaporation, the solvent and the micromolecule substance in the product are removed to obtain a solid substance, then the solid substance is added into ethanol, and the mixture is stirred to prepare a glue solution with the viscosity of 6200mPa.s, namely the polyurethane glue solution.
Example 7:
a preparation method of a high-temperature and high-humidity resistant polyurethane adhesive comprises the following specific preparation processes:
firstly, adding 800g of the bishydroxyvinyl acetate based silanized monomer prepared in the example 5 into a reaction kettle, decompressing, heating to 120 ℃ for dehydration treatment, then adding 140g of isophorone diisocyanate and 1.6g of dibutyltin dilaurate, heating to 85 ℃, stirring for reaction for 3 hours, then cooling to 60 ℃, adding 5g of 1, 4-butanediol, stirring for reaction for 50 minutes at constant temperature, and obtaining a polymer glue solution;
and secondly, weighing 165g of the antibacterial cross-linking agent prepared in the example 1 and 1kg of polymer glue solution, simultaneously adding the antibacterial cross-linking agent and the polymer glue solution into a reaction kettle, stirring and dissolving, heating to 110 ℃ for reaction for 2 hours, then adding 800g of triethylamine into the mixture, cooling to 75 ℃ for reaction for 7 hours, then cooling and discharging the mixture, performing rotary evaporation on the obtained product, removing a solvent and small molecular substances in the mixture to obtain a solid substance, then adding the solid substance into ethanol, and stirring to prepare a glue solution with the viscosity of 6200mPa.s, namely the polyurethane glue solution.
Example 8:
a preparation method of a high-temperature and high-humidity resistant polyurethane adhesive comprises the following specific preparation processes:
firstly, adding 800g of the bishydroxyvinyl acetate based silanized monomer prepared in the example 5 into a reaction kettle, decompressing, heating to 120 ℃ for dehydration treatment, then adding 140g of isophorone diisocyanate and 1.6g of dibutyltin dilaurate, heating to 85 ℃, stirring for reaction for 3 hours, then cooling to 60 ℃, adding 5g of 1, 4-butanediol, stirring for reaction for 50 minutes at constant temperature, and obtaining a polymer glue solution;
and secondly, weighing 165g of the antibacterial cross-linking agent prepared in the example 1 and 1kg of polymer glue solution, simultaneously adding the antibacterial cross-linking agent and the polymer glue solution into a reaction kettle, stirring and dissolving, heating to 110 ℃ for reaction for 2 hours, then adding 800g of triethylamine into the mixture, cooling to 75 ℃ for reaction for 7 hours, then cooling and discharging the mixture, performing rotary evaporation on the obtained product, removing a solvent and small molecular substances in the mixture to obtain a solid substance, then adding the solid substance and 36g of benzyltriethylammonium chloride into ethanol, and stirring to prepare glue solution with the viscosity of 6200mPa.s, namely the polyurethane glue solution.
Example 9:
a preparation method of a high temperature and high humidity resistant polyurethane adhesive is the same as that in example 7, and the antibacterial cross-linking agent prepared in example 1 and used in example 7 is replaced by the cross-linking agent prepared in example 2.
Example 10
A preparation method of a high-temperature and high-humidity resistant polyurethane adhesive is the same as that in example 7, the antibacterial cross-linking agent prepared in example 1 and used in example 7 is replaced by the cross-linking agent prepared in example 2, meanwhile, in the third step, a solid substance and 43g of 5-chloro-2-methyl-1-isothiazoline-3-ketone are added into ethanol, and the mixture is stirred to prepare a glue solution with the viscosity of 6200mPa.s, namely the polyurethane adhesive.
Example 11:
a preparation method of a high temperature and high humidity resistant polyurethane adhesive is the same as that in example 7, and the antibacterial cross-linking agent prepared in example 1 and used in example 7 is replaced by the cross-linking agent prepared in example 3.
Example 12:
a preparation method of a high temperature and high humidity resistant polyurethane adhesive is the same as that in example 7, and the antibacterial cross-linking agent prepared in example 1 and used in example 7 is replaced by the cross-linking agent prepared in example 4.
Example 13:
a preparation method of a high-temperature and high-humidity resistant polyurethane adhesive is the same as that in example 6, a bishydroxyvinyl acetate based silanized monomer used in the first step in example 6 is replaced by polyether glycol, and a second quaternization reaction is not carried out.
Test example:
(1) according to the GB/T2791-1995 standard, the adhesive prepared in the example 6-12 is coated between two polyamide plastic plates, after the two polyamide plastic plates are bonded, the pressure of 1MPa is applied to the bonding position, and then the bonded composite plate is subjected to curing treatment, and the peel strength is measured to be I1Placing the cured composite board prepared by the same method in a PCT aging oven for treatment for 50h, controlling the temperature and humidity to be 121 ℃/100% RH, and then measuring the peel strength I after the treatment2The peel strength reduction rate (I) was calculated1-I2)/I1X is 100%; the specific calculation results are shown in table 1;
table 1 peel strength N. (25mm) of the adhesives prepared in examples 6-12-1And the rate of change of peel strength after treatment in steam;
as can be seen from Table 1, the adhesives prepared in examples 6-12 all have high peel strength, while the adhesives prepared in examples 13 and 14 have low peel strength, and since the prepared polymers are crosslinked by the crosslinking agent in the process of preparing the adhesives prepared in examples 6-12 to form a compact network structure, the adhesives can be tightly attached to the surface of a test piece in the using process of the adhesives to realize high bonding performance, but the adhesives prepared in examples 13 and 14 are not crosslinked to cause the reduction of the bonding performance, and meanwhile, the peel strength of the adhesives prepared in examples 6-10 is not greatly changed in high-temperature hot water, and since the antioxidant-assisting polymer chains contain-NH-COO-bonds, the adhesives can be combined with epoxy groups in the antibacterial crosslinking agent at high temperatureThe ring-opening reaction is carried out to ensure that one end of the antibacterial cross-linking agent is fixed on the auxiliary antibacterial polymer chain in a cross-linking way, and simultaneously, the auxiliary antibacterial polymer chain is grafted with a branched chain
The group, methylene between two carbonyls has higher activity under the alkaline condition of adding triethylamine, can generate carbanions, one end of the antibacterial cross-linking agent contains alpha and beta unsaturated carbonyl, and can perform addition reaction, so that the other end of the antibacterial cross-linking agent is connected to the adjacent antibacterial polymer chains, the antibacterial polymer chains are connected through the antibacterial cross-linking agent to form a compact network structure, the cross-linking structural formula is shown in figure 1, the antibacterial cross-linking agent can be tightly attached to the surface of a test piece in the using process of the adhesive, high adhesion performance is realized, meanwhile, one end of the antibacterial cross-linking agent is connected with one side of carbonyl of an ester group in-NH-COO-and the other end of the carbonyl of the ester group is connected with one end of hydroxyl of the ester group, when the adhesive is hydrolyzed in high-temperature water, the polymer chains are still connected through the antibacterial cross-linking agent and can still be tightly compounded on, the adhesive strength of the adhesive is not reduced due to hydrolysis, but both ends of the cross-linking agent in example 11 are connected with one side of hydroxyl of the ester group in-NH-COO-, and are directly separated and the cross-linking system is destroyed during hydrolysis, and both ends of the cross-linking agent in example 12 are connected with one side of carbonyl of the ester group in-NH-COO-, and are directly separated and the cross-linking system is destroyed during hydrolysis, so that the adhesive strength of examples 11 and 12 is reduced, and the-NH-COO-bond in examples 13 and 14 is not cross-linked and protected to be directly hydrolyzed, destroyed and polymerized, so that the adhesive strength is greatly reduced.
(2) Coating the adhesive prepared in the examples 6-10 on the surface of a glass dish, curing the adhesive to form a layer of adhesive film on the surface of the glass dish, adding 0.2mL of escherichia coli and staphylococcus aureus into beef soup, culturing the beef soup at 37 ℃ for 24 hours to obtain mother liquor, and diluting the mother liquor to 10 times-5Or 10-6Taking the bacterial liquid as inoculated bacterial liquid, sucking 0.4mL of bacterial liquid to be inoculated according to GB/T4789.2-2003, uniformly and dropwise adding the bacterial liquid to be inoculated on the surfaces of a blank glass dish and the adhesive film prepared in the example 6-12, and placing the culture dish in an aseptic environment for cultureCulturing for 3h, washing the surface of the gel membrane with sterilized water, collecting the washed liquid, shaking, uniformly coating 0.2mL of washing liquid on solid agar culture medium, anaerobically culturing at 37 deg.C for 24h, counting the number of colonies on the agar culture medium, and calculating antibacterial rate P ═ R (R-R)1) R is 100%, R is the colony number of the blank control group, R1The colony counts for the adhesive films prepared in examples 6-10 were calculated as shown in Table 2;
table 2 determination results of antibacterial performance and antibacterial rate of adhesives prepared in examples 6 to 10%
| Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | |
| Escherichia coli | 100 | 87.2 | 95.8 | 84.9 | 95.1 |
| Staphylococcus aureus | 100 | 86.2 | 96.1 | 85.3 | 95.8 |
As can be seen from table 2, the adhesive prepared in example 6 has high antibacterial performance, because the ammonium chloride groups on the polymer main chain in the polyurethane adhesive network structure and the isothiazolinone groups on the antibacterial cross-linking agent are adjacent, the ammonium chloride damages the external cell wall of the bacteria on the surface of the bacteria, the isothiazolinone groups on the polymer directly damage DNA molecules inside the bacteria after the cell wall is damaged, and the synergistic effect of the ammonium chloride groups and the isothiazolinone groups can achieve high-efficiency bactericidal effect, and meanwhile, because the ammonium chloride groups and the isothiazolinone groups are uniformly distributed in the network structure, the polymer has uniform and high-efficiency bactericidal performance; in examples 7 and 9, no quaternary ammonium salt and isothiazolinone group is introduced, so that the antibacterial effect is reduced by only one antibacterial agent, and the antibacterial agent is easily dispersed unevenly by directly adding the antibacterial agent in examples 8 and 10, thereby affecting the antibacterial effect.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (9)
1. The preparation method of the high-temperature and high-humidity resistant polyurethane adhesive is characterized by comprising the following specific preparation processes of:
firstly, adding a dihydroxyvinyl acetate-based silanized monomer into a reaction kettle, reducing pressure, heating to 120 ℃ for dehydration, then adding isophorone diisocyanate and dibutyltin dilaurate, heating to 80-85 ℃, stirring for reaction for 2-3h, then cooling to 60 ℃, adding 1, 4-butanediol, stirring for reaction for 40-50min at constant temperature, and obtaining a polymer glue solution;
secondly, adding polymer colloid into a reaction kettle, cooling to 5 ℃, adding methyl bromide, stirring for 30min, heating and pressurizing to 0.7-0.8MPa, stopping heating, stirring for reaction for 7-8h, recovering excessive methyl bromide, adding absolute ethyl alcohol and activated carbon, heating for dissolving, driving up methyl bromide, heating to 90 ℃, recovering ethanol, adding acetone, filtering while hot, evaporating the filtrate to remove acetone, and drying to obtain the antibacterial assisting polymer;
thirdly, weighing a certain amount of antibacterial cross-linking agent, an antibacterial polymer and an ethanol solution, adding the antibacterial cross-linking agent, the antibacterial polymer and the ethanol solution into a reaction kettle, stirring and dissolving, heating to 110-115 ℃, reacting for 2 hours, adding triethylamine into the reaction kettle, cooling to 75-80 ℃, reacting for 6-7 hours, cooling and discharging, performing rotary evaporation on the obtained product, removing the solvent and micromolecule substances in the product to obtain a solid substance, adding the solid substance into ethanol, and stirring to prepare the polyurethane adhesive;
the specific preparation process of the antibacterial cross-linking agent is as follows:
(1) adding 3-mercaptopropionic acid methyl ester and 25 mass percent ammonia water into a reaction kettle at the temperature of 0-5 ℃, stirring for reaction for 2 hours, slowly heating to 50-60 ℃, preserving heat for reaction for 4-5 hours, and then evaporating unreacted ammonia water to obtain 3-mercaptopropionamide;
(2) adding 3-mercaptopropionamide and dichloromethane into a reaction kettle at the same time, heating to 40-45 ℃, dropwise adding sulfonyl chloride, controlling the dropwise adding to be complete within 1h, then carrying out heat preservation reaction for 7-8h, carrying out rotary evaporation, recovering a solvent, and then recrystallizing the obtained product with petroleum ether to obtain 5-chloroisothiazolinone;
(3) simultaneously adding 5-chloroisothiazolinone, 3-butene-2-one, paraformaldehyde, ethanol and concentrated hydrochloric acid into a reaction tank, stirring and heating to 80-85 ℃, carrying out reflux reaction for 8-9h, removing ethanol by rotary evaporation, adding the obtained solid into water, washing to be neutral, and then drying to obtain 5-chloro-ketene-isothiazolinone;
(4) simultaneously adding resorcinol, 5-chloro-ketene-isothiazolinone, potassium carbonate and potassium iodide into a reaction kettle, then adding an acetone solution into the reaction kettle, stirring and dissolving, heating to 95 ℃ under the protection of nitrogen, carrying out reflux reaction for 10-12h, standing overnight, filtering, adding water into filtrate for diluting, extracting with benzene, washing an extracting solution with water for 3 times, drying, and removing a solvent by rotary evaporation to obtain the phenolic ketene isothiazolinone;
(5) adding phenol ketene isothiazolinone, liquid alkali with the mass concentration of 40% and ethanol into a reaction kettle at the same time, stirring and dissolving, heating to 90 ℃, dropwise adding epoxy chloropropane during the reaction for 1-1.5h, controlling the dropwise adding completely within 30min, keeping the temperature and reacting for 8-9h after the dropwise adding is finished, heating to 100-105 ℃, evaporating an azeotrope of the epoxy chloropropane and the ethanol, washing the obtained solid to be neutral, and drying to obtain the antibacterial cross-linking agent.
2. The preparation method of the high temperature and high humidity resistant polyurethane adhesive according to claim 1, wherein the raw materials added in the first step are as follows in parts by weight: 78-85 parts of dihydroxyvinyl acetate-based silanized monomer, 13-15 parts of isophorone diisocyanate, 0.15-0.16 part of dibutyltin dilaurate and 0.4-0.6 part of 1, 4-butanediol.
3. The method for preparing the high temperature and high humidity resistant polyurethane adhesive according to claim 1, wherein the specific preparation process of the bishydroxyvinyl acetate based silanized monomer is as follows:
step 1: adding 4-methyl chloroacetoacetate into a reaction kettle, stirring and cooling to 0-5 ℃, dropwise adding a methylamine ethanol solution with the mass concentration of 33%, dropwise adding a liquid alkali solution with the mass concentration of 40% after dropwise adding for 5min, heating to 70-75 ℃ after completely dropwise adding, reacting for 3-4h, standing, separating an oil layer, and performing rotary evaporation to recover methylamine to obtain 4-methyl aminoacetoacetate;
step 2: adding 4-methyl amino methyl acetoacetate and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into a reaction kettle at the same time, heating to 80-85 ℃, stirring for reaction for 5-6h, and then performing rotary evaporation to collect unreacted 4-methyl amino methyl acetoacetate to obtain siloxane-based methyl acetoacetate;
and step 3: adding alpha, omega-dihydroxy polydimethylsiloxane into a reaction kettle, stirring and heating to 80-85 ℃, then adding siloxane-based methyl acetoacetate and 25% tetramethyl ammonium hydroxide aqueous solution, stirring and reacting for 2h, heating to 140-150 ℃, then carrying out reflux reaction for 6-7h, adding the product into ethyl acetate, stirring and layering, taking an upper oil layer, and then carrying out rotary evaporation to remove ethyl acetate, thus obtaining the dihydroxy-acetoacetate ethyl-ester-based polydimethylsiloxane;
and 4, step 4: installing an HCl absorption device in a reaction kettle, then simultaneously adding polyether glycol and diethyl ether into the reaction kettle, dropwise adding dimethyldichlorosilane into the reaction kettle at the temperature of 5-10 ℃, controlling the dropwise adding to be complete within 2h, then stirring for reacting for 8-10h, then adding dihydroxyacetoacetic acid ethyl ester-based polydimethylsiloxane, heating to 90-95 ℃, carrying out reflux reaction for 10-12h, and carrying out reduced pressure distillation to remove the solvent to obtain the dihydroxyacetic acid vinyl ester-based silanized monomer.
4. The method as claimed in claim 3, wherein step 1 is carried out by adding 750-770mL of 33% methylamine ethanol solution per kilogram of methyl 4-chloroacetoacetate.
5. The method for preparing the high temperature and high humidity resistant polyurethane adhesive according to claim 3, wherein the methyl 4-methylaminoacetoacetate and the gamma- (2, 3-glycidoxy) propyltrimethoxysilane are added in the step 2 according to the ratio of the amount of the substances of 1: 0.94-0.96.
6. The method as claimed in claim 3, wherein in step 3, 155-163g of methyl siloxane acetoacetate and 36-38g of 25% tetramethyl ammonium hydroxide aqueous solution are added per kg of α, ω -dihydroxy polydimethylsiloxane.
7. The method as claimed in claim 3, wherein 278 and 281g dimethyldichlorosilane and 1.63-1.64kg bishydroxyacetoacetoxyethyl polydimethylsiloxane are added to each kg of polyether glycol in step 4.
8. The method for preparing the high temperature and high humidity resistant polyurethane adhesive according to claim 1, wherein in the step (2), the 3-mercaptopropionamide and the sulfonyl chloride are added according to the mass ratio of 1:3, and 100mL of dichloromethane is added to each mole of the 3-mercaptopropionamide.
9. The method for preparing a polyurethane adhesive with high temperature and humidity resistance according to claim 1, wherein in the step (3), 5-chloroisothiazolinone and 3-buten-2-one are mixed according to the ratio of 1:1.1, and simultaneously, 58-61g of paraformaldehyde, 400mL of ethanol and 450mL of concentrated hydrochloric acid are added to each mole of 5-chloroisothiazolinone.
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| JP6095297B2 (en) * | 2012-08-24 | 2017-03-15 | ヘンケルジャパン株式会社 | Adhesive for laminated sheet |
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