CN114250056B - Highlight water-based vacuum plastic and preparation method thereof - Google Patents
Highlight water-based vacuum plastic and preparation method thereof Download PDFInfo
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- CN114250056B CN114250056B CN202111563937.6A CN202111563937A CN114250056B CN 114250056 B CN114250056 B CN 114250056B CN 202111563937 A CN202111563937 A CN 202111563937A CN 114250056 B CN114250056 B CN 114250056B
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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Abstract
The invention belongs to the technical field of water-based adhesives, and particularly relates to a preparation method of a highlight water-based vacuum plastic absorbing material, which comprises the following steps: 400-600 parts of modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 5-10% and 400-600 parts of modified polyurethane dispersoid are mixed according to parts by weight, and 1-5 parts of thickener is added to adjust the viscosity to be proper, so that the high gloss water-based vacuum plastic is obtained. The modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 5-10% is obtained by controlling hydrolysis, and the modified polyurethane dispersion is prepared by taking diamine modified polyether cyclodextrin as a chain extender, serving as an intramolecular leveling agent, and being matched with the modified polyethylene-vinyl acetate emulsion for use, so that the surface tension difference is reduced, the flow of liquid in a glue layer is reduced, the Beard vortex is inhibited, and the surface roughness of the glue layer is reduced. The high-gloss water-based vacuum plastic plate surface prepared by the method has good effect, good adhesion and strong heat resistance.
Description
Technical Field
The invention belongs to the technical field of water-based adhesives, and particularly relates to a preparation method of a highlight water-based vacuum plastic.
Background
The water-based vacuum plastic is widely applied to the adhesion of soft films such as PVC and the like with materials such as density boards, shaving boards, wood and the like. Generally, the water-based vacuum plastic is constructed in a spraying mode, the liquid drops of the glue are atomized by high-pressure gas and become fine liquid drops to be sprayed on the plate to be laminated, and the plastic can be absorbed after the moisture in the liquid drops volatilizes. During plastic suction, the PVC film is heated and softened, is close to the plate, and air between the PVC film and the plate is pumped away by vacuum, so that the PVC film is tightly adhered to the plate by means of atmospheric pressure. As various textures can be printed on the PVC film, the plate produced by the vacuum plastic sucking process presents the aesthetic feeling which cannot be achieved by the common plate and is popular with people.
With the increasing popularity of aqueous vacuum plastic, people have increasingly higher aesthetic requirements for panels attached with aqueous vacuum plastic, such as sliding doors, cabinets, soundbox boards, computer tables, and the like. The requirements for aqueous vacuum plastic are mainly expressed in the following aspects: plate effect, adhesion and heat resistance. In the effort of the skilled man, aqueous vacuum-absorbing resins have gradually tended to mature, meeting almost all customer demands in terms of adhesion and heat resistance. However, in some applications, such as a high gloss film coated board, any defects on the board surface are easily amplified during the plastic suction process due to the bright film surface of the high gloss film.
Aqueous vacuum-absorbing resins generally comprise aqueous polyurethane dispersions and ethylene-vinyl acetate copolymer emulsions as main components. The inventor finds that the compatibility of the two main components is poor in a large number of practical processes, if the adhesiveness of the aqueous vacuum plastic suction is low, the ethylene-vinyl acetate copolymer emulsion is found to be precipitated at the lower part after standing for a period of time, and the aqueous polyurethane dispersion floats at the upper layer. Therefore, the aqueous vacuum plastic is easy to form microphase separation state in the drying process on the board surface. Microphase separation means that there is a difference in the surface tension of the two regions, and under the driving of this difference in surface tension, the liquid in the phase with low surface tension will flow toward the interface between the two phases, with the end result that the thickness of the coating film at the interface is higher than in the middle, i.e. orange peel, which is the benard effect. At present, some orange marks exist in common water-based vacuum plastic on the market, and any orange marks on the surface of a plate are clearly exposed under the reflection of a high-gloss film, so that the expectation of a user cannot be reached.
Those skilled in the art have conducted intensive studies. CN111849405 discloses a water-based high-gloss vacuum plastic and a preparation method thereof, wherein the raw materials comprise 30-60 parts of water-based polyurethane-polyvinyl acetate emulsion, 5-30 parts of modifier, 30-50 parts of ethylene-vinyl acetate copolymer emulsion, 0.03-0.08 part of defoamer, 0.1-0.6 part of flatting agent, 0.5-5 parts of humectant, 0-4 parts of plasticizer and 0-0.2 part of thickener. The aqueous highlight vacuum plastic is obtained by mixing, adding and stirring the raw materials, and has excellent surface effect, heat resistance and good mechanical strength. However, the leveling agent is still added in the scheme, so that the leveling effect of the aqueous polyurethane-polyvinyl acetate emulsion is still poor. However, the proposal uses the modifier aqueous acrylic ester emulsion Adwell 1367 to increase the bonding strength, which proves that the bonding effect is not good enough. The proposal uses the humectant, delays the drying time of the plastic, and possibly reduces the production efficiency.
CN106916552 discloses a plastic absorbing adhesive, which comprises 60 parts of ethylene-vinyl acetate copolymer emulsion, 1 part of lauric acid monoglyceride, 0.5 part of triethanolamine, 2 parts of amino alcohol complex titanate, 15 parts of methyl isobutyl ketone, 55 parts of polyurethane emulsion, 2 parts of alkyl modified organosiloxane, 3 parts of polyacrylamide, 5 parts of carboxymethyl cellulose and 3 parts of sodium methyldinaphthyl sulfonate. The modified proposal has stable viscosity, moderate activation temperature, good blending performance, high temperature resistance, good bonding strength, high Wen Liuping performance, smooth and flat surface of the adhesive layer and long shelf life. However, this solution contains about 10% solvent methyl isobutyl ketone and has strong irritation and toxicity, which is contrary to the environment.
CN112961640 discloses a polyurethane adhesive film used as an absorbing plastic, a preparation method and application. The scheme uses aqueous polyurethane emulsion and ethylene-vinyl acetate copolymer emulsion as main agents, and uses anti-adhesion auxiliary agents, pH regulator, defoamer, wetting agent, plasticizer and thickener as auxiliary agents to prepare uniform aqueous vacuum plastic, and then the uniform aqueous vacuum plastic is coated and dried to form a film to obtain the polyurethane adhesive film used as the plastic, which has good tensile strength and elongation, good cohesiveness and heat resistance, and has good surface effect due to the coating film. However, since many plastic suction plates have personalized patterns such as engraving and hollowing, the production amount is not high, if a glue film is used for replacing glue spraying, large-scale preparation of the glue film pattern or machine shearing of the glue film cannot be performed by using a machine, and the production efficiency is greatly reduced.
Disclosure of Invention
In order to overcome the defects in the prior art, the technical problems to be solved by the invention are as follows: provides a strong high-gloss water-based vacuum plastic with good plate effect, good binding force and heat resistance, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme: the high-gloss water-based vacuum plastic comprises, by weight, 400-600 parts of modified polyurethane dispersion, 400-600 parts of modified polyethylene-vinyl acetate emulsion with 5-10% of alcoholysis degree and 1-5 parts of thickener;
the preparation method of the modified polyurethane dispersoid comprises the following steps: beta-cyclodextrin, propylene oxide and ethylene oxide react to generate polyether modified cyclodextrin, then the polyether modified cyclodextrin reacts with alkyl glycidyl ether to obtain alkyl polyether cyclodextrin, p-toluenesulfonyl chloride and diamine compound are sequentially added to react respectively to obtain diamine modified alkyl polyether cyclodextrin, and finally the diamine modified alkyl polyether cyclodextrin reacts with polyurethane prepolymer to obtain modified polyurethane dispersoid.
The preparation method of the modified aqueous polyurethane dispersion comprises the following steps:
step 1, heating up 1000 parts of beta-cyclodextrin, decompressing, adding 1-6 parts of catalyst, 200-440 parts of propylene oxide and 80-160 parts of ethylene oxide, heating up and reacting, and then cooling; 1000 parts of dimethylbenzene, 120-150 parts of alkyl glycidyl ether and 1 part of catalyst are added, heated and reacted, and cooled; adding 1 part of alkali solution to obtain alkyl polyether cyclodextrin in an organic phase;
Step 2, adding 2000 parts of N, N-dimethylformamide into the alkyl polyether cyclodextrin, cooling and adding 40-60 parts of solid alkali; 180-250 parts of p-toluenesulfonyl chloride is added, the temperature is raised after low-temperature reaction, and a pale yellow transparent first reaction solution is obtained after the reaction;
step 3, adding the first reaction solution into 400-500 parts of mixed solution containing diamine compound and N, N-dimethylformamide, and heating up for reaction in a nitrogen environment; dropping water into the mixture after cooling, stirring, adding 5000 parts of toluene, stirring to obtain an organic phase, washing, and discarding a water phase; anhydrous calcium chloride in an organic phase is filtered to obtain clear liquid, and the clear liquid is decompressed and distilled to obtain white waxy solid diamine modified alkyl polyether cyclodextrin;
step 4, heating 1000 parts of dihydroxy compound, reducing the water content in the material to 0.05-0.1%, cooling, adding 130-180 parts of diisocyanate, and cooling after heating reaction to obtain polyurethane prepolymer;
step 5, adding 10-20 parts of hydrophilic agent, 80-100 parts of diamine modified alkyl polyether cyclodextrin and a proper amount of acetone into the polyurethane prepolymer, stirring, heating, dripping water and distilling under reduced pressure; and when the acetone content is steamed to 0.5-1.0%, filtering and adding the rest water until the weight solid content is 45-55%, thus obtaining the modified aqueous polyurethane dispersoid.
The preparation method of the modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 5-10% comprises the following steps:
slowly adding 1000 parts of polyethylene-vinyl acetate emulsion into 30-60 parts of alkali solution, stirring, heating, reacting, cooling, adding 250-500 parts of mixed resin, stirring, filtering out the mixed resin, supplementing water to the solid content of 50% by weight, and obtaining the modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 5-10%.
400-600 parts of modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 5-10% and 400-600 parts of modified polyurethane dispersoid are mixed, and 1-5 parts of thickener is added to adjust the viscosity to be proper, so that the high-gloss water-based vacuum plastic is obtained.
The invention has the beneficial effects that: the high gloss aqueous vacuum plastic cement is formed by reacting modified polyethylene-vinyl acetate emulsion, modified aqueous polyurethane dispersion and thickener, wherein the modified polyurethane dispersion contains diamine modified alkyl polyether cyclodextrin. The polyoxypropylene polyoxyethylene ether chain segment in the polyether modified alkyl cyclodextrin can reduce the surface tension, and meanwhile, the hydrophilic and hydrophobic balance can be achieved by adjusting the ratio of ethylene oxide to propylene oxide; the alkyl-combined polyoxypropylene polyoxyethylene ether is a more hydrophobic chain segment, and the outer layer of the cyclodextrin has better hydrophilicity, so that the cyclodextrin has the hydrophobicity adjusted through modification, forms a partially compatible state in water, can be used as an intramolecular flatting agent, delays the benard effect and improves the surface flatness of the high-gloss aqueous vacuum plastic.
Detailed Description
In order to describe the technical contents, the achieved objects and effects of the present invention in detail, the following description will be made with reference to the embodiments.
The most critical concept of the invention is as follows: modified polyurethane dispersion containing diamine modified alkyl polyether cyclodextrin and a small amount of hydrolyzed modified polyethylene-vinyl acetate emulsion are introduced.
The invention provides a highlight water-based vacuum plastic, which comprises, by weight, 400-600 parts of modified polyurethane dispersoid, 400-600 parts of modified polyethylene-vinyl acetate emulsion with 5-10% of alcoholysis degree and 1-5 parts of thickener;
the preparation method of the modified polyurethane dispersoid comprises the following steps: beta-cyclodextrin, propylene oxide and ethylene oxide react to generate polyether modified cyclodextrin, alkyl glycidyl ether is added to react to obtain alkyl polyether cyclodextrin, p-toluenesulfonyl chloride and diamine compound are sequentially added to react respectively to obtain diamine modified alkyl polyether cyclodextrin, and polyurethane prepolymer is added to obtain modified polyurethane dispersoid.
From the above description, the beneficial effects of the invention are as follows: the polyoxypropylene and polyoxyethylene ether chain segments in the diamine modified alkyl polyether cyclodextrin can reduce the surface tension, and meanwhile, the hydrophilic and hydrophobic balance can be achieved by adjusting the ratio of ethylene oxide to propylene oxide; the alkyl-combined polyoxypropylene and polyoxyethylene ether has a more hydrophobic chain segment, and the cyclodextrin outer layer has better hydrophilicity, so that the cyclodextrin outer layer is modified to adjust the hydrophobicity, and a partially compatible state is formed in water, so that the cyclodextrin outer layer can be used as an intramolecular flatting agent, the benard effect is delayed, and the surface flatness of the high-gloss aqueous vacuum plastic is improved.
The invention optimizes the dosage and the synthesis condition of each modifier, the alkylation exists in most alkyl polyether cyclodextrin in a mono-alkyl substitution form, and a small amount of dialkyl substitution, trisubstituted and alkyl polyether cyclodextrin has good compatibility in the system, and does not influence the subsequent modification and application; the structure of the obtained diamine modified alkyl polyether cyclodextrin contains one primary amine and one secondary amine, and both amine groups can react with isocyanate at a lower temperature, namely at 50-55 ℃, so that the reaction rate of hydroxyl contained in the diamine modified alkyl polyether cyclodextrin and the isocyanate is extremely slow, and the final reaction degree is basically not influenced. The modified polyethylene-vinyl acetate emulsion is a polymer with the hydrolysis degree of 5-10%, the hydrolyzed chain segment is polyvinyl alcohol and has a large number of hydroxyl groups, and the hydroxyl groups and oxygen atoms in the polyether modified alkyl cyclodextrin in the modified polyurethane dispersion can form hydrogen bond action, so that the compatibility of the modified polyethylene-vinyl acetate emulsion and the modified polyurethane dispersion in the system is better, microphase separation is not generated, the surface tension difference in the system can be greatly reduced, the flow of glue layer liquid is reduced, the benard vortex is inhibited, and the surface roughness of the high-gloss water-based vacuum plastic absorbing surface is reduced.
The high-gloss water-based vacuum plastic cement prepared by the invention has good strength and heat resistance, and can meet the use requirements of the conventional water-based vacuum plastic cement.
Further, the preparation method of the modified aqueous polyurethane dispersion comprises the following steps:
step 1, after 1000 parts of beta-cyclodextrin is heated to 110-120 ℃ and dehydrated under reduced pressure, adding 1-6 parts of catalyst, heating to 100-120 ℃, introducing 200-440 parts of propylene oxide, keeping for 1-2 hours, continuously introducing 80-160 parts of ethylene oxide, keeping for 1-2 hours, cooling to 25-30 ℃, adding 1000 parts of dimethylbenzene, slowly dropwise adding 120-150 parts of alkyl glycidyl ether, dropwise adding 1 part of catalyst boron trifluoride diethyl ether, heating to 45-55 ℃, keeping for 3-8 hours, cooling to 20-30 ℃, adding 1 part of potassium hydroxide aqueous solution, stirring for 30 minutes, standing, separating an organic phase, volatilizing the solvent from the organic phase, and obtaining the alkyl polyether cyclodextrin;
step 2, adding 2000 parts of N, N-dimethylformamide into the alkyl polyether cyclodextrin, stirring until the N, N-dimethylformamide is completely dissolved, cooling to 0-5 ℃ in an ice water bath, adding 40-60 parts of solid potassium hydroxide, stirring, slowly dropwise adding 180-250 parts of p-toluenesulfonyl chloride, keeping the temperature at 0-5 ℃ for 2-4 hours, heating to 25-30 ℃ within 2 hours, and reacting to obtain pale yellow transparent first reaction liquid;
Step 3, slowly and dropwise adding 400-500 parts of mixed solution containing diamine compound and N, N-dimethylformamide into the first reaction solution, heating to 70-80 ℃, and reacting for 20 hours under the protection of nitrogen; cooling to 0-5 ℃, slowly dripping water with the temperature of 4-6 ℃, stirring at a high speed for 30 minutes, adding 5000 parts of toluene, continuously stirring for 30 minutes, and standing to separate an organic phase; washing the organic phase with deionized water for 2 times successively, discarding the water phase, removing residual water from the organic phase with anhydrous calcium chloride, filtering to obtain clear liquid, and distilling under reduced pressure to volatilize the solvent to obtain white waxy solid diamine modified alkyl polyether cyclodextrin;
step 4, heating 1000 parts of the dihydroxy compound to 110-120 ℃, vacuumizing to reduce the water content in the material to 0.05-0.1%, and cooling to 40-50 ℃; 130-180 parts of diisocyanate is added, the temperature is raised to 75-85 ℃, after 2-5 hours of reaction, the temperature is reduced to 30-40 ℃ to obtain polyurethane prepolymer;
and 5, adding 10-20 parts of hydrophilic agent, 80-100 parts of diamine modified alkyl polyether cyclodextrin and a proper amount of acetone into the polyurethane prepolymer, stirring and heating to 50-55 ℃, continuously reacting for 1-2 hours, dropwise adding water, distilling under reduced pressure to remove the acetone in the system, filtering to remove gel when the acetone content in the emulsion is evaporated to 0.5-1.0%, and supplementing the rest water until the solid content is 45-55%, thus obtaining the modified polyurethane dispersion.
Further, the preparation method of the modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 5-10% comprises the following steps:
slowly adding 30-60 parts of sodium hydroxide solution into 1000 parts of polyethylene-vinyl acetate emulsion, stirring and heating to 40-50 ℃, and reacting for 2-5 hours. Cooling to 15-25 ℃, adding 250-500 parts of mixed bed resin Purolite UltraCleanTM UCW3600 to remove micromolecular salts, stirring for 30 minutes, filtering out the mixed bed resin, and supplementing a small amount of water until the solid content is 50%, thereby obtaining the modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 5-10%.
Further, the alkyl glycidyl ether is one or more of butyl glycidyl ether (CAS number: 2426-08-6), octyl glycidyl ether (CAS number: 2461-15-6) and phenyl glycidyl ether (CAS number: 122-60-1).
Further, the diamine compound is one or more of isophorone diamine and hexamethylenediamine; the polyethylene-vinyl acetate emulsion is Dalian chemical VAE emulsion DA-102 with weight solid content of 55%.
Further, the diisocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate.
Further, the dihydroxy compound is one or more of polyoxypropylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol, neopentyl glycol hexanediol adipate glycol or polycaprolactone glycol with an average molecular weight of 2000 Da.
Further, the thickener adopts one or more of polyurethane associative thickeners Vesmody U902, vesmody U601, vesmody U905 and Vesmody U505.
Example 1 of the present invention is:
the high-gloss aqueous vacuum plastic comprises 400g of modified aqueous polyurethane dispersoid, 600g of modified polyethylene-vinyl acetate emulsion and 5g of thickener in parts by weight;
the modified aqueous polyurethane dispersion comprises the following raw materials in parts by weight: 1000g of beta-cyclodextrin, 1g of catalyst zinc hexacyanocobaltate, 200g of propylene oxide, 80g of ethylene oxide, 1000g of solvent xylene, 150g of octyl glycidyl ether, 1g of catalyst boron trifluoride diethyl ether and 1g of 1mol/L potassium hydroxide aqueous solution; 2000g of N, N-dimethylformamide, 40g of solid potassium hydroxide, 180g of p-toluenesulfonyl chloride, 500g of hexamethylenediamine and 5000g of toluene; 1000g of a dihydroxy compound; 180g of 4,4' -diphenylmethane diisocyanate, 10g of 2- (2-aminoethyl) aminoethyl sodium sulfamate as a hydrophilic agent and a proper amount of acetone;
Wherein the dihydroxyl compound is polyoxypropylene diol with average molecular weight of 2000Da and neopentyl glycol adipate diol.
The raw materials of the modified polyethylene-vinyl acetate emulsion comprise the following components in parts by weight: 1000g of polyethylene-vinyl acetate emulsion, 60g of 10mol/L sodium hydroxide solution, 500g of mixed bed resin Purolite UltraClean TM UCW3600。
Wherein the polyethylene-vinyl acetate emulsion is Dalian chemical VAE emulsion DA-102 with weight solid content of 55%.
The preparation method of the highlight water-based vacuum plastic comprises the following steps:
step 1, heating 1000g of beta-cyclodextrin to 120 ℃ to remove water; adding 1g of catalyst zinc hexacyanocobaltate, heating to 120 ℃, introducing 200g of propylene oxide, continuously introducing 80g of ethylene oxide after keeping for 1h, cooling to 30 ℃, adding 1000g of dimethylbenzene, slowly dropwise adding 150g of octyl glycidyl ether, dropwise adding 1g of boron trifluoride diethyl ether, heating to 45 ℃, keeping the temperature for 8h, cooling to 20 ℃, adding 1g of 1mol/L potassium hydroxide aqueous solution, stirring for 0.5h, standing, separating the organic phase, volatilizing the solvent from the organic phase, and obtaining the octyl polyether cyclodextrin.
And step 2, adding 2000g of N, N-dimethylformamide into the octyl polyether cyclodextrin, stirring until the N, N-dimethylformamide is completely dissolved, cooling to 0 ℃ in an ice water bath, adding 40g of solid potassium hydroxide, stirring, slowly dropwise adding 180g of p-toluenesulfonyl chloride, keeping the temperature at 0 ℃ for 4 hours, heating to 25 ℃ in 2 hours, and reacting for 2 hours to obtain pale yellow transparent first reaction liquid.
Step 3, slowly dropwise adding the first reaction solution into a solution containing 500g of hexamethylenediamine and 2000g of N, N-dimethylformamide, heating to 70 ℃, and reacting for 20 hours under the protection of nitrogen; cooling to 0 ℃, slowly dripping ice water, stirring at a high speed for 0.5h, adding 5000g of toluene, continuously stirring for 0.5h, and standing to separate an organic phase; the organic phase is washed with 5000g deionized water for 2 times, the water phase is discarded, the organic phase is filtered to obtain clear liquid after the residual water is removed by anhydrous calcium chloride, and the solvent is volatilized by reduced pressure distillation to obtain white waxy solid hexamethylenediamine modified alkyl polyether cyclodextrin.
Step 4, 730g of polyoxypropylene glycol and 270g of neopentyl glycol hexanediol adipate glycol are mixed and added into a clean and dry reactor, the temperature is raised to 120 ℃, the moisture in the materials is reduced to 0.05% by means of vacuumizing, and the temperature is reduced to 40 ℃; 180g of 4,4' -dicyclohexylmethane diisocyanate is added, the temperature is raised to 75 ℃, the reaction is carried out for 5 hours, and the temperature is reduced to 30 ℃ to obtain the polyurethane prepolymer.
And 5, adding 10g of a hydrophilic agent 2- (2-aminoethyl) sodium sulfonate, 100g of hexamethylenediamine modified alkyl polyether cyclodextrin and a proper amount of acetone into the polyurethane prepolymer, stirring and heating to 55 ℃, continuously reacting for 1h, dropwise adding 1000g of water, distilling under reduced pressure to remove the acetone in the system, filtering to remove gel when the acetone content in the emulsion is evaporated to 1.0%, and adding the rest water until the weight solid content is 55%, thus obtaining the modified polyurethane dispersion.
And 6, slowly adding 60g of 10mol/L sodium hydroxide solution into 1000g of DA-102, stirring and heating to 50 ℃, and reacting for 2 hours. Cooling to 15deg.C, adding 500g mixed treeGrease Purolite UltraClean TM UCW3600, stirring for 0.5h, filtering to remove the mixed bed resin, and supplementing a small amount of water until the weight solid content is 50%, thus obtaining the modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 9.54%.
And 7, mixing 600g of the modified polyurethane dispersion in the step 5 with 400g of the modified polyethylene-vinyl acetate emulsion in the step 6, and adding 5g of Vesmmdy U505 to stir uniformly to obtain the high-gloss water-based vacuum plastic A.
The high gloss aqueous vacuum plastic prepared in this example has aph=6.5, viscosity: 1240mpa.s (23 ℃ C.).
Example 2 of the present invention is:
the high-gloss aqueous vacuum plastic comprises, by weight, 500g of modified aqueous polyurethane dispersion, 500g of modified polyethylene-vinyl acetate emulsion and 1g of thickener;
the modified aqueous polyurethane dispersion comprises the following raw materials in parts by weight: 1000g of beta-cyclodextrin, 6g of catalyst zinc hexacyanocobaltate, 440g of propylene oxide, 160g of ethylene oxide, 1000g of solvent xylene, 120g of butyl glycidyl ether, 1g of catalyst boron trifluoride diethyl ether and 10g of 1mol/L potassium hydroxide aqueous solution; 2000g of N, N-dimethylformamide, 56g of solid potassium hydroxide, 250g of p-toluenesulfonyl chloride, 400g of isophoronediamine and 5000 parts of toluene; 1000g of a dihydroxy compound; 130g of hexamethylene diisocyanate, 20g of 2- (2-aminoethyl) aminoethyl sodium sulfamate as a hydrophilic agent and a proper amount of acetone;
Wherein the dihydroxyl compound is tetrahydrofuran ether glycol and polyhexamethylene adipate glycol with average molecular weight of 2000 Da.
The raw materials of the modified polyethylene-vinyl acetate emulsion comprise the following components in parts by weight: 1000g of polyethylene-vinyl acetate emulsion, 30g of 10mol/L sodium hydroxide solution, 300g of mixed bed resin Purolite UltraClean TM UCW3600；
Wherein the polyethylene-vinyl acetate emulsion is Dalian chemical VAE emulsion DA-102 with weight solid content of 55%.
Step 1, heating 1000g of beta-cyclodextrin to 110 ℃ to remove water, adding 6g of catalyst zinc hexacyanocobaltate, heating to 110 ℃, introducing 440g of propylene oxide, keeping for 2 hours, continuously introducing 160g of ethylene oxide, keeping for 2 hours, cooling to 25 ℃, adding 1000g of dimethylbenzene, slowly dropwise adding 120g of butyl glycidyl ether, dropwise adding 1g of boron trifluoride diethyl ether, heating to 55 ℃, keeping the temperature for 3 hours, cooling to 20 ℃, adding 10g of 0.1mol/L potassium hydroxide aqueous solution, stirring for 0.5 hour, standing, separating an organic phase, volatilizing a solvent from the organic phase, and obtaining the butyl polyether cyclodextrin.
And step 2, 2000g of N, N-dimethylformamide is added into the octyl polyether cyclodextrin, stirring is carried out until the N, N-dimethylformamide is completely dissolved, the temperature of an ice water bath is reduced to 5 ℃, 56g of solid potassium hydroxide is added, stirring is carried out, 250g of p-toluenesulfonyl chloride is slowly added dropwise, after the mixture is kept at 5 ℃ for 2 hours, the temperature is increased to 30 ℃ within 2 hours, and a pale yellow transparent first reaction solution is obtained after the reaction for 2 hours.
Step 3, slowly and dropwise adding the first reaction solution into a solution containing 400g of isophorone diamine and 2000g of N, N-dimethylformamide, heating to 80 ℃, and reacting for 20 hours under the protection of nitrogen; cooling to 5 ℃, slowly dripping ice water, stirring at a high speed for 0.5h, adding 5000g of toluene, continuously stirring for 0.5h, and standing to separate an organic phase; the organic phase is washed with 5000g deionized water for 2 times, the water phase is discarded, the organic phase is filtered to obtain clear liquid after the residual water is removed by anhydrous calcium chloride, the solvent is volatilized by reduced pressure distillation, and the white waxy solid isophorone diamine modified alkyl polyether cyclodextrin is obtained.
Step 4, 650g of polytetrahydrofuran ether glycol and 350g of polyhexamethylene adipate glycol are mixed and added into a clean and dry reactor, the temperature is raised to 110 ℃, and the water content in the materials is reduced to 0.08% in a vacuumizing mode and is reduced to 50 ℃; 130g of hexamethylene diisocyanate is added, the temperature is raised to 85 ℃, the reaction is carried out for 2 hours, and the temperature is reduced to 30 ℃ to obtain polyurethane prepolymer.
And 5, adding 20g of a hydrophilic agent 2- (2-aminoethyl) aminoethyl sodium sulfonate, 80g of isophorone diamine modified alkyl polyether cyclodextrin and a proper amount of acetone into the polyurethane prepolymer, stirring and heating to 50 ℃, continuously reacting for 2 hours, dropwise adding 1000g of water, distilling under reduced pressure to remove the acetone in the system, filtering to remove gel when the acetone content in the emulsion is evaporated to 0.5%, and supplementing the rest water until the weight solid content is 45%, thus obtaining the modified polyurethane dispersion.
Step 6, 30g of 10mol/L sodium hydroxide solution is slowly added into 1000g of DA-102, stirred and heated to 40 ℃ for reaction for 5h. Cooling to 15 ℃, adding 300g of mixed bed resin Purolite UltraClean TM UCW3600, stirring for 0.5h, filtering to remove the mixed bed resin, and supplementing a small amount of water until the weight solid content is 50%, thus obtaining the modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 5.18%.
Step 7, 500g of the modified polyurethane dispersion described in step 5 is mixed with 500g of the modified polyethylene-vinyl acetate emulsion described in step 6, and 1g is added
And U902 is stirred uniformly to obtain the highlight aqueous vacuum plastic B.
The high gloss aqueous vacuum plastic prepared in this example had bph=7.5, viscosity: 1325 Pa.s (23 ℃).
Example 3 of the present invention is:
the high-gloss aqueous vacuum plastic comprises 550g of modified polyurethane dispersoid, 450g of modified polyethylene-vinyl acetate emulsion and 2g of thickener in parts by weight;
the modified aqueous polyurethane dispersion comprises the following raw materials in parts by weight: 1000g of beta-cyclodextrin, 4g of catalyst zinc hexacyanocobaltate, 350g of propylene oxide, 110g of ethylene oxide, 1000g of solvent xylene, 136g of phenyl glycidyl ether, 1g of catalyst boron trifluoride diethyl ether and 10g of 1mol/L potassium hydroxide aqueous solution; 2000g of N, N-dimethylformamide, 50g of solid potassium hydroxide, 225g of p-toluenesulfonyl chloride, 400g of hexamethylenediamine and 5000g of toluene; 1000g of a dihydroxy compound; 175g of isophorone diisocyanate, 20g of hydrophilic agent 2- (2-aminoethyl) sodium aminoethyl sulfonate and proper amount of acetone;
Wherein the dihydroxy compound is polycaprolactone diol and polyoxypropylene diol with average molecular weight of 2000 Da.
The raw materials of the modified polyethylene-vinyl acetate emulsion comprise the following components in parts by weight: 1000g of polyethylene-vinyl acetate emulsion, 45g of 10mol/L sodium hydroxide solution, 400g of mixed bed resin Purolite UltraClean TM UCW3600；
Wherein the polyethylene-vinyl acetate emulsion is Dalian chemical VAE emulsion DA-102 with weight solid content of 55%.
Step 1, heating 1000g of beta-cyclodextrin to 110 ℃ to remove water, adding 4g of catalyst zinc hexacyanocobaltate, heating to 120 ℃, introducing 350g of propylene oxide, keeping for 1h, continuing to introduce 110g of ethylene oxide, keeping for 1h, cooling to 30 ℃, adding 1000g of dimethylbenzene, slowly dropwise adding 136g of phenyl glycidyl ether, dropwise adding 1g of boron trifluoride diethyl ether, heating to 50 ℃, keeping the temperature for 4h, cooling to 20 ℃, adding 10g of 0.1mol/L potassium hydroxide aqueous solution, stirring for 0.5h, standing, separating an organic phase, volatilizing a solvent from the organic phase, and obtaining the phenyl polyether cyclodextrin.
And step 2, adding 2000g of N, N-dimethylformamide into the phenyl polyether cyclodextrin, adding the phenyl polyether cyclodextrin into the octyl polyether cyclodextrin, stirring until the phenyl polyether cyclodextrin is completely dissolved, cooling to 0 ℃ in an ice water bath, adding 50g of solid potassium hydroxide, stirring, slowly dropwise adding 225g of p-toluenesulfonyl chloride, keeping the temperature at 2 ℃ for 5 hours, heating to 30 ℃ within 2 hours, and reacting for 2 hours to obtain pale yellow transparent first reaction liquid.
Step 3, slowly dropwise adding the first reaction solution into a solution containing 400g of hexamethylenediamine and 2000g of N, N-dimethylformamide, heating to 76 ℃, and reacting for 20 hours under the protection of nitrogen; cooling to 2 ℃, slowly dripping ice water, stirring at a high speed for 0.5h, adding 5000g of toluene, continuously stirring for 0.5h, and standing to separate an organic phase; the organic phase is washed with 5000g deionized water for 2 times, the water phase is discarded, the organic phase is filtered to obtain clear liquid after the residual water is removed by anhydrous calcium chloride, and the solvent is volatilized by reduced pressure distillation to obtain white waxy solid hexamethylenediamine modified alkyl polyether cyclodextrin.
Step 4, mixing 500g of polycaprolactone diol and 500g of polyoxypropylene diol, adding the mixture into a clean and dry reactor, heating to 120 ℃, and reducing the water content in the materials to 0.07% in a vacuumizing mode, and reducing the temperature to 45 ℃; 175g of isophorone diisocyanate is added, the temperature is raised to 80 ℃, after 4 hours of reaction, the temperature is reduced to 35 ℃, and the polyurethane prepolymer is obtained.
And 5, adding 20g of a hydrophilic agent 2- (2-aminoethyl) sodium sulfonate, 90g of hexamethylenediamine modified alkyl polyether cyclodextrin and a proper amount of acetone into the polyurethane prepolymer, stirring and heating to 53 ℃, continuously reacting for 2 hours, dropwise adding 1000g of water, distilling under reduced pressure to remove the acetone in the system, filtering to remove gel when the acetone content in the emulsion is evaporated to 0.5%, and adding the rest water until the weight solid content is 50%, thus obtaining the modified polyurethane dispersion.
Step 6, 1000g of DA-102 is added into 45g of 10mol/L sodium hydroxide solution, stirred and heated to 45 ℃ for 2h of reaction. Cooling to 15 ℃, adding 400g of mixed bed resin Purolite UltraClean TM UCW3600, stirring for 0.5h, filtering to remove the mixed bed resin, and supplementing a small amount of water until the weight solid content is 50%, thus obtaining the modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 7.29%.
Step 7, mixing 550g of the modified polyurethane dispersion obtained in the step 5 with 450g of the modified polyethylene-vinyl acetate emulsion obtained in the step 6, and adding 2g
And U905 is stirred uniformly to obtain the highlight aqueous vacuum plastic C.
The highlight aqueous vacuum plastic cph=8.0 prepared in this example, viscosity: 1280mpa.s (23 ℃).
Example 4 of the present invention is:
the high-gloss aqueous vacuum plastic comprises 480g of modified aqueous polyurethane dispersoid, 520g of modified polyethylene-vinyl acetate emulsion and 4g of thickener in parts by weight;
the modified aqueous polyurethane dispersion comprises the following raw materials in parts by weight: 1000g of beta-cyclodextrin, 3g of catalyst zinc hexacyanocobaltate, 400g of propylene oxide, 140g of ethylene oxide, 1000g of solvent xylene, 130g of phenyl glycidyl ether, 1 part of catalyst boron trifluoride diethyl ether and 10g of 1mol/L potassium hydroxide aqueous solution; 2000g of N, N-dimethylformamide, 44g of solid potassium hydroxide, 198g of p-toluenesulfonyl chloride, 450g of hexamethylenediamine and 5000g of toluene; 1000g of a dihydroxy compound; 150g of 4,4' -diphenylmethane diisocyanate, 15g of 2- (2-aminoethyl) aminoethyl sodium sulfamate as a hydrophilizing agent and a proper amount of acetone;
Wherein the dihydroxyl compound is tetrahydrofuran ether glycol and polyhexamethylene adipate glycol with average molecular weight of 2000 Da.
The raw materials of the modified polyethylene-vinyl acetate emulsion comprise the following components in parts by weight: 1000g of polyethylene-vinyl acetate emulsion, 50g of 10mol/L sodium hydroxide solution, 450g of mixed bed resin Purolite UltraClean TM UCW3600；
Wherein the polyethylene-vinyl acetate emulsion is Dalian chemical VAE emulsion DA-102 with weight solid content of 55%.
Step 1, adding 1000g of beta-cyclodextrin into an autoclave, and heating to 110 ℃ to remove water; 3g of catalyst zinc hexacyanocobaltate is added into a reaction kettle, the temperature is raised to 100 ℃, 400g of propylene oxide is introduced, 140g of ethylene oxide is continuously introduced after the reaction kettle is kept for 2 hours, the temperature is reduced to 25 ℃, 1000g of dimethylbenzene is added, 130g of phenyl glycidyl ether is slowly added dropwise, 1g of boron trifluoride diethyl etherate is added dropwise, the temperature is raised to 50 ℃, the temperature is kept for 5 hours, the temperature is reduced to 25 ℃, 10g of 0.1mol/L potassium hydroxide aqueous solution is added, after stirring for 0.5 hour, the reaction kettle is kept stand, the organic phase is separated, and the solvent is volatilized from the organic phase to obtain phenyl polyether cyclodextrin.
And step 2, stirring 2000g of N, N-dimethylformamide in the phenyl polyether cyclodextrin until the N, N-dimethylformamide is completely dissolved, cooling to 0 ℃ in an ice water bath, adding 44g of solid potassium hydroxide, stirring, slowly dropwise adding 198g of p-toluenesulfonyl chloride, maintaining at 0 ℃ for 4 hours, heating to 30 ℃ within 2 hours, and reacting for 2 hours to obtain pale yellow transparent first reaction liquid.
Step 3, slowly dropwise adding the first reaction solution into a solution containing 450g of hexamethylenediamine and 2000g of N, N-dimethylformamide, heating to 78 ℃, and reacting for 20 hours under the protection of nitrogen; cooling to 5 ℃, slowly dripping ice water, stirring at a high speed for 0.5h, adding 5000g of toluene, continuously stirring for 0.5h, and standing to separate an organic phase; the organic phase is washed with 5000g deionized water for 2 times, the water phase is discarded, the organic phase is filtered to obtain clear liquid after the residual water is removed by anhydrous calcium chloride, and the solvent is volatilized by reduced pressure distillation to obtain white waxy solid hexamethylenediamine modified alkyl polyether cyclodextrin.
Step 4, adding 620g of polytetrahydrofuran ether glycol and 270g of polyhexamethylene adipate glycol into a clean and dry reactor, heating to 110 ℃, and reducing the water content in the materials to 0.08% in a vacuumizing mode to 45 ℃; 150g of 4,4' -diphenylmethane diisocyanate is added, the temperature is raised to 75 ℃, after the reaction is carried out for 5 hours, the temperature is reduced to 30 ℃, and polyurethane prepolymer is obtained;
and 5, adding 15g of a hydrophilic agent 2- (2-aminoethyl) sodium sulfonate, 100g of hexamethylenediamine modified alkyl polyether cyclodextrin and a proper amount of acetone into the polyurethane prepolymer, stirring and heating to 55 ℃, continuously reacting for 1h, dropwise adding 1000g of water, distilling under reduced pressure to remove the acetone in the system, filtering to remove gel when the acetone content in the emulsion is evaporated to 0.7%, and adding the rest water until the weight solid content is 50%, thus obtaining the modified polyurethane dispersion.
Step 6, 1000g DA-102 is slowly added into 50g 10mol/L sodium hydroxide solution, stirred and heated to 50 ℃ for 2h. Cooling to 15 ℃, adding 450g of mixed bed resin Purolite UltraCleabTM UCW3600, stirring for 0.5h, filtering out the mixed bed resin, and supplementing a small amount of water until the weight solid content is 50%, thus obtaining the modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 8.82%.
Step 7, 480g of the modified polyurethane dispersion described in step 5 was mixed with 520g of the modified polyethylene-vinyl acetate emulsion described in step 6, and 4g was added
And uniformly stirring the U601 to obtain the highlight water-based vacuum plastic D.
The high gloss aqueous vacuum plastic prepared in this example D ph=7.5, viscosity: 1190mpa.s (23 ℃).
Example 5 of the present invention is:
the high-gloss aqueous vacuum plastic comprises, by weight, 450g of modified aqueous polyurethane dispersion, 550g of modified polyethylene-vinyl acetate emulsion and 4g of thickener;
the modified aqueous polyurethane dispersion comprises the following raw materials in parts by weight: 1000g of beta-cyclodextrin, 4g of catalyst zinc hexacyanocobaltate, 270g of propylene oxide, 90g of ethylene oxide, 1000g of solvent xylene, 165g of octyl glycidyl ether, 1g of catalyst boron trifluoride diethyl ether and 10g of 1mol/L potassium hydroxide aqueous solution; 2000g of N, N-dimethylformamide, 52g of solid potassium hydroxide, 234g of p-toluenesulfonyl chloride, 420g of isophoronediamine and 5000g of toluene; 1000g of a dihydroxy compound; 180g of 4,4' -diphenylmethane diisocyanate, 13g of 2- (2-aminoethyl) aminoethyl sodium sulfamate as a hydrophilizing agent and a proper amount of acetone;
Wherein the dihydroxy compound is poly (neopentyl glycol adipate) hexanediol glycol and polytetrahydrofuran ether glycol with average molecular weight of 2000 Da.
The raw materials of the modified polyethylene-vinyl acetate emulsion comprise the following components in parts by weight: 1000g of polyethylene-vinyl acetate emulsion, 40g of 10mol/L sodium hydroxide solution, 400g of mixed bed resin Purolite UltraCleanTM UCW3600;
wherein the polyethylene-vinyl acetate emulsion is Dalian chemical VAE emulsion DA-102 with weight solid content of 55%.
Step 1, heating 1000g of beta-cyclodextrin to 115 ℃ to remove water, adding 4g of catalyst zinc hexacyanocobaltate, heating to 120 ℃, introducing 270g of propylene oxide, keeping for 1h, continuing to introduce 90g of ethylene oxide, keeping for 1h, cooling to 30 ℃, adding 1000g of dimethylbenzene, slowly dropwise adding 165g of octyl glycidyl ether, dropwise adding 1g of boron trifluoride diethyl ether, heating to 50 ℃, keeping the temperature for 7h, cooling to 25 ℃, adding 10g of 0.1mol/L potassium hydroxide aqueous solution, stirring for 0.5h, standing, separating an organic phase, volatilizing a solvent from the organic phase, and obtaining the octyl polyether cyclodextrin.
And 2, adding 2000g of N, N-dimethylformamide into the octyl polyether cyclodextrin, stirring until the N, N-dimethylformamide is completely dissolved, cooling to 5 ℃ in an ice water bath, adding 52g of solid potassium hydroxide, stirring, slowly dropwise adding 234g of p-toluenesulfonyl chloride, keeping the temperature at 5 ℃ for 2 hours, heating to 25 ℃ within 2 hours, and reacting for 2 hours to obtain a shallow first reaction solution.
Step 3, slowly and dropwise adding the first reaction solution into a solution containing 420g of isophorone diamine and 2000g of N, N-dimethylformamide, heating to 80 ℃, and reacting for 20 hours under the protection of nitrogen; cooling to 0 ℃, slowly dripping ice water, stirring at a high speed for 0.5h, adding 5000g of toluene, continuously stirring for 0.5h, and standing to separate an organic phase; the organic phase is washed with 5000g deionized water for 2 times, the water phase is discarded, the organic phase is filtered to obtain clear liquid after the residual water is removed by anhydrous calcium chloride, the solvent is volatilized by reduced pressure distillation, and the white waxy solid isophorone diamine modified alkyl polyether cyclodextrin is obtained.
Step 4, mixing 360g of neopentyl glycol hexanediol adipate glycol and 640g of polytetrahydrofuran ether glycol, adding into a clean and dry reactor, heating to 120 ℃, and reducing the water content in the materials to 0.06% by means of vacuumizing, and cooling to 50 ℃; 180g of 4,4' -dicyclohexylmethane diisocyanate is added, the temperature is raised to 85 ℃, the reaction is carried out for 3 hours, and the temperature is reduced to 30 ℃ to obtain the polyurethane prepolymer.
And 5, adding 13g of a hydrophilic agent 2- (2-aminoethyl) sodium sulfonate, 95g of hexamethylenediamine modified alkyl polyether cyclodextrin and a proper amount of acetone into the polyurethane prepolymer, stirring and heating to 53 ℃, continuously reacting for 2 hours, dropwise adding 1000g of water, distilling under reduced pressure to remove the acetone in the system, filtering to remove gel when the acetone content in the emulsion is evaporated to 0.5%, and adding the rest water until the weight solid content is 55%, thus obtaining the modified polyurethane dispersion.
Step 6, 1000g of DA-102 is slowly added into 40g of 10mol/L sodium hydroxide solution, stirred and heated to 50 ℃ for 2h of reaction. Cooling to 15 ℃, adding 400g of mixed bed resin Purolite UltraCleanTM UCW3600, stirring for 0.5h, filtering out the mixed bed resin, and supplementing a small amount of water until the weight solid content is 50%, thereby obtaining the modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 6.93%.
Step 7, 450g of the modified polyethylene-vinyl acetate emulsion described in step 4 was mixed with 550g of the modified polyurethane dispersion described in step 6, and 4g was added
And uniformly stirring the U505 to obtain the highlight aqueous vacuum plastic E.
The high gloss aqueous vacuum plastic prepared in this example has E ph=7.0, viscosity: 1255 Pa.s (23 ℃).
Comparative example 1 of the present invention is:
comparative example 1 was based on example 1 using equimolar hexamethylenediamine instead of hexamethylenediamine modified alkyl polyether cyclodextrin.
Step 1, 730g of polyoxypropylene glycol and 270g of neopentyl glycol hexanediol adipate glycol are mixed and added into a clean and dry reactor, the temperature is raised to 120 ℃, the moisture in the materials is reduced to 0.05% by means of vacuumizing, and the temperature is reduced to 40 ℃; 180g of 4,4' -dicyclohexylmethane diisocyanate is added, the temperature is raised to 75 ℃, the reaction is carried out for 5 hours, and the temperature is reduced to 30 ℃ to obtain the polyurethane prepolymer.
And 2, adding 10g of a hydrophilic agent 2- (2-aminoethyl) sodium sulfamate, 7.3g of hexamethylenediamine and a proper amount of acetone into the polyurethane prepolymer, stirring and heating to 55 ℃, continuously reacting for 1h, dropwise adding 1000g of water, decompressing and distilling to remove the acetone in the system, filtering to remove gel when the acetone content in the emulsion is evaporated to 1.0%, and adding the rest water until the weight solid content is 55%, thus obtaining the aqueous polyurethane dispersion.
And step 3, mixing 600g of the aqueous polyurethane dispersion in the step 2 with 400g of DA-102 emulsion, adding 4g of Vesmody U505, and uniformly stirring to obtain the aqueous vacuum absorbent F.
The aqueous vacuum plastic FpH =7.5 prepared in this example has a viscosity: 1315mpa.s (23 ℃).
Spraying the high-gloss water-based vacuum plastic A-F on a medium density fiberboard respectively, naturally drying, and performing plastic suction by using PVC films with the thickness of 0.35mm and the thickness of 0.14mm respectively. The plastic sucking condition is as follows: 0.35mm PVC film: the temperature of the plastic sucking machine is 170 ℃, the preheating time is 50 seconds, the plastic sucking time is 170 seconds, and the pressure relief time is 220 seconds; 0.14mm PVC film: the temperature of the plastic sucking machine is 170 ℃, the preheating time is 20 seconds, the plastic sucking time is 100 seconds, and the pressure relief time is 220 seconds.
After the plastic suction is finished, the surface is naturally cooled to the temperature of about 35 ℃, and the smooth effect of the plate surface is visually observed and felt by the finger belly. And (5) observing the side light of the surface of the plastic-absorbed plate. The rating criteria are as follows: the PVC film has no obvious concave-convex feeling by visual inspection, no obvious convex points by hand touch, and 5 scores of evaluation; the PVC film has no obvious concave-convex feeling by visual inspection, and has a small number of convex points by hand touch, and the evaluation is 4 points; the PVC film has concave-convex feeling in a small number of visual inspection positions, and has a small number of convex points in a hand touch, and the evaluation is 3 minutes; the PVC film has obvious concave-convex feeling by visual inspection, and has large-area obvious convex points by hand touch, and the evaluation is 2 minutes; the PVC film has obvious concave-convex feeling by visual inspection, has large-area obvious roughness and unevenness by hand touch, and is rated for 1 minute.
The adhesion was tested by peeling the PVC film from the medium density fiberboard. The adhesive force is determined from the amount of fiber scraps of the medium density fiberboard on the PVC film. The rating criteria are as follows: the PVC film is provided with a large amount of fiber scraps, the medium density fiberboard has large damage depth, and the evaluation is 5 points; the PVC film is provided with more fiber scraps, and the damage depth of the medium density fiberboard is generally rated for 4 points; the PVC film is provided with a small amount of fiber scraps, the damage depth of the medium density fiberboard is shallow, and the grade is 3; the PVC film is provided with a very small amount of fiber scraps, the medium density fiberboard is not damaged obviously, and the evaluation is 2 points; the PVC film is basically free of fiber scraps, the surface of the medium density fiberboard is smooth, and the evaluation is 1.
The heat resistance rating is to place all plastic-sucked plates in an environment with the temperature of 25+/-2 ℃ and the humidity of 50+/-10% for 24 hours, place the plastic-sucked plates in a baking oven with the temperature of 60 ℃ for continuous heating for 4 hours, take out and cool the plastic-sucked plates, and observe the side edge opening or edge shrinking condition. The rating standard is that the side edge has no edge shrinkage and edge opening, and the rating is 5; the side edge has a small amount of shrinkage edges and no edge opening condition, and the score is 4; a small amount of side opening conditions exist on the side edges, and the evaluation is 3; the side edge has obvious side opening condition, and the evaluation is divided into 2; all sides are open, and the score is 1.
The surface roughness and adhesion ratings of the high gloss aqueous vacuum absorbers A-E obtained in the examples, the aqueous vacuum absorbers F obtained in the comparative examples, and the commercial aqueous vacuum absorbers G are shown in Table 1. As can be seen from Table 1, the surface roughness ratings of the highlight aqueous vacuum plastic foams A-E are all significantly higher than those of the aqueous vacuum plastic foam F obtained in comparative example 1 and the commercial aqueous vacuum plastic foam G, which indicates that the surface effect of the highlight aqueous vacuum plastic foam using the scheme of the invention is good; the effect of the plate surface of the 0.14mm PVC film is slightly poorer than that of the 0.35mm PVC film, mainly because the PVC film is thin and has lower strength, and a small number of protruding points cannot be flattened. As can be seen from the cohesive force rating, the high gloss aqueous vacuum plastic foams A-E all have good cohesive strength, which is comparable to those of the plastic foams F and G. The heat resistance rating results show that the high gloss aqueous vacuum plastic foams A-E have good heat resistance, which is equivalent to or slightly better than the plastic foams F and G.
TABLE 1 grading of surface roughness, adhesion and Heat resistance of aqueous vacuum suction Agents
In summary, the high gloss aqueous vacuum plastic provided by the invention, wherein the modified polyurethane dispersion contains diamine modified alkyl polyether cyclodextrin, and the diamine modified alkyl polyether cyclodextrin is obtained by the following steps: hydroxyl in the beta-cyclodextrin reacts with propylene oxide and ethylene oxide to generate polyether modified cyclodextrin, and alkyl is accessed through the reaction of alkyl glycidyl ether and hydroxyl; the next step, the tosyl chloride and part of primary hydroxyl groups generate tosyl groups, and finally react with excessive diamine compounds to generate diamine modified alkyl polyether cyclodextrin;
the invention optimizes the dosage and the synthesis condition of each modifier, the alkylation exists in most alkyl polyether cyclodextrin in a mono-alkyl substitution form, and a small amount of dialkyl substitution, trisubstituted and alkyl polyether cyclodextrin has good compatibility in the system, and does not influence the subsequent modification and application; the structure of the obtained diamine modified alkyl polyether cyclodextrin contains one primary amine and one secondary amine, and both amine groups can react with isocyanate at a lower temperature (50-55 ℃), so that the reaction rate of hydroxyl contained in the diamine modified alkyl polyether cyclodextrin and the isocyanate is extremely slow, and the final reaction degree is basically not influenced.
The polyoxypropylene polyoxyethylene ether chain segment in the polyether modified alkyl cyclodextrin can reduce the surface tension, and meanwhile, the hydrophilic and hydrophobic balance can be achieved by adjusting the ratio of ethylene oxide to propylene oxide; the alkyl-combined polyoxypropylene polyoxyethylene ether is a more hydrophobic chain segment, and the outer layer of the cyclodextrin has better hydrophilicity, so that the cyclodextrin has the hydrophobicity adjusted through modification, forms a partially compatible state in water, can be used as an intramolecular flatting agent, delays the benard effect and improves the surface flatness of the high-gloss aqueous vacuum plastic.
The modified polyethylene-vinyl acetate emulsion is a polymer with the hydrolysis degree of 5-10%, the hydrolyzed chain segment is polyvinyl alcohol and has a large number of hydroxyl groups, and the hydroxyl groups and oxygen atoms in the polyether modified alkyl cyclodextrin in the modified polyurethane dispersion can form hydrogen bond action, so that the compatibility of the polyethylene-vinyl acetate emulsion and the modified polyurethane dispersion in the system is better, microphase separation is not generated, the surface tension difference in the system can be greatly reduced, the flow of liquid in a glue layer is reduced, the benard vortex is inhibited, and the surface roughness of the high-gloss water-based vacuum plastic is reduced.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent modifications made by the teachings of the present invention, or direct or indirect application in the relevant art, are intended to be included within the scope of the present invention.
Claims (9)
1. The high-gloss water-based vacuum plastic cement is characterized by comprising, by weight, 400-600 parts of modified polyurethane dispersoid, 400-600 parts of modified polyethylene-vinyl acetate emulsion with 5-10% of alcoholysis degree and 1-5 parts of thickener;
the preparation method of the modified polyurethane dispersoid comprises the following steps: beta-cyclodextrin, propylene oxide and ethylene oxide react to generate polyether modified cyclodextrin, then the polyether modified cyclodextrin reacts with alkyl glycidyl ether to obtain alkyl polyether cyclodextrin, p-toluenesulfonyl chloride and a diamine compound are sequentially added to react respectively to obtain diamine modified alkyl polyether cyclodextrin, and finally the diamine modified alkyl polyether cyclodextrin reacts with polyurethane prepolymer to obtain modified polyurethane dispersoid;
the preparation method of the modified polyurethane dispersoid comprises the following steps:
step 1, heating up 1000 parts of beta-cyclodextrin, decompressing, adding 1-6 parts of catalyst, 200-440 parts of propylene oxide and 80-160 parts of ethylene oxide, heating up and reacting, and then cooling; 1000 parts of dimethylbenzene, 120-150 parts of alkyl glycidyl ether and 1 part of catalyst are added, heated and reacted, and cooled; adding 1 part of alkali solution to obtain alkyl polyether cyclodextrin in an organic phase;
step 2, adding 2000 parts of N, N-dimethylformamide into the alkyl polyether cyclodextrin, cooling and adding 40-60 parts of solid alkali; 180-250 parts of p-toluenesulfonyl chloride is added, the temperature is raised after low-temperature reaction, and a pale yellow transparent first reaction solution is obtained after the reaction;
Step 3, adding the first reaction solution into 400-500 parts of mixed solution containing diamine compound and N, N-dimethylformamide, and heating up for reaction in a nitrogen environment; dropping water into the mixture after cooling, stirring, adding 5000 parts of toluene, stirring to obtain an organic phase, washing, and discarding a water phase; anhydrous calcium chloride in an organic phase is filtered to obtain clear liquid, and the clear liquid is decompressed and distilled to obtain white waxy solid diamine modified alkyl polyether cyclodextrin;
step 4, heating 1000 parts of dihydroxy compound, reducing the water content in the material to 0.05-0.1%, cooling, adding 130-180 parts of diisocyanate, and cooling after heating reaction to obtain polyurethane prepolymer;
step 5, adding 10-20 parts of hydrophilic agent, 80-100 parts of diamine modified alkyl polyether cyclodextrin and a proper amount of acetone into the polyurethane prepolymer, stirring, heating to 50-55 ℃, continuing to react for 1-2h, dripping water and distilling under reduced pressure; when the acetone content is steamed to 0.5-1.0%, filtering and adding the rest water until the weight solid content is 45-55%, thus obtaining the modified polyurethane dispersoid.
2. The highlight aqueous vacuum plastic according to claim 1, wherein the preparation method of the modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 5-10% is as follows:
Slowly adding the polyethylene-vinyl acetate emulsion into an alkali solution, stirring, heating, reacting, cooling, adding mixed bed resin, stirring, filtering out the mixed bed resin, supplementing water until the weight solid content is 50%, and obtaining the modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 5-10%.
3. The high gloss aqueous vacuum absorbing plastic according to claim 1, wherein said alkyl glycidyl ether is one or more of butyl glycidyl ether, octyl glycidyl ether and phenyl glycidyl ether.
4. The high gloss aqueous vacuum plastic according to claim 1, wherein the diamine compound is one or more of isophorone diamine and hexamethylene diamine; the polyethylene-vinyl acetate emulsion is Dalian chemical VAE emulsion DA-102 with weight solid content of 55%.
5. The high gloss aqueous vacuum plastic according to claim 1, wherein said diisocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate.
6. The high gloss aqueous vacuum absorbing plastic according to claim 1, wherein the dihydroxy compound is one or more of polyoxypropylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol, neopentyl glycol adipate glycol or polycaprolactone glycol having an average molecular weight of 2000 Da.
7. The high gloss aqueous vacuum absorbing polymer according to claim 1, wherein said thickener is one or more of polyurethane associative thickeners vesbody U902, vesbody U601, vesbody U905, vesbody U505.
8. The high gloss aqueous vacuum plastic according to any one of claims 1 to 7, wherein the preparation method of the high gloss aqueous vacuum plastic comprises:
400-600 parts of modified polyethylene-vinyl acetate emulsion with the alcoholysis degree of 5-10% and 400-600 parts of modified polyurethane dispersoid are mixed, and 1-5 parts of thickener is added to adjust the viscosity to be proper, so that the high-gloss water-based vacuum plastic is obtained.
9. A method for preparing the highlight aqueous vacuum plastic according to claim 1, which comprises the following steps:
step 1, after 1000 parts of beta-cyclodextrin is heated to 110-120 ℃ and dehydrated under reduced pressure, adding 1-6 parts of catalyst, heating to 100-120 ℃, introducing 200-440 parts of propylene oxide, maintaining for 1-2 hours, introducing 80-160 parts of ethylene oxide, maintaining for 1-2 hours, cooling to 25-30 ℃, adding 1000 parts of dimethylbenzene, slowly dropwise adding 120-150 parts of alkyl glycidyl ether, dropwise adding 1 part of catalyst, heating to 45-55 ℃, maintaining for 3-8 hours, cooling to 20-30 ℃, adding 1 part of potassium hydroxide aqueous solution, stirring for 0.5 hour, standing, separating an organic phase, volatilizing the solvent from the organic phase, and obtaining the alkyl polyether cyclodextrin;
Step 2, adding 2000 parts of N, N-dimethylformamide into the alkyl polyether cyclodextrin, stirring until the N, N-dimethylformamide is completely dissolved, cooling to 0-5 ℃ in an ice water bath, adding 40-60 parts of solid potassium hydroxide, stirring, slowly dropwise adding 180-250 parts of p-toluenesulfonyl chloride, keeping the temperature at 0-5 ℃ for 2-4 hours, heating to 25-30 ℃ within 2 hours, and reacting to obtain pale yellow transparent first reaction liquid;
step 3, slowly and dropwise adding the first reaction solution into a mixed solution containing 400-500 parts of diamine compound and N, N-dimethylformamide, heating to 70-80 ℃, and reacting for 20 hours under the protection of nitrogen; cooling to 0-5 ℃, slowly dripping water with the temperature of 4-6 ℃, stirring at a high speed for 0.5h, adding 5000 parts of toluene, continuously stirring for 0.5h, and standing to separate an organic phase; washing the organic phase with deionized water for 2 times successively, discarding the water phase, removing residual water from the organic phase with anhydrous calcium chloride, filtering to obtain clear liquid, and distilling under reduced pressure to volatilize the solvent to obtain white waxy solid diamine modified alkyl polyether cyclodextrin;
step 4, heating 1000 parts of the dihydroxy compound to 110-120 ℃, vacuumizing to reduce the water content in the material to 0.05-0.1%, and cooling to 40-50 ℃; 130-180 parts of diisocyanate is added, the temperature is raised to 75-85 ℃, after 2-5 hours of reaction, the temperature is reduced to 30-40 ℃ to obtain polyurethane prepolymer;
Step 5, adding 10-20 parts of hydrophilic agent, 80-100 parts of diamine modified alkyl polyether cyclodextrin and a proper amount of acetone into the polyurethane prepolymer, stirring and heating to 50-55 ℃, continuously reacting for 1-2 hours, dropwise adding water, removing acetone in a system by reduced pressure distillation, filtering to remove gel when the acetone content in the emulsion is evaporated to 0.5-1.0%, and adding the rest water until the weight solid content is 45-55%, thus obtaining a modified polyurethane dispersion;
step 6, slowly adding sodium hydroxide solution into the polyethylene-vinyl acetate emulsion, stirring and heating to 40-50 ℃, reacting for 2-5h, reducing the temperature to 15-25 ℃, adding mixed bed resin Purolite UItraCleanTM UCW3600 to remove micromolecular salts, stirring for 0.5h, filtering out mixed bed resin, and supplementing a small amount of water until the weight solid content is 50%, thus obtaining modified polyethylene-vinyl acetate emulsion with an alcoholysis degree of 5-10%;
and 7, mixing 400-600 parts of the modified polyethylene-vinyl acetate emulsion with 400-600 parts of the modified polyurethane dispersion, and adding 1-5 parts of a thickener to adjust the viscosity to be proper, so as to obtain the high-gloss water-based vacuum plastic.
Priority Applications (1)
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