CN111849405A - Water-based high-gloss vacuum suction plastic and preparation method thereof - Google Patents
Water-based high-gloss vacuum suction plastic and preparation method thereof Download PDFInfo
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- CN111849405A CN111849405A CN201910352391.6A CN201910352391A CN111849405A CN 111849405 A CN111849405 A CN 111849405A CN 201910352391 A CN201910352391 A CN 201910352391A CN 111849405 A CN111849405 A CN 111849405A
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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
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a water-based high-gloss vacuum suction plastic and a preparation method thereof, wherein the water-based high-gloss vacuum suction plastic comprises the following raw materials in parts by weight: 30-60 parts of waterborne polyurethane-polyvinyl acetate emulsion, 5-30 parts of modifier, 30-50 parts of ethylene-vinyl acetate copolymer emulsion, 0.03-0.08 part of defoaming agent, 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, and the preparation method comprises the following steps: adding the aqueous polyurethane-polyvinyl acetate emulsion and the modifier into a dispersion kettle, then adding the ethylene-vinyl acetate copolymer emulsion, then sequentially adding the defoaming agent, the leveling agent, the humectant and the plasticizer under the stirring condition, and finally adding the thickener to adjust the viscosity to a proper value, thereby obtaining the aqueous high-gloss vacuum absorbing plastic. The vacuum plastic-absorbing glue has excellent surface effect, heat resistance and good strength.
Description
Technical Field
The invention belongs to the technical field of polyurethane adhesives, and relates to a water-based high-gloss vacuum absorbent plastic and a preparation method thereof.
Background
The vacuum-forming plastic is mainly compounded by aqueous polyurethane emulsion and other resins, is an adhesive used by a vacuum-forming process, has the function of bonding PVC with an artificial board, and is mainly used for vacuum-forming wooden doors, cabinets, sound box boards, computer desks, automobile consoles and the like.
With the rapid development and maturity of the decoration industry, the requirements of people on vacuum plastic-absorbing glue are continuously improved. Most of vacuum plastic-absorbing glue on the market at present has the problem of poor smoothness, and the phenomena of obvious orange peel, pockmarks and the like on the surfaces of sliding doors and cabinets used in daily life can be frequently seen, which are caused by uneven distribution of plastic-absorbing glue on the surfaces of wood boards.
Chinese published patent CN 106916552 a describes a plastic-absorbing adhesive. The formula of the modified polyurethane emulsion comprises 60 parts of ethylene-vinyl acetate copolymer emulsion, 55 parts of polyurethane emulsion, 1 part of glycerol monolaurate, 0.5 part of triethanolamine, 2 parts of amino alcohol complex titanate, 15 parts of methyl isobutyl ketone, 2 parts of alkyl modified organic siloxane, 3 parts of polyacrylamide, 5 parts of carboxymethyl cellulose and 3 parts of sodium methyl dinaphthalene sulfonate. The plastic uptake adhesive does not relate to highlight and polyurethane-polyvinyl acetate emulsion, and the adhesive formula is complex.
At present, the research on the high gloss of vacuum plastic-absorbing plastics in the market is few, and in order to solve the problems of poor smoothness of the vacuum plastic-absorbing plastics and the like, the development of the water-based high gloss vacuum plastic-absorbing plastics with good heat resistance and good strength and the preparation method thereof are needed.
Disclosure of Invention
The invention aims to provide a water-based high-gloss vacuum absorbent plastic which has high gloss and good strength and heat resistance.
The invention also aims to provide a preparation method of the water-based high-gloss vacuum absorbent plastic.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the water-based high-gloss vacuum suction plastic comprises the following raw materials in parts by weight:
30-60 parts of waterborne polyurethane-polyvinyl acetate emulsion, preferably 35-55 parts
5-30 parts of modifier, preferably 10-25 parts
30-50 parts of ethylene-vinyl acetate copolymer emulsion, preferably 35-45 parts
0.03-0.08 part of defoaming agent, preferably 0.04-0.06 part
0.1 to 0.6 part of leveling agent, preferably 0.2 to 0.5 part
0.5-5 parts of humectant, preferably 1-4 parts
0 to 4 parts of plasticizer, preferably 0.1 to 3 parts
0 to 2 parts of thickening agent, preferably 0.02 to 0.18 part.
In the invention, the number average molecular weight of the waterborne polyurethane-polyvinyl acetate emulsion is 3-10 ten thousand daltons, and the solid content is 48-52%.
In the invention, the waterborne polyurethane-polyvinyl acetate emulsion comprises the following raw materials in parts by weight:
(A) 80 to 120 parts, preferably 90 to 110 parts, of a diisocyanate-terminated prepolymer;
(B) 50-250 parts of solvent, preferably 100-200 parts;
(C) 2.5-7 parts of micromolecule amine chain extender, preferably 3.5-4.6 parts;
(D) 0.05-4 parts of monoamino small molecule end-capping agent, preferably 0.1-3 parts;
(E) 30-120 parts of vinyl acetate, preferably 50-100 parts;
(F) the protective colloid accounts for 0.4-1.6% of the mass of the (E), preferably 0.5-1.5%;
(G) the free radical initiator is 0.10-0.6%, preferably 0.15-0.5% of the mass of (E);
(H) 400 parts of water 115 and 350 parts of water are preferred;
in the invention, the diisocyanate-terminated prepolymer (A) is prepared by mixing and reacting the following raw materials in parts by weight: 15-60 parts of diisocyanate, 100 parts of polyol, 250 parts of hydrophilic compound, 5-20 parts of catalyst and 15-50 parts of solvent;
the diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, and is preferably isophorone diisocyanate and/or hexamethylene diisocyanate;
the polyalcohol is one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate diol, polyethylene glycol adipate diol, 1, 4-butanediol adipate diol, neopentyl glycol adipate diol, 1, 6-hexanediol adipate diol and 1, 6-hexanediol adipate diol, preferably the 1, 4-butanediol adipate diol and/or the 1, 6-hexanediol adipate diol;
The hydrophilic compound is polyoxyalkylene ether containing one hydroxyl or amino, preferably polyethylene glycol monomethyl ether and/or polypropylene glycol monomethyl ether;
the catalyst is one or more of triethylamine, 1, 4-diazabicyclo- [2,2,2] -octane, dibutyltin oxide, tin dioctoate, dibutyltin dilaurate, tin bis- (2-ethylhexanoate), bismuth neodecanoate and bismuth 2-ethylhexanoate, and preferably bismuth neodecanoate;
the solvent (B) is one or more of acetone or butanone, the micromolecule amine chain extender (C) is one or more of diamino polyether amine, pentamethylene diamine, isophorone diamine, hydroxyethyl ethylene diamine, 2- (2-aminoethyl) sodium amino propane sulfonate and 2- (2-aminoethyl) sodium amino ethane sulfonate, the (D) monoamino small molecule end-capping reagent is one or more of diethanolamine, diethylamine, diisopropanolamine, 1, 3-diamino-2-propanol and isopropylamine, the protective colloid (F) is one or more of polyvinyl alcohol, ethoxy alkylphenol and 1, 2-ethylene glycol crosslinked by urethane, the (G) free radical initiator is one or more of potassium persulfate, tert-butyl hydroperoxide, sodium hydrosulfite and sodium bisulfite.
In the invention, the waterborne polyurethane-polyvinyl acetate emulsion is anionic polyurethane-polyvinyl acetate emulsion, and the preparation process comprises the following steps:
(1) adding (A) a diisocyanate-terminated prepolymer into (B) a solvent to obtain a diluted diisocyanate-terminated prepolymer;
(2) adding (C) micromolecule amine chain extender into the solution obtained in the step (1) for chain extension reaction, adding (D) monoamino micromolecule end capping agent for end capping reaction after the reaction is finished, adding part of (E) vinyl acetate after the reaction is finished, adding water, shearing and dispersing to obtain the waterborne polyurethane-vinyl acetate mixed emulsion;
(3) adding the rest vinyl acetate into the reaction system in the step (2) for swelling, then adding (F) protective colloid for mixing, and then adding (G) free radical initiator for initiating polymerization to obtain the waterborne polyurethane-polyvinyl acetate crude emulsion;
(4) and (C) removing the solvent from the waterborne polyurethane-polyvinyl acetate coarse emulsion obtained in the step (3) to obtain the waterborne polyurethane-polyvinyl acetate emulsion.
In the step (2), the chain extension reaction is carried out, wherein the reaction temperature is 45-50 ℃, and the reaction time is 15-25 min; the end capping reaction is carried out at the temperature of 45-50 ℃ for 5-10 min; the addition amount of the vinyl acetate is 50-100%, preferably 50-70% of the total mass of the raw material vinyl acetate;
In the step (3), adding the protective colloid, and stirring and mixing for 0.5-1 h; the initiation polymerization is carried out at the temperature of 35-45 ℃, the polymerization reaction temperature of 40-45 ℃ and the polymerization reaction time of 2-3 h;
in the step (4), the desolventizing adopts a reduced pressure distillation mode.
It features low thermal activation temperature (50-55 deg.C), high initial strength and good heat resistance;
in the invention, the modifier is water-based acrylate emulsion, preferably Wanhua chemical Adwel 1367, with solid content of 61-63% and pH of 4-6. The emulsion has excellent rheological property, and can improve the spraying property and the flow spreading property of the absorbing plastic after being added, and the flatness of the absorbing plastic on a substrate can be improved more easily.
In the invention, the defoaming agent is a silicone defoaming agent, preferably one or more of BYK-024 and BYK-028; the leveling agent is an organic silicon leveling agent, and preferably one or more of YCK1130, Tego KL 245 and BYK 3455.
In the invention, the plasticizer is a non-phthalate environment-friendly plasticizer, and preferably one or more of dipropylene glycol dibenzoate, epoxy acetyl methyl linoleate, diethylene glycol dibenzoate and cyclohexane 1, 2-diisononyl phthalate.
In the invention, the humectant is one or more of glycerin, sorbitol, propylene glycol, hexanediol, xylitol, hyaluronic acid, sodium lactate, ethylene glycol butyl ether, polypropylene glycol and polyethylene glycol, preferably one or more of glycerin, hyaluronic acid, sodium lactate and ethylene glycol butyl ether.
In the invention, the thickener is a polyurethane associative thickener, preferably one or more of Vesmody U604 and Vesmody U300 in Wanhua chemistry.
The invention also provides a preparation method of the vacuum plastic, which comprises the following steps: adding the waterborne polyurethane-polyvinyl acetate emulsion and the modifier into a dispersion kettle, then adding the ethylene-vinyl acetate copolymer emulsion, then sequentially adding the defoamer, the flatting agent, the humectant and the plasticizer under the condition that the rotation speed of a stirring shaft is 400-800 r/min, and finally adding the thickener to adjust the viscosity to 600-1000mPa & s to obtain the waterborne highlight vacuum plastic.
As a preferable scheme, the preparation method comprises the following steps: adding the waterborne polyurethane-polyvinyl acetate emulsion and the modifier into a dispersion kettle, then adding the ethylene-vinyl acetate copolymer emulsion, wherein the rotation speed of a stirring shaft is 500-700 r/min, and stirring for 10-20 min; adding a defoaming agent, stirring for 8-15 minutes, wherein the rotating speed of a stirring shaft is 300-; adding a leveling agent, stirring for 8-15 minutes, wherein the rotating speed of a stirring shaft is 300-; adding a humectant and a plasticizer, stirring for 6-15 minutes at a stirring shaft rotation speed of 300-800 rpm, finally adding a thickener at a stirring shaft rotation speed of 500-800 rpm, and adjusting the viscosity to 600-1000mPa & s to prepare the water-based vacuum plastic.
As a further preferable scheme, the preparation method comprises the following steps: adding the waterborne polyurethane-polyvinyl acetate emulsion and the modifier into a dispersion kettle, then adding the ethylene-vinyl acetate copolymer emulsion, wherein the rotating speed of a stirring shaft is 500-700 r/min, and stirring for 15 min; adding a defoaming agent, stirring for 10 minutes, wherein the rotating speed of a stirring shaft is 300-500 rpm; adding a leveling agent, stirring for 10 minutes, wherein the rotating speed of a stirring shaft is 300-500 revolutions per minute; adding a humectant and a plasticizer, stirring for 15 minutes at a stirring shaft rotation speed of 300-800 rpm, finally adding a thickener at a stirring shaft rotation speed of 500-800 rpm, and adjusting the viscosity to 600-1000mPa & s to prepare the water-based vacuum plastic.
The invention has the positive effects that:
because the aqueous polyurethane-polyvinyl acetate emulsion and the ethylene-vinyl acetate copolymer emulsion have good compatibility, the excellent heat resistance and initial strength of the aqueous polyurethane-polyvinyl acetate emulsion can be kept after compounding, the excellent strength of the ethylene-vinyl acetate copolymer emulsion can also be kept, and meanwhile, the aqueous polyurethane-polyvinyl acetate copolymer emulsion has better affinity with a hydrophobic part in a polyurethane associated thickener, and is easy to construct. The plasticizer is a micromolecular substance, can play a role in lubricating among macromolecules, reduces the glass transition temperature of the material, and finally reduces the activation temperature; the leveling agent has the function of migrating to the surface of the adhesive and improving the flatness of the surface by influencing the surface tension; the humectant is a hydrophilic substance, has the capacity of combining water in a lower humidity range, has the function of delaying the volatilization of water, and can play a synergistic action with the leveling agent to ensure that the surface is smoother.
Therefore, the water-based high-gloss vacuum plastic disclosed by the invention has the advantages of good heat resistance, excellent strength, good flatness, high gloss and obviously better use effect than that of the existing vacuum plastic.
Detailed Description
Embodiments of the present invention are further illustrated by the following examples, but the present invention is not limited to the examples listed, and is intended to include any other known variations within the scope of the invention as claimed.
The first, the main raw materials adopted in the embodiment, and the source and the brand thereof:
1、
IPDI (isophorone diisocyanate, NCO content about 37.8%, Vanhua chemical group Co., Ltd.);
2. PBA-2000 (poly 1, 4-butanediol adipate diol, hydroxyl value of 56mgKOH/g, number average molecular weight 2000, functionality of 2, dawsonia macrochemical);
CMA-654 (poly (neopentyl glycol adipate) hexanediol adipate diol, hydroxyl value of 74.8mgKOH/g, number average molecular weight of about 1500, functionality of 2, large chemistry of Tahitian China);
3. MPEG1200 (polyethylene glycol monomethyl ether, hydroxyl number 46.75mgKOH/g, number average molecular weight 1200, functionality 1, clonidine, korea);
4. An organic bismuth catalyst (bismuth neodecanoate, advanced chemical company, usa);
5. organic solvents (acetone, nibowanghua);
6、
a95 (sodium 2- (2-aminoethyl) tauride, 51 + -2% solids aqueous solution, amine number 260 + -20 mgKOH/g, EVONIK, Germany);
7. IPDA (Isophorone diamine, Vanhua chemical group Ltd.);
hydroxyethylethylenediamine (Yangzhitin-Pasteur, Inc.);
ED-600 (bis-amino polyetheramines, of Hensman)
ED Series products);
8. DEOA (diethanolamine, raisin-basf llc);
9. VAc (vinyl acetate, Dow Aike reagent, Inc.);
10. polyvinyl alcohol 2488 low viscosity type (polyvinyl alcohol, alcoholysis rate of 88%, alatin);
polyvinyl alcohol 1788 low viscosity type (polyvinyl alcohol, alcoholysis rate of 88%, alatin);
11. t-butyl hydroperoxide (petrochemical, Lanzhou) and sodium hydrosulfite (sodium hydrosulfite, chemical, Szegaku).
12. AMP-95 (2-amino-2-methyl-1-propanol, dow chemical, usa);
secondly, the method for testing various performances of the water-based vacuum plastic comprises the following steps:
(1) heat resistance test
Spraying the prepared vacuum forming glue to a 15x15cm high-density fiberboard with a groove by using a spray gun with the caliber of 1.6, wherein the spraying glue applying amount is 1.5-1.8g, drying at room temperature, forming the plastic by using a vacuum forming process, placing a sample plate at 60 ℃ for baking for 4 hours after the plastic forming is finished for 24 hours, comparing the PVC pasting condition on the groove plate, and comparing with a standard sample for scoring to determine an experimental result.
(2) Peel Strength test
Spraying the prepared plastic uptake glue to a 10x15cm medium density fiberboard by using a spray gun with the caliber of 1.6, wherein the spraying glue applying amount is 0.4-0.5g, carrying out plastic uptake by using a vacuum plastic uptake process after drying in the air at room temperature, immediately tearing after the plastic uptake is finished, comparing the condition of wood dust on the PVC base material, and comparing and scoring with a standard sample to determine an experimental result.
(3) Surface effects
Spraying the prepared vacuum forming glue to a 15x15cm high-density fiberboard by using a spray gun with the caliber of 1.6, wherein the spraying glue amount is 0.8g, comparing the flatness of a glue film on the fiberboard after drying in the air at room temperature, and comparing and scoring with a standard sample to determine an experimental result.
The parts described in the examples are parts by weight.
Example 1
The water-based vacuum plastic is prepared from the following raw materials in parts by weight:
the waterborne polyurethane-polyvinyl acetate emulsion A of this example was prepared by the following steps:
(1) into a four-necked flask was charged 30g
HDI, 230g of PBA-2000, 9.7g of MPEG1200, 100ppm of an organic bismuth catalyst and 23g of acetone, and reacting at 70 ℃, sampling and monitoring NCO in the experimental process until the NCO reaches a theoretical value of 1.71 percent, preparing a diisocyanate-terminated prepolymer, cooling to about 60 ℃, and adding 381g of acetone to obtain the diluted diisocyanate-terminated prepolymer.
(2) 1.3g of hydroxyethylethylenediamine, 0.5gED-600 and 10.2g
A95 is diluted by 46g of deionized water, added into the solution in the step (1) at the temperature of 45 ℃ and stirred for 15min, 0.23g of diethanolamine is diluted by 1g of deionized water, added into a reaction system to react at the temperature of 45 ℃ for 5min, added with 67.4g of vinyl acetate and stirred for 2-3min, and added with 450g of water under the condition of shearing dispersion to obtain the waterborne polyurethane-vinyl acetate mixed emulsion.
(3) And (3) heating the reaction system in the step (2) to 45 ℃, adding 67.4g of vinyl acetate, stirring and swelling for 30min, adding 0.674g of polyvinyl alcohol 1788, stirring for 0.5h in a low-viscosity mode, adding 0.05g of tert-butyl hydroperoxide and 0.05g of sodium hydrosulfite (sodium hydrosulfite) to initiate polymerization, wherein the initiation temperature is 45 ℃, the polymerization reaction temperature is 45 ℃, adding the same amount of initiator again every 30min, initiating for 4 times, and preserving heat for 30min after the initiation is finished to obtain the waterborne polyurethane-polyvinyl acetate crude emulsion.
(4) And (3) distilling the aqueous polyurethane-polyvinyl acetate crude emulsion in the step (3) under reduced pressure to remove acetone to obtain a milky blue obvious aqueous polyurethane-polyvinyl acetate emulsion with the solid content of 51 wt% and the particle diameter of 163nm, and adjusting the pH to 7.0-9.0 by using AMP-95.
The vacuum-imbibed plastic of the example was prepared by the following steps:
Adding the waterborne polyurethane-polyvinyl acetate emulsion and a modifier into a dispersion kettle, then adding the ethylene-vinyl acetate copolymer emulsion, wherein the rotating speed of a stirring shaft is 500 revolutions per minute, and stirring for 15 minutes; adding a defoaming agent, and stirring for 10 minutes at the rotating speed of 500 revolutions per minute of a stirring shaft; adding a leveling agent, and stirring for 10 minutes at a stirring shaft rotating speed of 500 revolutions per minute; adding a plasticizer, stirring for 5 minutes at a stirring shaft rotation speed of 500 revolutions per minute, finally adding a thickening agent at a stirring shaft rotation speed of 600 revolutions per minute, adjusting the viscosity to 835mPa & s, and preparing the water-based vacuum plastic.
Example 2
The water-based vacuum plastic is prepared from the following raw materials in parts by weight:
this example waterborne polyurethane-polyvinyl acetate emulsion B was prepared by the following steps:
to a four-necked flask equipped with a reflux condenser, a thermometer and mechanical stirring was added 8g
IPDI、24g
HDI, 208.8g of PBA2000, 5.5g of MPEG1200, 100ppm of organic bismuth catalyst and 23g of acetone, reacting at 75 ℃, sampling and monitoring NCO in the experimental process until the NCO reaches a theoretical value of 2.24 percent, preparing a diisocyanate-terminated prepolymer, cooling to about 60 ℃, and adding 378g of acetone to obtain the diluted diisocyanate-terminated prepolymer.
(2) 1.3g of hydroxyethylethylenediamine, 2.7g of IPDA and 10.2g of
A95 is diluted by 47g deionized water, added into the solution in the step (1) at 45 ℃ and stirred for 20min, 0.60g diethanolamine is diluted by 2g deionized water, added into the reaction system to react for 5min at 45 ℃, and 81g vinyl acetate is addedStirring for 2-3min, and adding 427g of water under the condition of shearing dispersion to obtain the aqueous polyurethane-vinyl acetate mixed emulsion.
(3) And (3) heating the reaction system in the step (2) to 45 ℃, adding 80g of vinyl acetate, stirring for swelling for 30min, adding 0.805g of polyvinyl alcohol 1788, stirring for 0.5h in a low-viscosity mode, adding 0.48g of tert-butyl hydroperoxide and 0.54g of sodium hydrosulfite (sodium hydrosulfite) to initiate polymerization, wherein the initiation temperature is 45 ℃, the polymerization reaction temperature is 45 ℃, adding the same amount of initiator again every 30min, initiating for 4 times, and preserving heat for 30min after the initiation is finished to obtain the waterborne polyurethane-polyvinyl acetate crude emulsion.
(4) And (3) distilling the aqueous polyurethane-polyvinyl acetate crude emulsion in the step (3) under reduced pressure to remove acetone to obtain a milky blue obvious aqueous polyurethane-polyvinyl acetate emulsion with the solid content of 48 wt% and the particle size of 208nm, and adjusting the pH to 8.0 by using AMP-95. The procedure for the preparation of the water-based vacuum-absorbable plastic in this example was the same as in example 1.
The pH value of the water-based vacuum plastic cement prepared in the embodiment is as follows: 7.65, viscosity: 695 mPa.s.
Example 3
The water-based vacuum plastic is prepared from the following raw materials in parts by weight:
the procedure for the preparation of the water-based vacuum-absorbable plastic in this example was the same as in example 1.
The pH value of the water-based vacuum plastic cement prepared in the embodiment is as follows: 7.82, viscosity: 830 mpa.s.
Comparative example 1
The water-based vacuum plastic is prepared from the following raw materials in parts by weight:
the procedure for the preparation of the water-based vacuum-absorbable plastic in this example was the same as in example 1.
The pH value of the water-based vacuum plastic cement prepared in the embodiment is as follows: 7.74, viscosity: 951 mPa.s.
The vacuum-absorbent plastics prepared in the above examples were respectively tested according to the above methods, and the test results are shown in Table 1.
Table 1: results of Performance test of examples and comparative examples
Finally, it should be noted that the above-mentioned embodiments only illustrate the preferred embodiments of the present invention, and do not limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications can be made by modifying the technical solution of the present invention or equivalent substitutions within the scope of the present invention defined by the claims.
Claims (10)
1. The water-based high-gloss vacuum suction plastic is characterized by comprising the following raw materials in parts by weight:
30-60 parts of waterborne polyurethane-polyvinyl acetate emulsion, preferably 35-55 parts,
5 to 30 parts of modifier, preferably 10 to 25 parts,
30-50 parts of ethylene-vinyl acetate copolymer emulsion, preferably 35-45 parts,
0.03 to 0.08 part of defoaming agent, preferably 0.04 to 0.06 part,
0.1 to 0.6 part of leveling agent, preferably 0.2 to 0.5 part,
0.5 to 5 parts of humectant, preferably 1 to 4 parts,
0 to 3.5 parts, preferably 0.1 to 3 parts,
0 to 0.2 part of thickener, preferably 0.02 to 0.18 part.
2. The water-based high-gloss vacuum-absorbent plastic as claimed in claim 1, wherein the number average molecular weight of the water-based polyurethane-polyvinyl acetate emulsion is 3-10 ten thousand daltons, and the solid content is 48-52%.
3. The water-based high-gloss vacuum plastic cement according to claim 1, wherein the water-based polyurethane-polyvinyl acetate emulsion comprises the following raw materials in parts by weight:
(A) 80 to 120 parts, preferably 90 to 110 parts, of a diisocyanate-terminated prepolymer;
(B) 50-250 parts of solvent, preferably 100-200 parts;
(C) 2.5-7 parts of micromolecule amine chain extender, preferably 3.5-4.6 parts;
(D) 0.05-4 parts of monoamino small molecule end-capping agent, preferably 0.1-3 parts;
(E) 30-120 parts of vinyl acetate, preferably 50-100 parts;
(F) the protective colloid accounts for 0.4-1.6% of the mass of the (E), preferably 0.5-1.5%;
(G) the free radical initiator is 0.10-0.6%, preferably 0.15-0.5% of the mass of (E);
(H) water 115-400 parts, preferably 130-350 parts.
4. The water-based high-gloss vacuum plastic cement according to claim 3, wherein the diisocyanate-terminated prepolymer (A) is prepared by mixing and reacting the following raw materials in parts by weight: 15-60 parts of diisocyanate, 100 parts of polyol, 250 parts of hydrophilic compound, 5-20 parts of catalyst and 15-50 parts of solvent;
the diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, and is preferably isophorone diisocyanate and/or hexamethylene diisocyanate;
the polyalcohol is one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol, polytetrahydrofuran ether glycol, polycaprolactone diol, polycarbonate diol, polyethylene glycol adipate diol, 1, 4-butanediol adipate diol, neopentyl glycol adipate diol, 1, 6-hexanediol adipate diol and 1, 6-hexanediol adipate diol, preferably the 1, 4-butanediol adipate diol and/or the 1, 6-hexanediol adipate diol;
The hydrophilic compound is polyoxyalkylene ether containing one hydroxyl or amino, preferably polyethylene glycol monomethyl ether and/or polypropylene glycol monomethyl ether;
the catalyst is one or more of triethylamine, 1, 4-diazabicyclo- [2,2,2] -octane, dibutyltin oxide, tin dioctoate, dibutyltin dilaurate, tin bis- (2-ethylhexanoate), bismuth neodecanoate and bismuth 2-ethylhexanoate, and preferably bismuth neodecanoate;
the solvent (B) is one or more of acetone or butanone;
the micromolecular amine chain extender (C) is one or more of diamino polyether amine, pentamethylene diamine, isophorone diamine, hydroxyethyl ethylene diamine, sodium 2- (2-aminoethyl) aminopropanesulfonate and sodium 2- (2-aminoethyl) aminoethanesulfonate;
the (D) monoamino small molecule end-capping agent is one or more of diethanolamine, diethylamine, diisopropanolamine, 1, 3-diamino-2-propanol and isopropylamine;
the protective colloid (F) is one or more of polyvinyl alcohol, ethoxy alkylphenol and 1, 2-ethylene glycol crosslinked by urethane;
the (G) free radical initiator is one or more of potassium persulfate, tert-butyl hydroperoxide, sodium hydrosulfite and sodium bisulfite.
5. The water-based high-gloss vacuum plastic according to any one of claims 1-4, wherein the water-based polyurethane-polyvinyl acetate emulsion is an anionic polyurethane-polyvinyl acetate emulsion, and is prepared by the following steps:
(1) adding (A) a diisocyanate-terminated prepolymer into (B) a solvent to obtain a diluted diisocyanate-terminated prepolymer;
(2) adding (C) micromolecule amine chain extender into the solution obtained in the step (1) for chain extension reaction, adding (D) monoamino micromolecule end capping agent for end capping reaction after the reaction is finished, adding part of (E) vinyl acetate after the reaction is finished, adding water, shearing and dispersing to obtain the waterborne polyurethane-vinyl acetate mixed emulsion;
(3) adding the rest vinyl acetate into the reaction system in the step (2) for swelling, then adding (F) protective colloid for mixing, and then adding (G) free radical initiator for initiating polymerization to obtain the waterborne polyurethane-polyvinyl acetate crude emulsion;
(4) and (C) removing the solvent from the waterborne polyurethane-polyvinyl acetate coarse emulsion obtained in the step (3) to obtain the waterborne polyurethane-polyvinyl acetate emulsion.
6. The water-based high-gloss vacuum plastic cement as claimed in claim 1, wherein the modifier is a water-based acrylate emulsion, and the acrylate emulsion is preferably Adwel 1367 in Wanhua chemical industry.
7. The water-based high-gloss vacuum plastic according to claim 1, wherein the humectant is one or more selected from glycerol, sorbitol, propylene glycol, hexylene glycol, xylitol, hyaluronic acid, sodium lactate, butyl glycol ether, polypropylene glycol and polyethylene glycol, preferably one or more selected from glycerol, hyaluronic acid, sodium lactate and butyl glycol ether.
8. The water-based high-gloss vacuum absorbent plastic as claimed in claim 1, wherein the plasticizer is a non-phthalate environment-friendly plasticizer, preferably one or more of dipropylene glycol dibenzoate, epoxy acetyl methyl linoleate, diethylene glycol dibenzoate, cyclohexane, and diisononyl 1, 2-dicarboxylate.
9. The water-based high-gloss vacuum-absorbent plastic as claimed in claim 1, wherein the defoaming agent is a silicone defoaming agent, preferably one or more of BYK-024 and BYK-028; and/or
The leveling agent is an organic silicon leveling agent, and preferably one or more of YCK1130, Tego KL 245 and BYK 3455; and/or
The thickener is a polyurethane associative thickener, preferably one or more of VesmodyU604 and VesmodyU300 of Wanhua chemical group GmbH.
10. The preparation method of the water-based high-gloss vacuum plastic cement as claimed in any one of claims 1-9, wherein the water-based polyurethane-polyvinyl acetate emulsion and the modifier are added into a dispersion kettle, then the ethylene-vinyl acetate copolymer emulsion is added, then the defoamer, the leveling agent, the humectant and the plasticizer are sequentially added under the condition that the rotation speed of a stirring shaft is 400-;
preferably, the waterborne polyurethane-polyvinyl acetate emulsion and the modifier are added into a dispersion kettle, then the ethylene-vinyl acetate copolymer emulsion is added, the rotation speed of a stirring shaft is 500-700 r/min, and the stirring is carried out for 10-20 min; adding a defoaming agent, stirring for 8-15 minutes, wherein the rotating speed of a stirring shaft is 300-; adding a leveling agent, stirring for 8-15 minutes, wherein the rotating speed of a stirring shaft is 300-; adding a humectant and a plasticizer, stirring for 6-15 minutes at a stirring shaft rotation speed of 300-800 rpm, finally adding a thickener at a stirring shaft rotation speed of 500-800 rpm, adjusting the viscosity to 600-1000mPa & s, and preparing the water-based vacuum plastic;
further preferably, the preparation method comprises the following steps: adding the waterborne polyurethane-polyvinyl acetate emulsion and the modifier into a dispersion kettle, then adding the ethylene-vinyl acetate copolymer emulsion, wherein the rotating speed of a stirring shaft is 500-700 r/min, and stirring for 15 min; adding a defoaming agent, stirring for 10 minutes, wherein the rotating speed of a stirring shaft is 300-500 rpm; adding a leveling agent, stirring for 10 minutes, wherein the rotating speed of a stirring shaft is 300-500 revolutions per minute; adding a humectant and a plasticizer, stirring for 15 minutes at a stirring shaft rotation speed of 300-800 rpm, finally adding a thickener at a stirring shaft rotation speed of 500-800 rpm, and adjusting the viscosity to 600-1000mPa & s to prepare the water-based vacuum plastic.
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| CN114250056A (en) * | 2021-12-20 | 2022-03-29 | 福建华夏蓝新材料科技有限公司 | High-gloss water-based vacuum suction plastic and preparation method thereof |
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