CN102140219A - Water-base resin for plastic and preparation method and application thereof - Google Patents

Abstract

The invention belongs to the technical field of coating chemicals, and in particular relates to a plastic water-based resin with excellent adhesion to plastic substrates, a preparation method and application thereof. The present invention adopts free radical polymerization method, polyaddition reaction or polycondensation method to in-situ polymerize hydrophilic monomers, comonomers, and hydrophobic polymers with a molecular weight of 1000-200,000 in an organic solvent to synthesize a hydrophilic-hydrophobic polymer solution , In the case of adding or not adding a water-based neutralizer, add water "phase inversion" method to prepare a water-based resin for plastics. By adopting the preparation method provided by the invention, the hydrophobic polymer chain segment and the hydrophilic polymer chain segment form a uniform microphase separation structure. The water-based resin prepared by the invention has simple preparation process, good storage stability, high hardness, good water resistance and strong adhesion to the surface of plastic substrates, and can be used to prepare plastic coating materials with excellent performance.

Description

A kind of water-based resin for plastics and its preparation method and application

technical field

The invention belongs to the technical field of coating chemicals, and in particular relates to a plastic water-based resin with excellent adhesion to plastic substrates, a preparation method and application thereof.

Background technique

Since the invention of plastic products, they have been more and more widely used in industrial production because of their low density and light weight compared with other materials. For example, in the automotive industry, the lightweight design of vehicles helps to reduce unit energy consumption, so more and more components are replaced by various plastics, such as polypropylene, ABS, polycarbonate, etc. Another example is that in the home appliance and 3C industries, plastic parts have already accounted for a large proportion, and some can reach more than 80%. At present, the industrial coating of various plastics is basically based on solvent-based coatings from primers to topcoats. During production and construction, the solvent volatilizes a lot, which not only endangers the health of operators and construction personnel, but also causes volatile organic compounds to be discharged. There is a huge environmental problem. Therefore, it is urgent to develop resins for water-based plastics. Compared with traditional solvent-based coatings, water-based resins and coatings use water as the dispersion medium, and have the advantages of non-combustibility, low toxicity, low cost, and easy cleaning, saving resources and energy.

U.S. Patent US2007059530-A1 provides a multi-component water-based resin for consumer electronics market plastic substrates, the water-based resin includes water-based aliphatic polycarbonate-polyurethane dispersion, acrylic polyol resin dispersion and functional group The third component that can be cross-linked with the first two resins at the same time; the VOC content of this resin is very low, and it can form a coating film with good adhesion to various plastic substrates, good moisture resistance and hardness, but the coating The layer has poor adhesion to low polarity plastic substrates. The method of U.S. Patent No. 6184281-B2 has prepared a kind of metal ion cross-linked plastic substrate coating film, and it comprises the polycarboxyl water-based dispersion resin of amine neutralization and the complex zinc ammonium salt that provides crosslinking point, and coating film has good It has the advantages of flexibility, high gloss, moisture resistance, etc., and is mainly used for the external protection of high polarity plastic substrates. Chinese invention patent CN200610026688.6 and Chinese invention patent CN200610026686.7 have reported a kind of water-based polyurethane coating and water-based polyester-amino resin coating material prepared by water-based nano-composite polyester resin, which can be used for plastic surface coating, but it is difficult to For use on low polarity plastic surfaces. Chinese invention patent CN101006147A has reported a kind of combination water-based primer, and it is made up of the water dispersion of modified polyolefin, the polyol resin of water-soluble or water dispersion and pigment, and the primer composition of this three components is to plastics The molded product has good adhesion, excellent water resistance and solvent resistance, but its matrix resin is a combination of two different resin dispersions. Two different process routes increase the complexity of its operation and increase the cost. Invention patent CN101376684A reports that emulsion polymerization is carried out on the basis of modified polyolefin dispersion, and coatings are formulated to form water-based coatings with excellent adhesion to plastic substrates. The modified polymerization is carried out in two steps, which increases the operating cost, and the polymerizable unsaturated monomer of the emulsion polymerization is limited to the free radical polymerizable monomer of the olefin, and its application is limited.

Contents of the invention

The object of the present invention is to provide a water-based resin for plastics with simple preparation process, good storage stability, high hardness, strong adaptability, good adhesion to various plastics and water resistance.

Another object of the present invention is to propose a preparation method of the above-mentioned water-based resin for plastics. The water-based resin is directly prepared by the "phase inversion" method of adding water to a hydrophilic-hydrophobic polymer solution with microphase separation. Furthermore, using hydrophilic monomers, comonomers and hydrophobic polymers with a molecular weight of 1000-200,000 as raw materials, the hydrophilic polymer with microphase separation structure is obtained by solution radical polymerization method or polyaddition reaction or polycondensation method. - A solution of a hydrophobic polymer, and the hydrophilic-hydrophobic polymer can be stably dispersed in water with or without the addition of a neutralizing agent.

Another object of the present invention is to propose the scope of application of the above-mentioned water-based resin and its application method.

The water-based resin for plastics proposed by the present invention is made of hydrophilic monomers, comonomers and hydrophobic polymers with a molecular weight of 1000-200,000 as raw materials, and is prepared by free radical polymerization, addition polymerization or polycondensation. A hydrophilic-hydrophobic polymer solution is obtained, which has a microphase-separated structure and can be stably dispersed in water, wherein the hydrophilic-hydrophobic polymer prepared from a hydrophilic monomer with an ionizable hydrophilic group Hydrophobic polymer solution in which an aqueous neutralizing agent is added to ionize the hydrophilic polymer and then dispersed with water to form an aqueous resin; hydrophilic-hydrophobic polymerization prepared from hydrophilic monomers with non-ionic hydrophilic groups solution, which can be directly dispersed in water.

The water-based resin for plastics proposed by the present invention, wherein the glass transition temperature of the hydrophilic-hydrophobic polymer is -20-150°C, the solid content of the hydrophilic-hydrophobic polymer solution is 30-85wt%, and the solid content of the water-based resin It is 10-60wt%.

The water-based resin proposed by the present invention has good adhesion to plastic substrates such as PVC, Epoxy, ABS, PC, PS, HIPS, POM, PP, PE and the like.

The glass transition temperature of the hydrophilic-hydrophobic polymer of the present invention is preferably 0-100°C.

The hydrophilic-hydrophobic polymer of the present invention has a microphase separation structure, and the size of the hydrophilic or hydrophobic phase separation microdomains is less than 10 μm.

The size of the hydrophilic or hydrophobic phase-separated domains of the hydrophilic-hydrophobic polymer of the present invention is preferably less than 2 μm.

The hydrophilic monomer in the present invention is selected from ionizable hydrophilic monomers, or hydrophilic monomers with non-ionic hydrophilic groups.

The ionizable hydrophilic monomers of the present invention are selected from the group of alkenes with ionizable hydrophilic groups -COOH, -SO ₃ H, -PO ₄ H ₂ , -NH ₂ , -NH or -SH One or two kinds of monomers, alcohol monomers or thiol monomers are used in an amount of 5-40wt% of the total amount of the hydrophilic-hydrophobic polymer.

Non-limiting examples of ionizable hydrophilic monomers described in the present invention are acrylic acid, methacrylic acid, vinylsulfonic acid, propenylsulfonic acid, vinylbenzenesulfonic acid, vinylphosphonic acid, 1,2 -Allenylphosphonic acid, phenylvinyl-1-phosphonic acid, diallylamine, 2,2-dimethylolpropionic acid, dimethylolbutyric acid, 9,10-dihydroxyoctadecanoic acid acid, 2,4-dihydroxybenzoic acid, urethane acrylate, dimethylaminoethyl acrylate, 2-methyl-2-propenoic acid-2-(dimethylamino)ethyl acetate, triethanolamine, 1-amino -2-propanol, phenylpropanolamine, allyl mercaptan, 2-diethylaminoethanethiol, 1,2-ethanedithiol, 1,3-propanedithiol.

The hydrophilic monomers with non-ionic hydrophilic groups in the present invention are selected from molecular weights of 100-50000 with polyoxyethylene chain segments, polyoxypropylene chain segments, Sorbitan ester chain segment, sucrose fatty acid ester chain segment and other non-ionic hydrophilic group ethylenic monomers, alcohol monomers or thiol monomers.

According to the present invention, the hydrophilic monomer with non-ionic hydrophilic group is preferably selected from the molecular weight of 500-10000 that can participate in polycondensation or free radical polymerization, and has polyoxyethylene chain segment, polyoxypropylene chain segment, loss Sorbitan ester chain segment, sucrose fatty acid ester chain segment and other non-ionic hydrophilic group ethylenic monomers, alcohol monomers or thiol monomers.

The hydrophilic monomers with non-ionic hydrophilic groups in the present invention are selected from polyoxyethylene ethers, polyoxypropylene ethers, alkylphenol polyoxyethylene ethers, High-carbon fatty alcohol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene amines, polyoxyethylene amides, polypropylene glycol ethylene oxide adducts (polyether nonionic surfactants), Ethylene oxide adducts of polypropylene glycol with vinyl groups, polyoxyethylene ethers with vinyl groups, polyoxypropylene ethers with vinyl groups, sorbitan esters, sucrose fatty acid esters, hydrophilic One or two of vinyl monomers, alcohol monomers or thiol monomers used in the group account for 5-40 wt% of the total amount of the hydrophilic-hydrophobic polymer.

Non-limiting examples of the hydrophilic monomers with non-ionic hydrophilic groups in the present invention are polyethylene glycol, polyoxyethylene ether glycol, polyoxypropylene ether glycol, polyoxyethylene Ether triol, polyoxypropylene ether triol, polyoxyethylene ether dithiol, polyoxypropylene ether dithiol, castor oil polyoxyethylene ether diol, polyoxypropylene polyoxyethylene glycerol, hydrogenated Castor oil polyoxyethylene ester, dodecyl primary amine polyoxyethylene ester, polyoxyethylene methacrylate, polyoxypropylene methacrylate, polyoxyethylene acrylate, polyurethane modified polyoxyethylene ether glycol , Acrylate modified oxyethylene ether glycol.

The comonomer in the present invention is selected from two kinds of ethylenic comonomers participating in radical polymerization, or isocyanate and alcohol monomers participating in addition polymerization, or acid and alcohol monomers participating in polyester condensation polymerization Or more than two kinds, the amount accounts for 20-75wt% of the total amount of hydrophilic-hydrophobic polymer.

The non-limiting examples of vinyl comonomers involved in free radical polymerization described in the present invention are vinyl acetate, 2-propenyl acetate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, Isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, n-octyl methacrylate, 2-methyl methacrylate, hydroxyethyl acrylate , epoxy vinyl acrylate, hydroxyethyl methacrylate, styrene, α-methylstyrene, 3-tert-butylstyrene, 4-ethoxystyrene, vinyltrimethoxysilane, ethylene Triethoxysilane, Vinylphenyldimethoxysilane, Vinyltris(dimethylsiloxane)silane, 1-(trimethylsiloxane)cyclohexene, Allyldisilazane oxane, methacryloxypropyldiethoxysilane and methacryloxypropyldimethoxysilane.

The non-limiting examples of isocyanate comonomers involved in polyurethane addition polymerization described in the present invention are toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenyl polymethyl polyisocyanate (PAPI ), naphthalene-1,5 diisocyanate, aliphatic 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), isocyanate methoxysilane, isocyanate ethoxysilane, isocyanate alkyl methoxy silanes and isocyanate alkylethoxysilanes.

Polybasic acid comonomers involved in polyester condensation polymerization described in the present invention, non-limiting examples are succinic acid, adipic acid, azelaic acid, pimelic acid, suberic acid, dodecanedioic acid, Isophthalic acid, terephthalic acid, phthalic acid, isophthalic anhydride, terephthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and 1,4-cyclohexanedicarboxylic acid .

The polyhydric alcohols used in polyurethane addition polymerization or polyester condensation polymerization mentioned in the present invention, non-limiting examples are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol , 1,3-butanediol, 1,6-hexanediol, cyclohexanedimethanol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, diethylene diol Alcohol, 2-ethyl-2-propyl-1,3-propanediol, 1,4-cyclohexanediol, glycerol, trimethylolpropane, pentaerythritol, polyether diol, polyether triol , Polyester diol, polyester triol, epoxy diol, amino polyether and polytetrahydrofuran ether.

The molecular weight of the hydrophobic polymer in the present invention is 1000-200,000.

The molecular weight of the hydrophobic polymer in the present invention is preferably 5000-100,000.

The hydrophobic polymer of the present invention consists of a hydrophobic main chain and a hydrophilic group.

The hydrophobic main chain of the hydrophobic polymer of the present invention is selected from C3-C30 alkanes, C3-C30 olefins, C3-C30 cycloalkanes, C6-C30 aromatic hydrocarbons, C3-C30 One or two of alkyl siloxanes and C3-C30 alkyl isocyanates.

The hydrophilic functional group of the hydrophobic polymer of the present invention is selected from one or two of hydroxyl, amino or amino groups, carboxyl groups, sulfonic acid groups, phosphonic acid groups, and halogen groups. 2-50 wt% of the amount of hydrophobic polymer.

Non-limiting examples of the hydrophobic polymers of the present invention are acrylate resins, polyurethane resins, silicone-acrylate resins, epoxy-acrylate resins, silicone-polyurethane resins, polyester resins, olefin-acrylate resins 1. Halogenated olefin resin or cycloolefin resin, the amount used is 5-40wt% of the hydrophilic-hydrophobic polymer.

The hydrophilic-hydrophobic polymer solution of the present invention uses an organic solvent as the medium, and the solid content is 30-85wt%. The organic solvent is selected from hydrophilic organic solvents, hydrophobic organic solvents or mixtures thereof. It is miscible with water or the solubility in water is greater than 14wt%, and the solubility of the hydrophobic organic solvent in water is less than 6wt%.

The hydrophilic-hydrophobic polymer solution of the present invention is based on hydrophilic monomers, comonomers, and hydrophobic polymers with a molecular weight of 1000-200,000 as raw materials, and is prepared by free radical polymerization or addition polymerization or polycondensation. obtained, with a microphase-separated structure.

The solid content of the hydrophilic-hydrophobic polymer solution in the present invention is 30-85wt%.

The water-based resin of the present invention, for the hydrophilic-hydrophobic polymer solution prepared by using a hydrophilic monomer with an ionizable hydrophilic group, adding a water-based neutralizer to ionize the hydrophilic polymer, Obtained by adding water to disperse.

The water-based neutralizing agent of the present invention is used to neutralize the ionizable hydrophilic group on the hydrophilic-hydrophobic polymer segment in an equivalent or non-equivalent amount, and is selected from ammonia, alkylamine, alcoholamine, morpholine, One or more of mercaptans, carboxylic acids, organic sulfonic acids or organic phosphonic acids.

The water-based neutralizing agent of the present invention: the molar ratio of the ionizable hydrophilic group in the hydrophilic-hydrophobic polymer is 0.4-3.

The water-based neutralizing agent of the present invention: the molar ratio of the ionizable hydrophilic group in the hydrophilic-hydrophobic polymer is preferably 0.6-2.

The water-based resin of the present invention can be directly dispersed into water without an aqueous neutralizing agent for the hydrophilic-hydrophobic polymer solution prepared by using hydrophilic monomers with non-ionic hydrophilic groups.

The solid content of the water-based resin in the present invention is 10-60wt%.

The preparation method of plastic water-based resin proposed by the present invention, it comprises the following steps:

(1) Mix hydrophilic monomers with ionizable hydrophilic groups, comonomers, and hydrophobic polymers with a molecular weight of 1000-200,000 in an organic solvent, and use free radical polymerization or polyaddition or polycondensation The method is to prepare a hydrophilic-hydrophobic polymer solution with a microphase separation structure by in-situ polymerization;

(2) Under stirring conditions, at a temperature of 0-100°C, add a water-based neutralizer to the hydrophilic-hydrophobic polymer solution for mixing, and stir evenly at a speed of 100-1500rpm;

(3) Add water to the mixture obtained in step (2) at a temperature of 0-100° C. and a rotational speed of 100-3000 rpm under stirring conditions, and “phase invert” to obtain a water-based resin.

In step (1), the hydrophilic-hydrophobic polymer solution with microphase separation structure is prepared by free radical polymerization method or polyaddition reaction or polycondensation method, and the organic solvent used is divided into hydrophilic organic solvent, hydrophobic organic solvent or a mixture thereof.

In step (2), preferably at a temperature of 0-100° C., an aqueous neutralizing agent is added to the polymer solution for mixing, and stirred at 100-1500 rpm for 2-30 minutes to form an ionized polymer.

In step (3), it is preferable to stir the ionized polymer solution at a temperature of 0-100° C. at a rotational speed of 100-3000 rpm, and add water to obtain a water-based resin for plastics in a “phase inversion” method.

The preparation method of plastic water-based resin proposed by the present invention, it comprises the following steps:

(1) Mix hydrophilic monomers with non-ionic hydrophilic groups, comonomers, and hydrophobic polymers with a molecular weight of 1000-200,000 in an organic solvent, and use free radical polymerization or polyaddition or polycondensation The method is to prepare a hydrophilic-hydrophobic polymer solution with a microphase separation structure by in-situ polymerization;

(2) Add the hydrophilic-hydrophobic polymer solution directly into water at a temperature of 0-100° C., stir at 300-5000 rpm for 2-60 minutes, and disperse it directly in water to obtain a water-based resin.

In step (1), the hydrophilic-hydrophobic polymer solution with microphase separation structure is prepared by free radical polymerization method or polyaddition reaction or polycondensation method, and the organic solvent used is divided into hydrophilic organic solvent, hydrophobic organic solvent or a mixture thereof.

In step (2), water is preferably added to the hydrophilic-hydrophobic polymer solution at a temperature of 0-100° C. at a rotational speed of 100-3000 rpm, and stirred to directly obtain a water-based resin for plastics.

When the plastic water-based resin of the present invention is used for a plastic base material, it can be applied to the surface of the plastic base material after being cured by adding a common curing agent in the paint.

When the water-based resin for plastics of the present invention is used for plastic substrates, it can be formulated into water-based coatings together with additives such as dispersants, defoamers, film-forming aids, pigments and fillers, and then applied to the surface of plastic substrates.

The preparation process of the water-based resin for plastics of the present invention has no special requirement on the pressure, as long as it does not obviously adversely affect the preparation process of the water-based resin for plastics of the present invention. Other process conditions that are not mentioned in the preparation process of the above-mentioned water-based resin for plastics and hydrophilic-hydrophobic polymers of the present invention but may be involved can be the same as the preparation conditions of conventional water-based resins for plastics and hydrophilic-hydrophobic polymers.

The invention proposes a method for preparing plastic water-based resin by the phase inversion method. Its advantages are: compared with the previous water-based resin synthesis method, the present invention adopts solution radical polymerization method or polyaddition reaction or polycondensation method to obtain micro Hydrophilic-hydrophobic polymer solution with phase separation structure, adding or not adding a neutralizer, can directly obtain a water-based resin with a hydrophobic structure in the water phase in one step, with strong adhesion to the surface of the plastic substrate, high hardness, and water resistance Good sex. The preparation process of the invention is very simple, easy to realize industrialized production, can be widely used on the surface of plastic substrates such as ABS, PS, HIPS, PE, HDPE, PP, POM, PVC, etc., and can be used as surface decoration and protection of plastic substrates.

All percentages and ratios used herein are by weight unless otherwise specified.

The term "phase inversion" involved in this article originally refers to the process of mutual transformation of the continuous phase of a multi-component system such as a polymer/oil/water system under certain conditions, such as the transformation of the continuous phase from the water phase to the oil phase or from the oil phase to the water phase , the interfacial tension of the system is the lowest in the continuous phase transition region, so the size of the dispersed phase is the smallest. In the present invention, it is a method for preparing an aqueous polymer dispersion, the specific process is to add a neutralizing agent to the polymer with a hydrophilic group and an organic solution system to ionize the hydrophilic group, and then in a certain Slowly add water to the system under shearing conditions. As the amount of water added increases, the entire system gradually changes from water-in-oil to oil-in-water, forming a uniform and stable water-dilutable or water-soluble system. Alternatively, the polymer solution prepared by polymerizing monomers with non-ionic hydrophilic groups in the present invention can be directly dispersed in water to form a stable dispersion.

Description of drawings

Figure 1 is an atomic force microscope (AFM) photo of a hydrophilic-hydrophobic polymer prepared by the method of the present invention, which shows that the hydrophilic-hydrophobic polymer has a microphase separation structure (500nm * 500nm).

Fig. 2 is a cross-sectional scanning electron microscope (SEM) photograph of a water-based resin coating prepared by the method of the present invention attached to a PP plastic substrate, showing excellent adhesion between the water-based resin coating and the PP plastic substrate.

Detailed ways

The following examples further describe and demonstrate preferred embodiments within the scope of the present invention. These examples are given for illustrative purposes only and should not be construed as limiting the invention.

The steps for preparing the water-based resin for plastics in the following examples are all carried out under normal pressure, unless otherwise specified.

The plastic water-based resin performance characterization that the present invention makes is as follows:

The phase separation phenomenon of hydrophilic-hydrophobic polymers was observed by SPA 300HV-DFM atomic force microscope (AFM) of Seiko Company, Japan.

The morphology of the water-based resin coating film was observed by S-360 field emission scanning electron microscope (FE-SEM) of Cambridge Company, UK.

The adhesion test of the paint film on the plastic substrate is carried out by the cross-cut test method of paint and varnish paint film in accordance with the national standard GB/T 9286-1998. The adhesion to the base material is represented by grades 0 to 5, with grade 0 being the best and grade 5 being the worst.

All tests were performed under ambient conditions unless otherwise stated.

Example 1:

In a 250mL four-necked flask equipped with a thermometer, a condenser, a stirrer, and nitrogen gas, 10 grams of ethylene-acrylic acid copolymer with a molecular weight of 10,000, 20 grams of butyl methacrylate, 10 grams of styrene, and 20 grams of acrylsulfonate Add 40 g of mesitylene to the acid, stir and heat up to reflux at 90° C. under the protection of nitrogen, and perform free radical copolymerization for 5 hours. Cool down after the polymerization reaction, add triethylamine equivalent to the sulfonic acid group and mix, add measured deionized water to make the resin solid content 19wt%, and obtain a water-based resin for plastics. The adhesion of the coating film on PVC and ABS substrates is grade 1.

Example 2:

In a 250mL four-necked flask equipped with a thermometer, a condenser, a stirrer, and nitrogen, 20 grams of chlorinated polypropylene resin with a molecular weight of 100,000, 10 grams of α-methylstyrene, and 15 grams of lauryl methacrylate (LMA ), 25 grams of dimethylaminoethyl acrylate were added to a mixed solvent of 10 grams of butyl acetate and 20 grams of xylene to dissolve and mix uniformly, stirring and heating up to 70-80°C under nitrogen protection, and free radical copolymerization for 8 hours . After the polymerization reaction, cool down, add a little acetic acid aqueous solution with double amino equivalent, mix, add measured deionized water, make the solid content of the resin 30wt%, and obtain milky white water-based resin. The adhesion of the coating film on the ABS substrate is grade 0, and the adhesion on PP and PE substrates is grade 1.

Example 3:

In a 250mL four-necked flask equipped with a thermometer, a condenser and a stirrer, 5 grams of silicone-acrylate resin with a molecular weight of 25,000, 10 grams of phthalic anhydride, 5 grams of pentadecanedioic acid, 5 grams of 1 , 6-hexanediol, 30 grams of dimethylol butyric acid were added to 20 grams of dimethyl succinate and 25 grams of dimethyl glutarate in a mixed solvent, and reacted at 150-180 ° C for 15 hours to obtain a polyester resin . After the polymerization reaction is finished, cool down, add 2 times of carboxyl equivalents of N-methylmorpholine to neutralize the acid in the resin, add metered deionized water, and stir at a high speed at 3000rpm for 30 minutes to make the resin solid content 40wt%. That is, the water-based resin for plastics is obtained. Add water-based polyurethane curing agent, the adhesion of the obtained coating film on the Epoxy plastic substrate is 0 grade, and the adhesion on the POM plastic substrate is 1 grade.

Example 4:

In a 250mL four-necked flask equipped with a thermometer, a condenser and a stirrer, 25 grams of ethylene-vinyl acetate resin with a molecular weight of 40,000, 30 grams of 1,4-butanediol, 5 grams of dodecanedioic acid, 20 grams Add 2,4-dihydroxybenzoic acid into a mixed solvent of 50 grams of xylene and 20 grams of dipropylene glycol dimethyl ether, and react at 120-170° C. for 7 hours to obtain a polyester resin. Cool down after the polymerization reaction, add 0.8 times carboxyl equivalent of N,N-dimethylethanolamine to neutralize the acid in the resin, add measured deionized water to make the solid content of the resin 55wt%, and obtain a water-based resin for plastics. Then add titanium dioxide, talcum powder pigments to disperse, and then add water-based polyurethane curing agent, the adhesion of the obtained coating film on the PS plastic substrate is 0 grade.

Example 5:

In a 250mL four-necked flask equipped with a thermometer, a condenser and a stirrer, 5 grams of epoxy-acrylate resin with a molecular weight of 50,000, 5 grams of terpene resin with a molecular weight of 10,000, and 15 grams of polyether diol with a molecular weight of 3000 5 g of isophorone diisocyanate and 10 g of dimethylol propionic acid were dissolved in a mixed solvent of 30 g of xylene and 30 g of tetrahydrofuran, dissolved and mixed, heated to 80° C. and reacted for 6 hours to obtain a polyurethane resin. Cool down after the polymerization reaction, add 0.6 times carboxyl equivalent ammonia water to neutralize the acid in the resin, add measured deionized water to make the resin solid content 20wt%, and obtain the plastic water-based resin. Add the water-based amino resin curing agent, and the adhesion of the obtained coating film on the ABS plastic substrate is grade 0.

Embodiment 6:

In a 250mL four-necked flask equipped with a thermometer, a condenser, and a stirrer, 10 grams of vinyl chloride resin with a molecular weight of 19,000, 15 grams of polymerizable polyoxyethylene ether with a molecular weight of 6,000-8,000, 20 grams of methyl methacrylate, Add 5 grams of n-ethyl acrylate to 20 grams of xylene and 30 grams of trimethylbenzene to dissolve and mix, raise the temperature to 70-90° C. and react for 6 hours to obtain benzene-acrylic resin. Cool down after the polymerization reaction, add measured deionized water directly to make the solid content of the resin 30wt%, and disperse at 4000rpm to obtain the water-based resin for plastics. The adhesion of the obtained coating film on the PMMA plastic substrate is grade 1.

Embodiment 7:

In a 250mL four-necked flask equipped with a thermometer, a condenser, and a stirrer, 20 grams of polyurethane-acrylate resin with a molecular weight of 8000, 10 grams of polyethylene glycol with a molecular weight of 2000, 10 grams of butanediol, and 30 grams of ophthalmic Diformic acid was dissolved in 30 grams of butyl acetate and mixed, and the temperature was raised to 150-210°C for condensation reaction for 15 hours to obtain a modified polyester resin. Cool down after the polymerization reaction, add measured deionized water directly, and disperse at 3800 rpm to make the solid content of the resin 30wt%, and then obtain the water-based resin for plastics. Add water-based epoxy resin to cure, and the adhesion of the obtained coating film on the PC plastic substrate is 0 grade.

Embodiment 8:

In a 250mL four-necked flask equipped with a thermometer, a condenser, and a stirrer, mix 10 grams of ethylene-vinyl acetate copolymer with a molecular weight of 20,000, 30 grams of polyoxypropylene glycerol ether with a molecular weight of 2,800 to 3,400, and 5 grams of propylene glycol. 20 g of maleic anhydride was dissolved in 10 g of toluene and 25 g of isopropanol and mixed, heated to 140-160° C. for condensation reaction for 25 hours to obtain a modified polyester resin. Cool down after the polymerization reaction, add measured deionized water directly, and disperse at 5000 rpm to make the solid content of the resin 40 wt%, to obtain a water-based resin for plastics. Then add wetting agent, dispersant, titanium dioxide, and barium sulfate to mix, disperse and stir at 5000 rpm, and then add water-based polyurethane curing agent to cure. The adhesion of the obtained coating film on the PVC plastic substrate is grade 1.

Claims (19)

1. plastics use resin, it is characterized in that adopting free radical polymerisation process or polyaddition reaction or polycondensation method, with hydrophilic monomer, comonomer and molecular weight 1000-200,000 hydrophobic polymer in-situ polymerization in organic solvent, synthesize and have the hydrophilic-hydrophobic polymer solution of micro phase separation structure, hydrophilic-the hydrophobic polymer solution that has the hydrophilic monomer preparation of ionizable hydrophilic radical for employing, add the water-based neutralizing agent therein and make the hydrophilic polymer ionization, obtain water-base resin by adding water " phase reversion " method, hydrophilic-hydrophobic polymer solution for the hydrophilic monomer preparation of adopting non-ionic hydrophilic group directly is distributed to it and obtains water-base resin in water;

Wherein, the second-order transition temperature of hydrophilic-hydrophobic polymer is-20-150 ℃, the solid content of hydrophilic-hydrophobic polymer solution is 30-85wt%, the solid content of water-base resin is 10-60wt%.

2. plastics use resin according to claim 1, it is characterized in that described hydrophilic-second-order transition temperature of hydrophobic polymer is for-20-150 ℃, has micro phase separation structure, the size of the microcell that is separated that it is hydrophilic or hydrophobic is less than 10 μ m.

3. plastics use resin according to claim 1 is characterized in that described hydrophilic monomer is selected from ionizable hydrophilic monomer, or has the hydrophilic monomer of non-ionic hydrophilic group.

4. ionizable hydrophilic monomer according to claim 3, it is characterized in that being selected from have ionizable hydrophilic radical-COOH ,-SO ₃H ,-PO ₄H ₂,-NH ₂,-NH or-in vinyl monomer, alcohols monomer or the thio-alcohol monomer of SH one or both, the 5-40wt% of hydrophilic-hydrophobic polymer total amount that consumption accounts for.

5. the hydrophilic monomer that has non-ionic hydrophilic group according to claim 3, it is characterized in that being selected from the molecular weight that to participate in polycondensation or radical polymerization and be in vinyl monomer, alcohols monomer or the thio-alcohol monomer that 100-50000 has non-ionic hydrophilic group such as polyoxyethylene segment, polyoxypropylene segment, sorbitan ester segment, sucrose fatty ester segment one or both, the 5-40wt% of hydrophilic-hydrophobic polymer total amount that consumption accounts for.

6. plastics use resin according to claim 1, it is characterized in that described comonomer is selected from two or more in the alkene class comonomer that participates in radical polymerization or the isocyanic ester that participates in addition polymerization and alcohols monomer or participation polyester condensation polymeric acid and the alcohols monomer, the 20-75wt% of hydrophilic-hydrophobic polymer total amount that consumption accounts for.

7. plastics use resin according to claim 1 is characterized in that hydrophobic polymer is made up of hydrophobic backbone and wetting ability functional group, and molecular weight is 1000-200,000.

8. hydrophobic polymer according to claim 7 is characterized in that hydrophobic backbone is selected from one or more in the alkyl isocyanate of the alkylsiloxane class of the arene of the cycloalkane of the olefines of the alkanes of C3-C45, C3-C45, C3-C45, C6-C45, C3-C45, C3-C45.

9. hydrophobic polymer according to claim 7 is characterized in that the wetting ability functional group is selected from one or both in hydroxyl, amino or amido, carboxyl, sulfonic acid group, phosphonyl group, the halogen group.

10. hydrophobic polymer according to claim 7, it is characterized in that being selected from any one or two kinds of acrylate resin, urethane resin, organic silicon-acrylate resin, epoxy-acrylate resin, organosilicon-urethane resin, vibrin, olefin-acrylic ester resin, haloolefin resin or cyclic olefin resins, the 5-40wt% of hydrophilic-hydrophobic polymer amount that consumption accounts for.

11. plastics use resin according to claim 1, it is characterized in that hydrophilic-hydrophobic polymer solution is medium with the organic solvent, solid content is 30-85wt%, organic solvent is selected from hydrophilic organic solvent, hydrophobic organic solvent or its mixture, in the time of 20 ℃, hydrophilic organic solvent and water dissolve each other or the solubleness in water greater than 14wt%, the solubleness of hydrophobic organic solvent in water is less than 6wt%.

12. plastics use resin according to claim 1, it is characterized in that the water-based neutralizing agent that adds be used in equivalent or the non-equivalent and hydrophilic-hydrophobic polymer segment on ionogenic hydrophilic radical, be selected from ammonia, alkylamine, hydramine, morpholine, mercaptan, carboxylic acid, organic sulfonic acid or the organic phospho acid one or more.

13. water-based neutralizing agent according to claim 12 is characterized in that the water-based neutralizing agent: ionizable hydrophilic radical mole dosage is than being 0.4-3 in hydrophilic-hydrophobic polymer, and the solid content of water-base resin is 10-60wt%.

14. plastics use resin according to claim 1, it is characterized in that having the hydrophilic-hydrophobic polymer solution of the hydrophilic monomer preparation of non-ionic hydrophilic group for employing, can be under the situation of aquosity neutralizing agent not, directly be distributed in the water, the solid content of water-base resin is 10-60wt%.

15. the preparation method as plastics use resin as described in the claim 1-14, it comprises following steps:

(1) will have hydrophilic monomer, comonomer, the molecular weight 1000-200 of ionizable hydrophilic radical, 000 hydrophobic polymer mixes in organic solvent, adopt free radical polymerisation process or polyaddition reaction or polycondensation method, the in-situ polymerization preparation has the hydrophilic-hydrophobic polymer solution of micro phase separation structure;

(2) under 0-100 ℃ temperature, in hydrophilic-hydrophobic polymer solution, add the water-based neutralizing agent and mix, stir under the 100-1500rpm rotating speed;

(3) under 0-100 ℃ temperature, add water in the mixture that under the 100-3000rpm rotating speed, in step (2), obtains, " phase reversion " obtains water-base resin.

16. the preparation method as plastics use resin as described in the claim 1-14, it comprises following steps:

(1) will have hydrophilic monomer, comonomer, the molecular weight 1000-200 of non-ionic hydrophilic group, 000 hydrophobic polymer mixes in organic solvent, adopt free radical polymerisation process or polyaddition reaction or polycondensation method, the in-situ polymerization preparation has the hydrophilic-hydrophobic polymer solution of micro phase separation structure;

(2) under 0-100 ℃ temperature, hydrophilic-hydrophobic polymer solution is directly added in the entry, under the 300-5000rpm rotating speed, stirred 2-60 minute, directly it is dispersed in the water, obtain water-base resin.

17. can be applied to the protection and the decoration on plastic basis material surface according to each plastics use resin of claim 1 to 16; as Resins, epoxy (Epoxy); polycarbonate (PC); polyester (PET); polyoxymethylene (POM); polyvinyl chloride (PVC); polyethylene (PE); polypropylene (PP); polyisobutene (PIB); polystyrene (PS); acrylic (PMMA); (acrylonitrile-styrene-butadienecopolymer (ABS) and their mixed and modified plastic basis materials or based on their plastic basis material with the modification of additive method chemical process, and multiple plastic basis material wherein had good sticking power and water tolerance.

18. when being used for plastic basis material, can add after solidifying agent commonly used solidifies in the coating, be applied to the plastic basis material surface again according to each plastics use resin of claim 1 to 16.

19. when being used for plastic basis material, can be mixed with water-borne coatings with auxiliary agents such as dispersion agent, defoamer, film coalescence aid and pigment, filler earlier, be applied to the plastic basis material surface again according to each plastics use resin of claim 1 to 16.

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