WO2015058681A1

WO2015058681A1 - Preparation method for water-based acrylic-modified saturated polyester resin

Info

Publication number: WO2015058681A1
Application number: PCT/CN2014/089104
Authority: WO
Inventors: 程建军; 秦文; 王英
Original assignee: 北京金汇利应用化工制品有限公司; 廊坊金汇利工业涂料有限公司
Priority date: 2013-10-21
Filing date: 2014-10-21
Publication date: 2015-04-30
Also published as: CN103554381A; WO2015058685A1; CN104761684A; CN104761685A

Abstract

The present invention relates to a preparation method for a water-based acrylic-modified saturated polyester resin. First, a polyacid, a polyol, and a glycidyl versatate are used to synthesize a saturated polyester resin, then, the saturated polyester resin is modified using an acrylic monomer under the effect of an initiator, and then, a neutralizer is added while solid content is adjusted with water, thus acquiring the water-based acrylic-modified saturated polyester resin. The water-based acrylic-modified saturated polyester resin prepared per the present invention is provided with excellent stability, high solid content, low viscosity, and low VOC content and is applicable primarily as an amino paint for use in a water-based coating.

Description

Preparation method of water-based acrylic modified saturated polyester resin

Technical field

The invention relates to a preparation method of an aqueous acrylic modified saturated polyester resin, and belongs to the field of water-based coatings.

Background technique

Waterborne coatings are becoming more and more widely used as a low VOC coating. However, because of the low solid content of the water-based paint, it is difficult to achieve a high decorative effect of the soluble type. Water-based resin as a film-forming substance for aqueous coatings, the solid content, viscosity and VOC content of the aqueous dispersion play a decisive role in the performance of the paint film and on the environment. Saturated polyester has high gloss, high fullness and excellent weather resistance for medium and high grade amino baking varnishes and polyurethane topcoats. However, the current aqueous saturated polyester resin products have the defects of low solid content, easy hydrolysis, and high VOC content.

Summary of the invention

The technical problem to be solved by the present invention is to provide a preparation method of an aqueous acrylic modified saturated polyester resin, which has excellent stability, high solid content, low viscosity and low VOC. The characteristics of the content are of great significance. The resin is mainly used in the amino baking varnish for waterborne coatings.

The technical solution of the present invention to solve the above technical problems is as follows: an aqueous acrylic modified saturated polyester resin, which is synthesized from the following raw materials by weight of the raw materials: 5 to 25 parts of polybasic acid, 15 to 40 parts of polyhydric alcohol, 1 to 3 parts of cosolvent, 5 to 20 parts of acrylic monomer I, 0.5 to 10 parts of acrylic monomer II, 0.01 to 8 parts of initiator, 0.5 to 10 parts of neutralizing agent, 2 to 20 parts of glycidyl tert-carbonate, 40 to 50 parts of deionized water.

Wherein the acrylic monomer I is isobornyl methacrylate, methyl acrylate, methyl propyl acrylate Methyl enoate, ethyl acrylate, ethyl methacrylate, styrene, butyl acrylate, butyl methacrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-ethyl acrylate One or more of hexyl ester, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate;

The acrylic monomer II is acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, methyl acrylate, methacrylic acid One or more of the esters.

For the aqueous acrylic modified saturated polyester resin, the preferred range of various raw materials is: 15 to 25 parts of polybasic acid, 15 to 25 parts of polyhydric alcohol, 1 to 3 parts of a cosolvent, and 5 to 15 parts of an acrylic monomer I. 0.5 to 2 parts of acrylic monomer II, 1 to 5 parts of initiator, 0.5 to 5 parts of neutralizing agent, 3 to 8 parts of glycidyl tert-carbonate, and 40 to 50 parts of deionized water.

Based on the above technical solutions, the present invention can also be improved as follows.

Further, the polybasic acid is adipic acid, 1,4-succinic acid, adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, hexahydrophthalic anhydride, cis One or more of butylene dianhydride and fumaric acid.

Further, the polyol is 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, hydroxypivalic acid hydroxyl new Amyl ester, 2,2,4-trimethyl-1,3 pentanediol, 2-butyl-2-ethyl-1,3-propanediol, pentaerythritol, trimethylolpropane, trimethylolethane One or several of them.

Further, the co-solvent is propylene glycol monobutyl ether, isopropanol, isobutanol, n-butanol, ethylene glycol monobutyl ether, propylene glycol methyl ether, diethylene glycol butyl ether, propylene glycol methyl ether acetate, ethylene One or more of alcohol ether and dipropylene glycol methyl ether.

Further, the initiator is azobisisobutyronitrile, benzoyl peroxide, t-butyl hydroperoxide, di-tert-butyl peroxide, di-tert-amyl peroxide, cumene hydroperoxide, One or more of tert-butyl peroxybenzoate and t-butyl peroxypivalate.

Further, the neutralizing agent is one or more of triethylamine, 2-amino-2-methyl-1-propanol, triethanolamine, diethanolamine, N,N-dimethylethanolamine, and ammonia water.

The present invention provides a method for preparing an aqueous acrylic modified saturated polyester resin as described above, comprising:

1) In a reaction vessel equipped with a stirring device, a reflux condensing device, a dropping device and a temperature control device, a polybasic acid, glycidyl dicarbonate (E10P), a polyhydric alcohol, a nitrogen gas, and a slow heating to 110 to 190 ° C are charged. , heat preservation 0.5 ~ 3h, slowly warming to 200 ~ 250 ° C, heat stirring for 3 ~ 6h, adding 2 ~ 4% of the feed amount of this step back to the acid value of 0 ~ 20mgKOH / g, the reaction process control head temperature is less than 100 ° C;

2) Cool down to 80 ~ 190 ° C, add cosolvent;

3) cooling to 80 ~ 190 ° C, adding 50 ~ 70% of the total amount of initiator initiator and acrylic monomer I mixture, 3.5 ~ 4h stirring and dropping;

4) 80 to 190 ° C dropwise addition of 20-30% of the total amount of initiator and a mixture of acrylic monomer II, 0.5 ~ 1h with stirring to complete;

5) adding the remaining initiator, stirring at 80 ~ 190 ° C for 4h;

6) The temperature is controlled at 50-160 ° C, the neutralizer is added, and stirred for 30 min;

7) When the temperature of the reaction vessel is less than 100 ° C, deionized water is slowly added, the solid content of the resin is adjusted to 45 to 50%, and the discharged material is filtered to obtain an aqueous acrylic modified saturated polyester resin.

Further, the first stage reaction temperature in the step (1) is 150 to 185 ° C, and the second stage reaction temperature is 210 to 235 ° C;

Further, the reaction temperature in the step (3) and the step (4) is in the range of 125 to 180 °C.

In the preparation process, the raw material range is 5 to 25 parts of polybasic acid, 15 to 40 parts of polyhydric alcohol, 1 to 3 parts of a cosolvent, 5 to 20 parts of an acrylic monomer I, and 0.5 to 10 parts of acrylic acid. Monomer II, 0.01-8 parts of initiator, 0.5-10 parts neutralizer, 2-20 parts of glycidyl tert-carbonate, 40~ 50 parts of deionized water.

The preferred range of various raw materials is: 15 to 25 parts of polybasic acid, 15 to 25 parts of polyhydric alcohol, 1 to 3 parts of a co-solvent, 5 to 15 parts of an acrylic monomer I, 0.5 to 2 parts of an acrylic monomer II, 1 to 5 Ingredients, 0.5 to 5 parts neutralizer, 3 to 8 parts of glycidyl tert-carbonate, 40 to 50 parts of deionized water.

The reaction principle of the invention:

1. Synthesis of a polyester resin having an unsaturated bond and a sterically hindered structure;

2. Grafting adjustment of TG acrylic monomer and or functional acrylic monomer;

3. Grafting provides a water-soluble and or functional acrylic monomer to form a spherical-like structure that is hydrolyzed outside the molecule. This special structure protects both ester and entanglement between resin molecules. Reduce the viscosity of the resin and increase the solid content of the construction.

The beneficial effects of the invention are:

a. The prepared aqueous acrylic modified saturated polyester resin modified with glycidyl tert-carbonate increases the protection of the sterically hindered group on the ester and improves the hydrolysis resistance of the resin.

b. Adding the acrylic monomer stepwise, that is, first adding the acryl monomer and the functional acrylic monomer to adjust the TG, and then adding the water-soluble and or functional acrylic monomer to form a molecular internal hydrophobic external pro The spherical structure of water enables the acrylic resin to modify the saturated polyester resin to lower the viscosity of the resin, reduce the amount of the co-solvent added, and increase the solid content of the construction, thereby reducing the VOC content.

The structure diagram is as follows:

The aqueous dispersion of the aqueous acrylic modified saturated polyester resin prepared by the invention has solid content of 45-50%, viscosity ≤1000CP, VOC content≤20g/kg (aqueous dispersion), storage at room temperature for 6 months without delamination, sedimentation, etc. Stability problem, at the same time, the amino baking varnish prepared with the resin and fully methylated amino resin or high imino amino resin is baked at 140-160 ° C for 20-30 min or 110-130 ° C for 20-30 min, 60 ° angle Gloss ≥ 95, vividness (DOI) ≥ 95. It can also be used as a color paint. The decorative effect is comparable to that of a soluble polyester amino baking varnish. It has high hardness and good flexibility. It also has excellent water resistance, solvent resistance, chemical resistance and aging resistance.

detailed description

The principles and features of the present invention are described below, and the examples are intended to be illustrative only and not to limit the scope of the invention.

The specific implementation steps are as follows:

1) In a 1L reaction bottle equipped with a stirring device, a reflux condensing device, a dropping device and a temperature control device, put a polybasic acid, E10P, polyol, and pass nitrogen gas, slowly heat to 190 ° C, keep warm for 1 h, and slowly heat up to 250 ° C, heat preservation 6h, adding 3% of the feed amount of this step of xylene reflux to acid value of less than 20mgKOH / g, the reaction process control head temperature is less than 100 ° C;

2) Cool down to 110 ° C, add cosolvent;

3) dropwise adding a mixture of acrylic monomer I and a total amount of initiator of 60% at 120 ° C, and stirring for 4 hours;

4) dropwise adding a mixture of acrylic monomer II and 25% of the total amount of the initiator at 120 ° C, and dropping it under stirring for 1 hour;

5) Add the remaining initiator, stir at 120 ° C for 4 h, and cool down;

6) When the temperature inside the reaction flask drops to 80 ° C, the neutralizer is added and stirred for 30 min;

7) When the temperature inside the reaction flask drops to 40 ° C, deionized water is slowly added, and the solid content of the resin is adjusted to 45 to 50%, and the discharged material is filtered to obtain an aqueous acrylic modified saturated polyester resin.

The specific ratio is shown in Table 1.

Table 1

The aqueous acrylic modified saturated polyester resin prepared in the above Examples 1, 2, 3, 4, 5 and the cyano amino resin 303 were (10-5):1 or with the cyanoamino resin 327 (10-6). :1 mixed Evenly, add water to adjust the viscosity to 30-40s (coating - 4 cups) spray plate (the substrate is tinplate and matt black glass plate), baking at 140-150 ° C for 20-40min or 110-130 ° C for 20-40min . The varnish formula is as follows:

Table 2

The above leveling agent BYK381 is a product purchased from BYK (bikehuaxue), and CYCAT600 is a product purchased from Cytec Industries Inc. (CYTEC, qingtegongchengcailiao).

The properties of the paint film are as follows:

table 3

Remarks:

BYK Freshness Analyzer: Brightness is the objective criterion for brightness and gloss. BYK is a kind of instrument for measuring the vividness of BYK Chemical. The measurement range is from 0 to 100. The larger the value, The better the better.

The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalents, improvements, etc., which are within the spirit and scope of the present invention, should be included in the protection of the present invention. Within the scope.

Claims

A method for preparing a water-based acrylic modified saturated polyester resin, characterized in that the preparation steps include:

(1) In a reaction vessel equipped with a stirring device, a reflux condensing device, a dropping device and a temperature control device, a polybasic acid, a glycidyl dicarbonate, a polyhydric alcohol, a nitrogen gas, and a slow heating to a first reaction temperature of 110 are charged. ～190°C, heat preservation for 0.5～3h, slowly increase the temperature to the second reaction temperature of 200～250°C, heat and stir for 3~6h, add 2-4% of the total weight of the above feed to reflux to the acid value of 0～20mgKOH/g. , the reaction process controls the head temperature to be less than 100 ° C;

(2) cooling to 80 ~ 190 ° C, adding a cosolvent;

(3) cooling to 80 ~ 190 ° C, adding 50 ~ 70% of the total amount of the initiator of the initiator and the mixture of acrylic acid I, and stirring for 3.5 ~ 4h;

(4) adding 80 to 30% of the total amount of the initiator to the mixture of the initiator and the acrylic monomer II at 80 to 190 ° C, and dropping the mixture under stirring for 0.5 to 1 hour;

(5) adding the remaining initiator, stirring at 80 ~ 190 ° C for 4h;

(6) The temperature is controlled at 50-160 ° C, the neutralizer is added, and stirred for 30 min;

(7) When the temperature in the reaction vessel is less than 100 ° C, deionized water is slowly added, the solid content of the resin is adjusted to 45 to 50%, and the discharged material is filtered to obtain an aqueous acrylic modified saturated polyester resin.
The method for preparing an aqueous acrylic modified saturated polyester resin according to claim 1, wherein the first reaction temperature in the step (1) is 150 to 185 ° C, and the second reaction temperature is 210 ° 235 ° C.
A method of producing an aqueous acrylic modified saturated polyester resin according to claim 1, wherein the reaction temperature in the step (3) and the step (4) is in the range of from 125 to 180 °C.
The method for preparing an aqueous acrylic modified saturated polyester resin according to claim 1, wherein the raw material ranges from 5 to 25 parts of polybasic acid and from 15 to 40 parts by weight of the raw material. Monool, 1-3 parts of co-solvent, 5-20 parts of acrylic monomer I, 0.5-10 parts of acrylic monomer II, 0.01-8 parts of initiator, 0.5-10 parts of neutralizer, 2-20 parts of tert-carbonate Glyceride, 40 to 50 parts of deionized water.
The method for preparing an aqueous acrylic modified saturated polyester resin according to claim 1, wherein the range of the various raw materials is 15 to 25 parts of polybasic acid, 15 to 25 parts of polyhydric alcohol, and 1 to 3 parts. Cosolvent, 5 to 15 parts of acrylic monomer I, 0.5 to 2 parts of acrylic monomer II, 1 to 5 parts of initiator, 0.5 to 5 parts of neutralizing agent, 3 to 8 parts of glycidyl tert-carbonate, 40 to 50 parts Deionized water.
The method for preparing an aqueous acrylic modified saturated polyester resin according to any one of claims 1 to 5, wherein the acrylic monomer I is isobornyl methacrylate, methyl acrylate, and Methyl acrylate, ethyl acrylate, ethyl methacrylate, styrene, butyl acrylate, butyl methacrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-ethyl acrylate One or more of hexyl ester, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate; The acrylic monomer II is acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, methyl acrylate, methacrylic acid One or more of the esters.
The method for preparing an aqueous acrylic modified saturated polyester resin according to any one of claims 1 to 5, wherein the polybasic acid is adipic acid, 1,4-succinic acid or m-benzene. One or more of dicarboxylic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid; the polyol is 1,3- Propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, hydroxypivalic acid hydroxypivalate, 2,2,4-trimethyl One or more of keto-1,3 pentanediol, 2-butyl-2-ethyl-1,3-propanediol, pentaerythritol, glycerol, trimethylolpropane, trimethylolethane .
The method for preparing an aqueous acrylic modified saturated polyester resin according to any one of claims 1 to 5, wherein the auxiliary solvent is propylene glycol monobutyl ether, isopropanol or isobutanol. One or more of n-butanol, ethylene glycol monobutyl ether, propylene glycol methyl ether, diethylene glycol butyl ether, propylene glycol methyl ether acetate, ethylene glycol ethyl ether, and dipropylene glycol methyl ether.
The method for preparing an aqueous acrylic modified saturated polyester resin according to any one of claims 1 to 5, wherein the initiator is azobisisobutyronitrile, benzoyl peroxide, and tertiary One of butyl hydroperoxide, di-tert-butyl peroxide, di-tert-amyl peroxide, cumene hydroperoxide, tert-butyl peroxybenzoate, t-butyl peroxypivalate or Several.
A method for preparing an aqueous acrylic modified saturated polyester resin according to any one of claims 1 to 5, wherein the neutralizing agent is triethylamine or 2-amino-2-methyl- One or more of 1-propanol, triethanolamine, diethanolamine, N,N-dimethylethanolamine, and ammonia.