WO2015058682A1 - Water-soluble saturated polyester resin - Google Patents

Water-soluble saturated polyester resin Download PDF

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WO2015058682A1
WO2015058682A1 PCT/CN2014/089105 CN2014089105W WO2015058682A1 WO 2015058682 A1 WO2015058682 A1 WO 2015058682A1 CN 2014089105 W CN2014089105 W CN 2014089105W WO 2015058682 A1 WO2015058682 A1 WO 2015058682A1
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parts
water
acid
polyester resin
saturated polyester
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PCT/CN2014/089105
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French (fr)
Chinese (zh)
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陈明
秦文
王英
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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
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Publication of WO2015058682A1 publication Critical patent/WO2015058682A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes

Definitions

  • the invention relates to a water-soluble saturated polyester resin, belonging to the field of chemistry.
  • Saturated polyester resin is widely used in medium and high-grade coatings such as amino, polyurethane, etc. due to its high gloss, high fullness and excellent weather resistance.
  • various preparation methods of water-soluble saturated polyesters are as follows: one is that the polyester resin contains an excessive amount of carboxyl groups, and is neutralized with an amine or ammonia to form a salt and has water solubility; the other is A strong hydrophilic group is introduced into the resin.
  • a carboxylic acid of a water-soluble sulfonate or an ester thereof can be made water-soluble by esterification or transesterification; and another is an emulsifier or a resin which can be emulsified by itself.
  • the acid value of the first method is generally 50-60 mg.KOH/g, and the amine has a higher pH after neutralization, while the ester is more susceptible to hydrolysis under alkaline conditions, so the storage period of the resin is short;
  • the water solubility of the resin is very good, because the introduction of strong hydrophilic groups makes the water resistance of the resin decrease, and is mostly used for dispersants, cleaning agents, textiles, etc.; and the third method has the disadvantage of poor chemical resistance and molecular weight due to the presence of an external emulsifier. Low, affecting the appearance of the paint film.
  • the technical problem to be solved by the present invention is to provide a water-soluble saturated polyester resin, which is used in the present invention:
  • the sterically hindered group protects the ester, that is, the method of modifying the saturated polyester by E10P to improve the hydrolytic stability of the water-soluble saturated polyester;
  • the structure is as follows:
  • a water-soluble saturated polyester resin which is synthesized from the following raw materials by the following raw materials: 5-30 parts of glycidyl tert-carbonate, 0.5-10 parts of sulphur Acid group dibasic acid, 15-45 parts diol, 0.05-2 parts catalyst, 10-50 parts polybasic acid without sulfonate groups, 5-20 parts triol, 2-20 parts Aqueous monomer, 10-40 parts cosolvent.
  • the aqueous monomer is one or more of dimethylolpropionic acid, trimellitic anhydride, and dimethylolbutanoic acid.
  • each material preferably ranges from 5 to 15 parts of glycidyl tert-carbonate, 1 to 5 parts of a dibasic acid having a sulfonic acid group, 15 to 30 parts of a diol, and 0.05 to 1 part.
  • the dibasic acid having a sulfonic acid group is sodium 1,4-butanediol-2-sulfonate, sodium isophthalate-5-sulfonate, lithium isophthalate-5-sulfonate One or several of them.
  • the polybasic acid having no sulfonic acid group is one or more of adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, and hexahydrophthalic anhydride.
  • adipic acid isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, and hexahydrophthalic anhydride.
  • the diol is 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, hydroxypivalic acid hydroxyl group
  • neopentyl ester 2,2,4-trimethyl-1,3 pentanediol, 2-butyl-2-ethyl-1,3-propanediol.
  • triol is one or more of glycerin, trimethylolpropane, and trimethylolethane.
  • the catalyst is one or both of an organotin catalyst and tetraisopropyl titanate.
  • the co-solvent is one or more of propylene glycol monobutyl ether, isopropanol, n-butanol, ethylene glycol monobutyl ether, propylene glycol methyl ether, diethylene glycol butyl ether, and propylene glycol methyl ether acetate. .
  • the water-soluble saturated polyester resin is composed of the following raw materials in parts by weight of the raw materials: 5-30 parts of glycidyl tert-carbonate, 0.5-10 parts of dibasic acid having a sulfonic acid group, 15-45 a diol, 0.05-2 parts catalyst, 10-50 parts polybasic acid without sulfonate groups, 5-20 parts triol, 2-20 parts of aqueous monomer, 10-40 parts of co-solvent.
  • the aqueous monomer is one or more of dimethylolpropionic acid, trimellitic anhydride, and dimethylolbutanoic acid.
  • the dibasic acid having a sulfonic acid group is sodium 1,4-butanediol-2-sulfonate, sodium isophthalate-5-sulfonate, lithium isophthalate-5-sulfonate One or several of them.
  • the polybasic acid without a sulfonic acid group is one or more of adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, and hexahydrophthalic anhydride.
  • adipic acid isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, and hexahydrophthalic anhydride.
  • the diol is 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, hydroxypivalic acid hydroxyl
  • neopentyl ester 2,2,4-trimethyl-1,3 pentanediol, 2-butyl-2-ethyl-1,3-propanediol.
  • triol is one or more of glycerol, trimethylolpropane and trimethylolethane.
  • the catalyst is one or both of an organotin catalyst and tetraisopropyl titanate.
  • the co-solvent is one or more of propylene glycol monobutyl ether, isopropanol, n-butanol, ethylene glycol monobutyl ether, propylene glycol methyl ether, diethylene glycol butyl ether, and propylene glycol methyl ether acetate. .
  • the prepared aqueous dispersion of the water-soluble saturated polyester resin is stored at room temperature for 6 months without stability problems such as delamination and precipitation;
  • the water-resistance of the amino baking varnish cured by the resin and the amino resin can be comparable to the soluble polyester amino baking varnish.
  • a reaction bottle equipped with a stirring device, a reflux condensing device, a dropping device and a temperature controlling device, a diol, a dibasic acid having a sulfonic acid group, and a catalyst containing 10% to 70% of the total amount of the catalyst are introduced. After nitrogen is introduced, the temperature is slowly raised to 200-205 ° C, and the reaction is carried out until the acid value is ⁇ 3 mg KOH/g. The temperature of the head is less than 100 ° C during the reaction process; the temperature is lowered to 135 ° C, and the sulfonic acid group is not added in order.
  • the polybasic acid, triol, E10p and the remaining catalyst are slowly heated to 150 ° C under nitrogen protection, the reaction is kept for 2 h, the temperature is further increased to 230 ° C, and the reaction is carried out until the acid value is 8-10 mg KOH / g.
  • the reaction process controls the head temperature. It is less than 100 ° C; the temperature is lowered to 170 ° C, water-soluble monomer is added, and the reaction is carried out at 175 ° C to an acid value of 20 to 25 mg KOH / g; the temperature is lowered to 110 ° C, a co-solvent is added, and the material is filtered to obtain a water-soluble saturated polyester resin.
  • the above wetting leveling agent BYK346 is a product of BYK (bikehuaxue) chemistry
  • the catalyst CYCAT600 is a product of Cytec Industries Inc., CYTEC, qingtegongchengcailiao.
  • the properties of the varnish film obtained are as follows:
  • 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.
  • BYK Orange Peel The surface appearance changes with the size and visibility of the structure. If the edge of the image reflected by the surface has a high contrast and sharpness, the surface structure is observed to be very noticeable. Orange peel can assess the size of the surface structure, ie ultrashort wave to ultra long wave.
  • BYK Orange Peel is an instrument for measuring orange peel produced by BYK Chemical Company. Measuring range, long wave: 0 ⁇ 100; short wave: 0 ⁇ 100.

Abstract

The present invention relates to a water-soluble saturated polyester resin, comprising the following materials by parts: 5-30 parts of glycidyl ester tertcarbonate, 0.5-10 parts of a diacid having a sulfonic acid group, 15-45 parts of a diol, 0.05-2 parts of a catalyst, 10-50 parts of a polyacid not having a sulfonate group, 5-20 parts of a triol, 2-20 parts of an aqueous monomer, and 10-40 parts of a solubilizing agent. The aqueous dispersion of the water-soluble saturated polyester resin prepared according to the present recipe can be stored in room temperature for six months without stability problems such as layering and precipitation. The water-proof property of the amino baked-on coating made by cross-linking and solidifying the present resin and an amino resin is comparable to that of a soluble polyester amino baked-on coating.

Description

一种水溶性饱和聚酯树脂Water-soluble saturated polyester resin 技术领域Technical field
本发明涉及一种水溶性饱和聚酯树脂，属于化学领域。The invention relates to a water-soluble saturated polyester resin, belonging to the field of chemistry.
背景技术Background technique
饱和聚酯树脂由于具有高光泽、高饱满度、优异的耐候性而广泛应用于氨基、聚氨酯等中高档涂料中。目前水溶性饱和聚酯的制备方法有多种,目前主要应用的有以下几种:一种是聚酯树脂含过量的羧基，并用胺或氨中和成盐而具有水溶性；另一种是将强亲水基团引入到树脂中。例如水溶性磺酸盐的羧酸或其酯通过酯化或酯交换反应使饱和聚酯获得水溶性；还有一种是利用乳化剂或配制本身能乳化的树脂。方法一的酸值一般在50-60mg.KOH/g，胺中和后有较高的PH值，而碱性条件下酯健极易水解，因此该类树脂的储存期短；方法二合成的树脂的水溶性很好，因强亲水性基团的引入使得树脂的耐水性能下降，多用于分散剂、清洗剂、纺织品等；而方法三由于存在外加乳化剂，缺点是耐化学性差、分子量低，影响漆膜的外观。Saturated polyester resin is widely used in medium and high-grade coatings such as amino, polyurethane, etc. due to its high gloss, high fullness and excellent weather resistance. At present, there are various preparation methods of water-soluble saturated polyesters. At present, the main applications are as follows: one is that the polyester resin contains an excessive amount of carboxyl groups, and is neutralized with an amine or ammonia to form a salt and has water solubility; the other is A strong hydrophilic group is introduced into the resin. For example, a carboxylic acid of a water-soluble sulfonate or an ester thereof can be made water-soluble by esterification or transesterification; and another is an emulsifier or a resin which can be emulsified by itself. The acid value of the first method is generally 50-60 mg.KOH/g, and the amine has a higher pH after neutralization, while the ester is more susceptible to hydrolysis under alkaline conditions, so the storage period of the resin is short; The water solubility of the resin is very good, because the introduction of strong hydrophilic groups makes the water resistance of the resin decrease, and is mostly used for dispersants, cleaning agents, textiles, etc.; and the third method has the disadvantage of poor chemical resistance and molecular weight due to the presence of an external emulsifier. Low, affecting the appearance of the paint film.
发明内容Summary of the invention
本发明所要解决的技术问题是提供一种水溶性饱和聚酯树脂，本发明采用：The technical problem to be solved by the present invention is to provide a water-soluble saturated polyester resin, which is used in the present invention:
1.空间位阻基团保护酯健,即通过E10P改性饱和聚酯的方法，提高该水溶性饱和聚酯的水解稳定性；1. The sterically hindered group protects the ester, that is, the method of modifying the saturated polyester by E10P to improve the hydrolytic stability of the water-soluble saturated polyester;
2.过量羧基与适量磺酸盐基团同时提供树脂的水溶性，在较低的酸值与PH和少量磺酸盐基团下就能实现水溶性饱和聚酯的水溶性和稳定性，同时改善了强亲水基团磺酸盐树脂耐水性差的缺点。 2. Excess carboxyl group and appropriate amount of sulfonate group simultaneously provide water solubility of the resin, and water solubility and stability of the water-soluble saturated polyester can be achieved at a lower acid value and pH and a small amount of sulfonate groups. The disadvantage of poor water resistance of the strong hydrophilic group sulfonate resin is improved.
结构示意图如下：The structure is as follows:
Figure PCTCN2014089105-appb-000001
Figure PCTCN2014089105-appb-000001
本发明解决上述技术问题的技术方案如下：一种水溶性饱和聚酯树脂，以各个原料的份数计，由以下原料合成：5-30份叔碳酸缩水甘油酯，0.5-10份带有磺酸基团的二元酸，15-45份二元醇，0.05-2份催化剂，10-50份不带有磺酸盐基团的多元酸，5-20份三元醇，2-20份水性单体,10-40份助溶剂。其中所述水性单体为二羟甲基丙酸、偏苯三酸酐、二羟甲基丁酸中的一种或几种。The technical solution of the present invention to solve the above technical problems is as follows: a water-soluble saturated polyester resin, which is synthesized from the following raw materials by the following raw materials: 5-30 parts of glycidyl tert-carbonate, 0.5-10 parts of sulphur Acid group dibasic acid, 15-45 parts diol, 0.05-2 parts catalyst, 10-50 parts polybasic acid without sulfonate groups, 5-20 parts triol, 2-20 parts Aqueous monomer, 10-40 parts cosolvent. The aqueous monomer is one or more of dimethylolpropionic acid, trimellitic anhydride, and dimethylolbutanoic acid.
如上所述之原料配方，其中各个材料优选范围：5-15份叔碳酸缩水甘油酯，1-5份带有磺酸基团的二元酸，15-30份二元醇，0.05-1份催化剂，30-50份不带有磺酸盐基团的多元酸，5-15份三元醇，5-15份水性单体，10-20份助溶剂。a raw material formulation as described above, wherein each material preferably ranges from 5 to 15 parts of glycidyl tert-carbonate, 1 to 5 parts of a dibasic acid having a sulfonic acid group, 15 to 30 parts of a diol, and 0.05 to 1 part. Catalyst, 30-50 parts of polybasic acid without sulfonate groups, 5-15 parts of triol, 5-15 parts of aqueous monomer, 10-20 parts of co-solvent.
进一步，所述带有磺酸基团的二元酸为1,4-丁二醇-2-磺酸钠、间苯二甲酸-5-磺酸钠、间苯二甲酸-5-磺酸锂中的一种或几种。Further, the dibasic acid having a sulfonic acid group is sodium 1,4-butanediol-2-sulfonate, sodium isophthalate-5-sulfonate, lithium isophthalate-5-sulfonate One or several of them.
进一步，所述不带有磺酸基团的多元酸为己二酸、间苯二甲酸、对苯二甲酸，1,4-环己烷二甲酸、偏苯三酸酐、六氢苯酐中的一种或几种。 Further, the polybasic acid having no sulfonic acid group is one or more of adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, and hexahydrophthalic anhydride. Kind.
进一步，所述二元醇为1，3-丙二醇、新戊二醇、1,4-丁二醇、1，6-己二醇、1,4-环己烷二甲醇、羟基新戊酸羟基新戊酯、2,2,4-三甲基-1,3戊二醇、2-丁基-2-乙基-1,3-丙二醇中的一种或几种。Further, the diol is 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, hydroxypivalic acid hydroxyl group One or more of neopentyl ester, 2,2,4-trimethyl-1,3 pentanediol, 2-butyl-2-ethyl-1,3-propanediol.
进一步，所述三元醇为丙三醇、三羟甲基丙烷、三羟甲基乙烷中的一种或几种。Further, the triol is one or more of glycerin, trimethylolpropane, and trimethylolethane.
进一步，所述催化剂为有机锡催化剂、四异丙基钛酸酯中的一种或两种。Further, the catalyst is one or both of an organotin catalyst and tetraisopropyl titanate.
进一步，所述助溶剂为丙二醇单丁醚、异丙醇、正丁醇、乙二醇单丁醚、丙二醇甲醚、二乙二醇丁醚、丙二醇甲醚醋酸酯中的一种或几种。Further, the co-solvent is one or more of propylene glycol monobutyl ether, isopropanol, n-butanol, ethylene glycol monobutyl ether, propylene glycol methyl ether, diethylene glycol butyl ether, and propylene glycol methyl ether acetate. .
如上所述水溶性饱和聚酯树脂的制备方法，包括：A method for preparing a water-soluble saturated polyester resin as described above, comprising:
1)向装有搅拌装置、回流冷凝装置、滴加装置和控温装置反应釜中投入带有磺酸盐基团的二元酸、二元醇与占催化剂总量10％～70％的催化剂，通入氮气，缓慢加热至80～100℃开动搅拌，再缓慢升温至180～210℃，反应过程控制馏头温度小于100℃，搅拌反应至酸值为0～10mgKOH/g；1) introducing a dibasic acid having a sulfonate group, a diol, and a catalyst containing 10% to 70% of the total amount of the catalyst into a reaction vessel equipped with a stirring device, a reflux condensing device, a dropping device, and a temperature controlling device. , nitrogen gas is introduced, slowly heated to 80 ~ 100 ° C to start stirring, and then slowly heated to 180 ~ 210 ° C, the reaction process control head temperature is less than 100 ° C, stirring reaction to acid value of 0 ~ 10mgKOH / g;
2)降温至小于170℃，加入不带有磺酸盐基团的多元酸、三元醇、叔碳酸缩水甘油酯(E10P，购自迈图高新材料集团)和剩余的催化剂，保持搅拌缓慢升温至140～190℃，保温反应0.5～2h，继续升温至210～250℃，反应过程控制馏头温度小于100℃，搅拌反应至酸值为0～15mgKOH/g；2) Cool down to less than 170 ° C, add polybasic acid, triol, glycidyl tert-carbonate (E10P, purchased from Momentive Advanced Materials Group) without sulfonate groups and the remaining catalyst, keep stirring slowly To 140 ~ 190 ° C, the incubation reaction for 0.5 ~ 2h, continue to raise the temperature to 210 ~ 250 ° C, the reaction process control head temperature is less than 100 ° C, stirring reaction to an acid value of 0 ~ 15mgKOH / g;
3)降温至小于180℃，加入水性单体，170～190℃搅拌反应，至酸值为20～40mgKOH/g；3) cooling to less than 180 ° C, adding aqueous monomer, stirring reaction at 170 ~ 190 ° C, to an acid value of 20 ~ 40mgKOH / g;
4)降温至小于180℃，加助溶剂稀释，至树脂固含为75～85％，边加边搅拌，然后过滤出料，即得水溶性饱和聚酯树脂。4) Cool down to less than 180 ° C, add solvent to dilute, to 75 ~ 85% of the resin solids, while stirring, and then filter out the material to obtain a water-soluble saturated polyester resin.
其中，所述水溶性饱和聚酯树脂以原料重量份数计，由以下原料组成：5-30份叔碳酸缩水甘油酯，0.5-10份带有磺酸基团的二元酸，15-45份二元醇，0.05-2份催化剂，10-50份不带有磺酸盐基团的多元酸，5-20份三元醇， 2-20份水性单体，10-40份助溶剂。Wherein, the water-soluble saturated polyester resin is composed of the following raw materials in parts by weight of the raw materials: 5-30 parts of glycidyl tert-carbonate, 0.5-10 parts of dibasic acid having a sulfonic acid group, 15-45 a diol, 0.05-2 parts catalyst, 10-50 parts polybasic acid without sulfonate groups, 5-20 parts triol, 2-20 parts of aqueous monomer, 10-40 parts of co-solvent.
其中，所述水性单体为二羟甲基丙酸、偏苯三酸酐、二羟甲基丁酸中的一种或几种。Wherein, the aqueous monomer is one or more of dimethylolpropionic acid, trimellitic anhydride, and dimethylolbutanoic acid.
其中，所述带有磺酸基团的二元酸为1,4-丁二醇-2-磺酸钠、间苯二甲酸-5-磺酸钠、间苯二甲酸-5-磺酸锂中的一种或几种。Wherein the dibasic acid having a sulfonic acid group is sodium 1,4-butanediol-2-sulfonate, sodium isophthalate-5-sulfonate, lithium isophthalate-5-sulfonate One or several of them.
其中，所述不带有磺酸基团的多元酸为己二酸、间苯二甲酸、对苯二甲酸，1,4-环己烷二甲酸、偏苯三酸酐、六氢苯酐中的一种或几种。Wherein the polybasic acid without a sulfonic acid group is one or more of adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, and hexahydrophthalic anhydride. Kind.
其中，所述二元醇为1，3-丙二醇、新戊二醇、1,4-丁二醇、1，6-己二醇、1,4-环己烷二甲醇、羟基新戊酸羟基新戊酯、2,2,4-三甲基-1,3戊二醇、2-丁基-2-乙基-1,3-丙二醇中的一种或几种。Wherein the diol is 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, hydroxypivalic acid hydroxyl One or more of neopentyl ester, 2,2,4-trimethyl-1,3 pentanediol, 2-butyl-2-ethyl-1,3-propanediol.
其中，所述三元醇为丙三醇、三羟甲基丙烷、三羟甲基乙烷中的一种或几种。Wherein the triol is one or more of glycerol, trimethylolpropane and trimethylolethane.
其中，所述催化剂为有机锡催化剂、四异丙基钛酸酯中的一种或两种。Wherein the catalyst is one or both of an organotin catalyst and tetraisopropyl titanate.
其中，所述助溶剂为丙二醇单丁醚、异丙醇、正丁醇、乙二醇单丁醚、丙二醇甲醚、二乙二醇丁醚、丙二醇甲醚醋酸酯中的一种或几种。Wherein, the co-solvent is one or more of propylene glycol monobutyl ether, isopropanol, n-butanol, ethylene glycol monobutyl ether, propylene glycol methyl ether, diethylene glycol butyl ether, and propylene glycol methyl ether acetate. .
本发明的有益效果是：The beneficial effects of the invention are:
1.制备的水溶性饱和聚酯树脂的水分散体常温储存6个月无分层、沉淀等稳定性问题；1. The prepared aqueous dispersion of the water-soluble saturated polyester resin is stored at room temperature for 6 months without stability problems such as delamination and precipitation;
2.用本树脂与氨基树脂交联固化的氨基烤漆的耐水性能够与溶性型聚酯氨基烤漆相媲美。2. The water-resistance of the amino baking varnish cured by the resin and the amino resin can be comparable to the soluble polyester amino baking varnish.
具体实施方式detailed description
向装有搅拌装置、回流冷凝装置、滴加装置和控温装置1L反应瓶中投入二元醇、带有磺酸基团的二元酸和占催化剂总量10％～70％的催化剂，通 入氮气后，缓慢升温至200～205℃，保温反应至酸值<3mgKOH/g，反应过程控制馏头温度小于100℃；将温度降至135℃，按顺序加入不带有磺酸基团的多元酸、三元醇、E10p和剩余的催化剂，在氮气保护下缓慢升温至150℃，保温反应2h，继续升温至230℃，保温反应至酸值8～10mgKOH/g，反应过程控制馏头温度小于100℃；降温至170℃，加入水溶性单体，175℃保温反应至酸值20～25mgKOH/g；降温至110℃，加入助溶剂，过滤出料，得到水溶性饱和聚酯树脂。Into a reaction bottle equipped with a stirring device, a reflux condensing device, a dropping device and a temperature controlling device, a diol, a dibasic acid having a sulfonic acid group, and a catalyst containing 10% to 70% of the total amount of the catalyst are introduced. After nitrogen is introduced, the temperature is slowly raised to 200-205 ° C, and the reaction is carried out until the acid value is <3 mg KOH/g. The temperature of the head is less than 100 ° C during the reaction process; the temperature is lowered to 135 ° C, and the sulfonic acid group is not added in order. The polybasic acid, triol, E10p and the remaining catalyst are slowly heated to 150 ° C under nitrogen protection, the reaction is kept for 2 h, the temperature is further increased to 230 ° C, and the reaction is carried out until the acid value is 8-10 mg KOH / g. The reaction process controls the head temperature. It is less than 100 ° C; the temperature is lowered to 170 ° C, water-soluble monomer is added, and the reaction is carried out at 175 ° C to an acid value of 20 to 25 mg KOH / g; the temperature is lowered to 110 ° C, a co-solvent is added, and the material is filtered to obtain a water-soluble saturated polyester resin.
表1：实施例配方Table 1: Example Formulation
Figure PCTCN2014089105-appb-000002
Figure PCTCN2014089105-appb-000002
将实施例1、2、3、4、5制备的水溶性饱和聚酯树脂100g与氰特全甲醚化氨基树脂303或与氰特高亚氨基树脂327混合均匀，加水及助剂按照表2的配比混合均匀，粘度范围30～40s(涂-4杯)喷板(基材是马口铁和亚 光黑玻璃板)，140～150℃烘烤20～40min或110～130℃烘烤20～40min。100 g of the water-soluble saturated polyester resin prepared in Examples 1, 2, 3, 4, and 5 was mixed with the cyano-ethylated amino resin 303 or the cyano-high imino resin 327, and water and additives were added according to Table 2. The ratio is evenly mixed, the viscosity range is 30 ~ 40s (coating - 4 cups) spray plate (the substrate is tinplate and Asia Light black glass plate), baked at 140 ~ 150 ° C for 20 ~ 40min or 110 ~ 130 ° C for 20 ~ 40min.
表2Table 2
Figure PCTCN2014089105-appb-000003
Figure PCTCN2014089105-appb-000003
以上润湿流平剂BYK346是毕克(BYK,bikehuaxue)化学的产品，催化剂CYCAT600是氰特(Cytec Industries Inc.,CYTEC,qingtegongchengcailiao)的产品。The above wetting leveling agent BYK346 is a product of BYK (bikehuaxue) chemistry, and the catalyst CYCAT600 is a product of Cytec Industries Inc., CYTEC, qingtegongchengcailiao.
得到清漆漆膜性能如下表3：The properties of the varnish film obtained are as follows:
表3table 3
Figure PCTCN2014089105-appb-000004
Figure PCTCN2014089105-appb-000004
备注: Remarks:
BYK鲜映性仪:鲜映性是明亮度和光泽的客观判定标准,BYK鲜映性仪是德国毕克化学生产的一款测量鲜映性的仪器，测量范围0～100，数值越大，鲜映性越好。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.
BYK桔皮仪：表面外观随着改变结构的大小和明显程度面改变。如果表面反射的影像边缘有着较高的对比度和轮廓分明度，则可观察到表面结构非常明显。桔皮可评估表面结构的大小即超短波到超长波。BYK桔皮仪是德国毕克化学公司生产的测量桔皮性的仪器。测量范围，长波：0～100；短波：0～100。BYK Orange Peel: The surface appearance changes with the size and visibility of the structure. If the edge of the image reflected by the surface has a high contrast and sharpness, the surface structure is observed to be very noticeable. Orange peel can assess the size of the surface structure, ie ultrashort wave to ultra long wave. BYK Orange Peel is an instrument for measuring orange peel produced by BYK Chemical Company. Measuring range, long wave: 0 ~ 100; short wave: 0 ~ 100.
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 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 (7)

  1. 一种水溶性饱和聚酯树脂，其特征在于，以各原料重量份数计算，由以下原料合成：5-30份叔碳酸缩水甘油酯，0.5-10份带有磺酸基团的二元酸，15-45份二元醇，0.05-2份催化剂，10-50份不带有磺酸盐基团的多元酸，5-20份三元醇，2-20份水性单体，10-40份助溶剂；A water-soluble saturated polyester resin characterized by being synthesized from the following raw materials by weight fraction of each raw material: 5-30 parts of glycidyl tert-carbonate, 0.5-10 parts of dibasic acid having a sulfonic acid group , 15-45 parts of diol, 0.05-2 parts of catalyst, 10-50 parts of polybasic acid without sulfonate groups, 5-20 parts of triol, 2-20 parts of water-based monomer, 10-40 Cosolvent
    其中，所述水性单体为二羟甲基丙酸、偏苯三酸酐、二羟甲基丁酸中的一种或几种。Wherein, the aqueous monomer is one or more of dimethylolpropionic acid, trimellitic anhydride, and dimethylolbutanoic acid.
  2. 根据权利要求1所述的一种水溶性饱和聚酯树脂，其特征在于，原料的范围为：5-15份叔碳酸缩水甘油酯，1-5份带有磺酸基团的二元酸，15-30份二元醇，0.05-1份催化剂，30-50份不带有磺酸盐基团的多元酸，5-15份三元醇，5-15份水性单体，10-20份助溶剂。A water-soluble saturated polyester resin according to claim 1, wherein the raw material ranges from 5 to 15 parts of glycidyl tert-carbonate, and 1 to 5 parts of a dibasic acid having a sulfonic acid group. 15-30 parts of diol, 0.05-1 part of catalyst, 30-50 parts of polybasic acid without sulfonate groups, 5-15 parts of triol, 5-15 parts of aqueous monomer, 10-20 parts Cosolvent.
  3. 根据权利要求1或2所述的一种水溶性饱和聚酯树脂，其特征在于：所述带有磺酸基团的二元酸为1,4-丁二醇-2-磺酸钠、间苯二甲酸-5-磺酸钠、间苯二甲酸-5-磺酸锂中的一种或几种；A water-soluble saturated polyester resin according to claim 1 or 2, wherein the dibasic acid having a sulfonic acid group is sodium 1,4-butanediol-2-sulfonate, One or more of sodium phthalate-5-sulfonate and lithium isophthalate-5-sulfonate;
    所述不带有磺酸基团的多元酸为己二酸、间苯二甲酸、对苯二甲酸，1,4-环己烷二甲酸、偏苯三酸酐、六氢苯酐中的一种或几种。The polybasic acid having no sulfonic acid group is one or more of adipic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, and hexahydrophthalic anhydride.
  4. 根据权利要求1或2所述的一种水溶性饱和聚酯树脂，其特征在于：所述二元醇为1，3-丙二醇、新戊二醇、1,4-丁二醇、1，6-己二醇、1,4-环己烷二甲醇、羟基新戊酸羟基新戊酯、2,2,4-三甲基-1,3戊二醇、2-丁基-2-乙基-1,3-丙二醇中的一种或几种。A water-soluble saturated polyester resin according to claim 1 or 2, wherein the diol is 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,6 - hexanediol, 1,4-cyclohexanedimethanol, hydroxypivalyl hydroxypivalate, 2,2,4-trimethyl-1,3 pentanediol, 2-butyl-2-ethyl One or more of -1,3-propanediol.
  5. 根据权利要求1或2所述的一种水溶性饱和聚酯树脂，其特征在于：所述三元醇为丙三醇、三羟甲基丙烷、三羟甲基乙烷中的一种或几种。A water-soluble saturated polyester resin according to claim 1 or 2, wherein the triol is one or more of glycerin, trimethylolpropane and trimethylolethane Kind.
  6. 根据权利要求1或2所述的一种水溶性饱和聚酯树脂，其特征在于：所述催化剂为有机锡催化剂、四异丙基钛酸酯中的一种或两种。 A water-soluble saturated polyester resin according to claim 1 or 2, wherein the catalyst is one or both of an organotin catalyst and tetraisopropyl titanate.
  7. 根据权利要求1或2所述的一种水溶性饱和聚酯树脂，其特征在于：所述助溶剂为丙二醇单丁醚、异丙醇、正丁醇、乙二醇单丁醚、丙二醇甲醚、二乙二醇丁醚、丙二醇甲醚醋酸酯中的一种或几种。 A water-soluble saturated polyester resin according to claim 1 or 2, wherein the co-solvent is propylene glycol monobutyl ether, isopropanol, n-butanol, ethylene glycol monobutyl ether, and propylene glycol methyl ether. One or more of diethylene glycol butyl ether and propylene glycol methyl ether acetate.
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