阅读说明：本技术 一种马来酸酐聚酯多元醇及其制备方法 (Maleic anhydride polyester polyol and preparation method thereof ) 是由 蒋国强 吴晓明 陶晓龙 缪世军 黄东 万鹏 梁国成 袁庆庆 夏海峰 周国君 于 2021-06-03 设计创作，主要内容包括：本发明公开了一种马来酸酐聚酯多元醇及其制备方法,它涉及漆包线漆的制备技术领域。制备方法包括以下步骤：在清洗干净的反应釜中通入氮气保护,加入乙二醇、丙二醇、丙三醇、三羟甲基丙烷、醋酸锌、正钛酸丁酯；逐步加入马来酸酐进行反应；加入己二酸进行反应脱水；保持釜温,直至反应釜精馏柱顶部温度下降,反应出液放缓；反应结束后进行取样观察,并进行送样检测粘度和酸值；利用二甲苯回流共沸将反应釜中生成的水带入分水器；在分水过程中取样检测,直至满足指标；取样检测合格后加入苯酚。本发明的优点在于：制得的马来酸酐聚酯多元醇为原料制备的聚氨酯漆包线漆,在卧式漆包机上进行涂线,涂线检测线样的性能优良,满足市场对产品的要求。(The invention discloses maleic anhydride polyester polyol and a preparation method thereof, and relates to the technical field of wire enamel preparation. The preparation method comprises the following steps: introducing nitrogen into a clean reaction kettle for protection, and adding ethylene glycol, propylene glycol, glycerol, trimethylolpropane, zinc acetate and butyl orthotitanate; gradually adding maleic anhydride to react; adding adipic acid for reaction and dehydration; keeping the temperature of the reaction kettle until the temperature of the top of the rectifying column of the reaction kettle is reduced, and slowing down the reaction liquid; after the reaction is finished, sampling and observing, and sending a sample to detect the viscosity and the acid value; carrying water generated in the reaction kettle into a water separator by utilizing xylene reflux azeotropy; sampling and detecting in the water diversion process until the indexes are met; and (5) adding phenol after sampling and detecting are qualified. The invention has the advantages that: the prepared polyurethane enamelled wire paint prepared by taking maleic anhydride polyester polyol as a raw material is coated on a horizontal enamelling machine, and the performance of a coated wire detection line sample is excellent, so that the requirements of the market on products are met.)

1. A maleic anhydride polyester polyol characterized in that: the composition is prepared from the following components in parts by mass:

2. a method for preparing maleic anhydride polyester polyol according to claim 1, characterized in that: the method comprises the following steps:

s1, introducing nitrogen into a clean reaction kettle for protection, adding ethylene glycol, propylene glycol, glycerol, trimethylolpropane, zinc acetate and n-butyl titanate under a stirring state, heating to 40-50 ℃ while adding materials, and keeping the stirring speed at 45 r/min;

s2, gradually adding maleic anhydride, heating to 105-125 ℃ and reacting for 2 h;

s3, adding adipic acid, heating to 200-205 ℃ for reaction and dehydration;

s4, keeping the temperature of the reaction kettle at 200 ℃ and 205 ℃ for at least 3h until the temperature at the top of the rectifying column of the reaction kettle is reduced and the reaction liquid is slowed down;

s5, sampling after the reaction is finished to observe whether the resin is transparent or not, and sending a sample to detect the viscosity and the acid value;

s6, maintaining the temperature of the kettle at 200 ℃, adding dimethylbenzene into the water separator, and carrying water generated in the reaction kettle into the water separator by utilizing dimethylbenzene reflux azeotropy;

s7, sampling and detecting every 20min in the water diversion process until the indexes of the effluent liquid such as weighing, viscosity and acid value are met;

s8, adding phenol after sampling and detecting are qualified, stirring until the resin is completely dissolved, and cooling the resin solution to below 60 ℃ for later use.

3. The method for preparing maleic anhydride polyester polyol according to claim 2, wherein: in step S7, the sampling test needs to satisfy the following criteria:

the weight of the discharged liquid is 4.8-5.2% of the total mass of the fed materials;

viscosity 450 mPa.s, measured in m-cresol at 25 ℃ cone at 1: 2;

acid value of 0-5mg KOH/g, measured in butyrolactone.

Technical Field

The invention relates to the technical field of wire enamel preparation, in particular to maleic anhydride polyester polyol and a preparation method thereof.

Background

The polyester polyol is one of important components of polyurethane wire enamel, is a reactive oligomer with active hydroxyl, and when a wire is coated to form a film, the active hydroxyl in the polyester polyol and free isocyanate quickly react under the action of a catalyst to form a polyurethane wire enamel film. The polyurethane wire enamel has the characteristic of direct weldability, meets the requirement of high-speed development in the industrial production fields of electronics, electrical industry, electrician industry and the like, and has good application prospect. Polyester polyol, one of the main raw materials for producing polyurethane wire enamel, is increasingly in demand as the field of polyurethane is continuously expanded. At present, there are two types of polyester polyols used in the wire enamel industry, one is an aromatic polyester polyol using phthalic anhydride and phthalic acid (dimethyl phthalate) as main raw materials, and the other is a saturated aliphatic polyester polyol using adipic acid as a main raw material.

Due to the introduction of benzene rings in the molecular structure of the aromatic polyester polyol, the polyester polyol has better thermal stability, simple processing and low price, but when the aromatic polyester polyol is used for preparing a polyurethane enameled wire paint film, the performances of the polyurethane enameled wire paint film such as soldering tin property, saline water pinholes, heat resistance grade and the like are limited. From the aspect of environmental protection, the structure of the material contains benzene rings, so that the material is difficult to degrade after being used and is difficult to meet the requirements of green environment-friendly materials. In the synthesis process of the aliphatic polyester polyol, the alkyd polycondensation activity is high, but the strength is weak, and the prepared polyurethane wire enamel has low heat-resistant grade and cannot well meet the requirements of the market on products.

Disclosure of Invention

The invention aims to solve the technical problem of providing maleic anhydride polyester polyol and a preparation method thereof, and can solve the problem that performances such as soldering tin property, saline water pinholes, heat resistance grade and the like of polyurethane wire enamel prepared from aromatic polyester polyol in the prior art are limited.

In order to solve the technical problems, the technical scheme of the invention is as follows: the maleic anhydride polyester polyol is prepared from the following components in parts by mass:

1 to 3 percent of ethylene glycol

1 to 3 percent of propylene glycol

15-17% of glycerol

Trimethylolpropane 9.5-10.5%

0.01 to 0.03 percent of zinc acetate

0.1 to 0.2 percent of n-butyl titanate

18-25% of maleic anhydride

3 to 10 percent of adipic acid

35 to 45 percent of phenol

A preparation method of maleic anhydride polyester polyol comprises the following steps:

s1, introducing nitrogen into a clean reaction kettle for protection, adding ethylene glycol, propylene glycol, glycerol, trimethylolpropane, zinc acetate and n-butyl titanate under a stirring state, heating to 40-50 ℃ while adding materials, and keeping the stirring speed at 45 r/min;

s2, gradually adding maleic anhydride, heating to 105-125 ℃ and reacting for 2 h;

s3, adding adipic acid, heating to 200-205 ℃ for reaction and dehydration;

s4, keeping the temperature of the reaction kettle at 200 ℃ and 205 ℃ for at least 3h until the temperature at the top of the rectifying column of the reaction kettle is reduced and the reaction liquid is slowed down;

s5, sampling after the reaction is finished to observe whether the resin is transparent or not, and sending a sample to detect the viscosity and the acid value;

s6, maintaining the temperature of the kettle at 200 ℃, adding dimethylbenzene into the water separator, and carrying water generated in the reaction kettle into the water separator by utilizing dimethylbenzene reflux azeotropy;

s7, sampling and detecting every 20min in the water diversion process until the indexes of the effluent liquid such as weighing, viscosity and acid value are met;

s8, adding phenol after sampling and detecting are qualified, stirring until the resin is completely dissolved, and cooling the resin solution to below 60 ℃ for later use.

Further, in step S7, the sampling test needs to satisfy the following criteria:

the weight of the discharged liquid is =4.8-5.2% of the total mass of the fed materials;

viscosity = 450-;

acid number =0-5mg KOH/g, measured in butyrolactone.

The invention has the advantages that: the maleic anhydride polyester polyol is prepared by adopting the component formula and the production process designed by the invention, the prepared maleic anhydride polyester polyol is uniformly mixed with isocyanate closure (polyurethane component), cresol, xylene and n-butyl aldehyde aniline condensation compound according to a certain proportion to prepare polyurethane enamelled wire paint, wire coating is carried out on a horizontal enamelling machine, a wire coating detection line sample can stretch 3 percent and 5 percent of saline water with zero pinhole, the softening breakdown temperature can reach more than 230 ℃, direct welding can be carried out at the soldering tin temperature of 330 ℃, the soldering tin surface is clean and has no residue, and the novel polyurethane enamelled wire paint with the heat-resistant grade of 155 is met.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the scope of the embodiments described herein.

Example 1:

the preparation method of the maleic anhydride polyester polyol comprises the following specific steps:

s1, introducing nitrogen into a clean reaction kettle for protection, adding 2.5Kg of ethylene glycol, 2.8Kg of propylene glycol, 16Kg of glycerol, 10Kg of trimethylolpropane, 20g of zinc acetate and 120g of n-butyl titanate under the stirring state, heating to 45 ℃ while adding materials, and keeping the stirring speed at 45 r/min;

s2, gradually adding 22Kg of maleic anhydride, heating to 110 ℃ and reacting for 2 h;

s3, adding 3.5Kg of adipic acid, heating to 200 ℃ for reaction and dehydration, wherein the top temperature of the rectifying column is 98-105 ℃;

s4, keeping the temperature of the kettle at 200 ℃ for reacting for 3h, reducing the temperature at the top of the rectifying column to 75 ℃, and slowly weighing and increasing the liquid discharged from the collecting tank;

s5, after the reaction is finished, sampling and observing, and sending a sample to detect the viscosity and the acid value, wherein the prepared maleic anhydride polyester polyol resin is not transparent, the viscosity is 350 mPa.s, the acid value is 10.8 mg KOH/g, and the weight of the discharged liquid is 38.2 Kg;

s6, maintaining the temperature of the kettle at 200 ℃, adding dimethylbenzene into the water separator, and carrying water generated in the reaction kettle into the water separator by utilizing dimethylbenzene reflux azeotropy;

s7, discharging the water carried out by the water separator into a collection tank, and sampling and detecting every 20min in the water separating process until the indexes of discharged liquid weighing, viscosity and acid value are met;

s8, when the weight of the effluent in the collection tank reaches 5.0Kg, sampling and observing that the prepared maleic anhydride polyester polyol resin is clear and transparent, the viscosity is 515mPa.s, the acid value is 3.8mg KOH/g, the acid value and the viscosity both meet the requirements, the viscosity testing instrument is a Hake VT-550 cone-plate viscometer, and the testing method is that the maleic anhydride polyester polyol resin is dissolved in m-cresol/25 ℃ cone-plate in a ratio of 1: 2;

s9, adding 42Kg of phenol, stirring until the resin is completely dissolved, and cooling the resin solution to below 60 ℃ for later use.

Example 2:

in the specific embodiment, the maleic anhydride polyester polyol is prepared, compared with the embodiment 1, the specific gravity of the maleic anhydride is reduced, and the specific gravity of the adipic acid is increased, and the specific preparation steps are as follows:

s1, introducing nitrogen into a clean reaction kettle for protection, adding 2.5Kg of ethylene glycol, 2.8Kg of propylene glycol, 16Kg of glycerol, 10Kg of trimethylolpropane, 20g of zinc acetate and 120g of n-butyl titanate under the stirring state, heating to 45 ℃ while adding materials, and keeping the stirring speed at 45 r/min;

s2, gradually adding 18Kg of maleic anhydride, heating to 110 ℃ and reacting for 2 h;

s3, adding 10Kg of adipic acid, heating to 200 ℃ for reaction and dehydration, wherein the top temperature of the rectifying column is 98-105 ℃;

s4, keeping the temperature of the kettle at 200 ℃ for reacting for 3h, reducing the temperature at the top of the rectifying column to 75 ℃, and slowly weighing and increasing the liquid discharged from the collecting tank;

s5, after the reaction is finished, sampling and observing, sending samples to detect the viscosity and the acid value, wherein the prepared maleic anhydride polyester polyol resin is not transparent, the viscosity is 395mPa.s, the acid value is 12.3 mg KOH/g, and the weight of the discharged liquid is 42.3 Kg;

s6, maintaining the temperature of the kettle at 200 ℃, adding dimethylbenzene into the water separator, and carrying water generated in the reaction kettle into the water separator by utilizing dimethylbenzene reflux azeotropy;

s7, discharging the water carried out by the water separator into a collection tank, and sampling and detecting every 20min in the water separating process until the indexes of discharged liquid weighing, viscosity and acid value are met;

s8, when the weight of the effluent in the collection tank reaches 5.1Kg, sampling and observing that the prepared maleic anhydride polyester polyol resin is clear and transparent, the viscosity is 565mPa.s, the acid value is 4.5mg KOH/g, the acid value and the viscosity both meet the requirements, the viscosity testing instrument is a Hake VT-550 cone-plate viscometer, and the testing method is that the maleic anhydride polyester polyol resin is dissolved in m-cresol/25 ℃ cone-plate in a ratio of 1: 2;

s9, adding 42Kg of phenol, stirring until the resin is completely dissolved, and cooling the resin solution to below 60 ℃ for later use.

The maleic anhydride polyester polyol prepared in example 1 and example 2 was uniformly mixed with an isocyanate blocking material (polyurethane component), cresol, xylene, n-butyl aldehyde aniline condensate in a certain ratio to prepare a polyurethane wire enamel, and the wire enamel was applied to a horizontal enameling machine and tested, and the test results are shown in table 1.

Table 1: comparison of Performance in coating test of polyurethane wire enamels prepared from maleic anhydride polyester polyols obtained in example 1 and example 2 as raw materials

As can be seen from the above table, the maleic anhydride polyester polyol prepared in examples 1 and 2, the isocyanate sealer (polyurethane component), the cresol, the xylene, and the n-butyl aldehyde aniline condensate are uniformly mixed in a certain proportion to prepare the polyurethane wire enamel, and the wire enamel is coated on a horizontal enamelling machine, so that the wire enamel has good soldering property, salt water pinholes, heat resistance grade, elongation, breakdown voltage resistance, thermal shock resistance and other properties. Further, when examples 1 and 2 are compared with each other, it can be seen that each of the performances of example 1 is superior to that of example 2, and thus example 1 is the most preferable example.

The maleic anhydride polyester polyol prepared by the invention is uniformly mixed with other substances according to a certain proportion to prepare the polyurethane wire enamel, and the wire is coated on a horizontal enamelling machine, so that the performance of a wire coating detection line sample is excellent, and the requirements of the market on products are met.

The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.