阅读说明：本技术 一种冰箱隔热聚氨酯泡沫组合料用聚酯多元醇及其制备方法 (Polyester polyol for refrigerator heat insulation polyurethane foam composite material and preparation method thereof ) 是由 徐礼文 徐春翼 刘礼华 王琳 于 2019-12-23 设计创作，主要内容包括：本发明涉及聚酯多元醇及其制备方法,具体公开了一种冰箱隔热聚氨酯泡沫组合料用聚酯多元醇及其制备方法,旨在解决现有反应原料多为易燃物,其产物的阻燃性能较差的问题。所述聚酯多元醇包括多元醇系统与二元/多元酸,所述多元醇系统中至少含有一种单糖或二糖1～30％,以及至少含有一种二元/多元醇70～99％。其制备方法包括：将多元醇系统与二元/多元酸装入反应器中,加热熔融并搅拌反应；温度上升至120～150℃时脱水,升温至200～250℃反应12～48小时,降温、过滤得到聚酯多元醇。本发明以单糖或二糖作为多元醇的一部分进行反应制备聚酯多元醇,明显降低了易燃性。与其它阻燃剂配合,作为制备冰箱隔热聚氨酯泡沫组合料的原料,显著提高其阻燃性能。(The invention relates to polyester polyol and a preparation method thereof, and particularly discloses polyester polyol for a refrigerator heat-insulating polyurethane foam composite material and a preparation method thereof, aiming at solving the problems that most of the existing reaction raw materials are inflammable substances, and the flame retardant property of the product is poor. The polyester polyol comprises a polyol system and a dibasic/polybasic acid, wherein the polyol system at least contains 1-30% of monosaccharide or disaccharide and 70-99% of the dibasic/polybasic acid. The preparation method comprises the following steps: charging a polyol system and dibasic/polybasic acid into a reactor, heating, melting and stirring for reaction; dewatering when the temperature rises to 120-150 ℃, heating to 200-250 ℃ for reaction for 12-48 hours, cooling, and filtering to obtain the polyester polyol. The invention takes monosaccharide or disaccharide as a part of the polyol to react to prepare the polyester polyol, thereby obviously reducing the inflammability. The flame retardant is matched with other flame retardants to be used as a raw material for preparing the refrigerator heat-insulation polyurethane foam composite material, so that the flame retardant property of the composite material is obviously improved.)

1. The polyester polyol for the refrigerator heat-insulation polyurethane foam composite material comprises the following raw material components: the polyol system and the dibasic/polybasic acid are characterized in that the polyol system at least contains 1-30% of monosaccharide or disaccharide and 70-99% of dibasic/polybasic alcohol.

2. The polyester polyol for the polyurethane foam composition for refrigerator insulation according to claim 1, wherein the polyol system comprises 1 to 20% of at least one monosaccharide or disaccharide and 80 to 99% of at least one di/polyol.

3. The polyester polyol for the refrigerator heat insulation polyurethane foam composition as claimed in claim 1 or 2, wherein the molar ratio of the dibasic/polybasic acid to the polyol system is 1 (1.0-1.5).

4. The polyester polyol for the refrigerator insulation polyurethane foam composition as claimed in claim 3, wherein the monosaccharide is one or a mixture of glucose, fructose and arabinose.

5. The polyester polyol for the refrigerator insulation polyurethane foam composition according to claim 1, wherein the disaccharide is one or a mixture of xylose, sucrose and maltose.

6. The polyester polyol for refrigerator insulation polyurethane foam composition according to claim 1, wherein the dihydric/polyhydric alcohol includes but is not limited to one or more of ethylene glycol, propylene glycol, methyl propylene glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, 1, 3-butanediol, 1, 4-butanediol, pentanediol, neopentyl glycol, 1, 6-hexanediol, pentaerythritol, and the like.

7. The polyester polyol for refrigerator insulation polyurethane foam composition according to claim 1, wherein the binary/polybasic acid is selected from aliphatic or aromatic binary/polybasic acids, including but not limited to succinic acid, glutaric acid, adipic acid, sebacic acid, butenedioic acid, maleic anhydride, phthalic acid, phthalate, halogenated phthalic acid, halogenated phthalate, phthalic anhydride, and the like, in one or more combinations.

8. The method for preparing polyester polyol for refrigerator insulation polyurethane foam composition as claimed in claim 1, comprising the steps of:

(1) charging a polyol system and dibasic/polybasic acid into a reactor according to the formula amount, heating and melting under the protection of nitrogen, and stirring for reaction;

(2) dehydrating when the temperature rises to 120-150 ℃, and continuously heating to 200-250 ℃ for reaction for 12-48 hours;

(3) and when the acid value is less than 0.4, cooling to finish the reaction, cooling, filtering and packaging to obtain the polyester polyol.

Technical Field

The invention relates to polyester polyol and a preparation method thereof, in particular to polyester polyol for a refrigerator heat-insulation polyurethane foam composite material and a preparation method thereof.

Background

Polyurethane materials are widely used in various fields such as adhesives, foams, elastomers, and coatings because of their excellent strength, elasticity, and abrasion resistance. Wherein the polyester polyol is one of core raw materials for producing the polyester polyurethane. In the polyurethane industry, polyester polyol is one of the most important raw material intermediates, is commonly used in products such as PU slurry, elastomers, sole stock solution, adhesives and the like, and is used as a soft segment in a polyurethane structure to provide mechanical properties such as good elongation, rebound resilience, softness and the like for the products.

Polyester polyols are typically prepared by the condensation of di/polyhydric alcohols with di/polycarboxylic acids. Polyester polyols exhibit different properties depending on the raw materials. However, the condensation reaction is mostly flammable, and the condensation product has poor flame retardant property, so the application is greatly limited. In order to improve the flame retardant property, a flame retardant is generally added, so that the production cost is increased.

The fire performance ratings of the materials are A, B1, B2, and B3, which are incombustibility (self-extinguishing after leaving the fire source, or extinguishing within 10 seconds), flammability (no increase in fire after ignition, and no ignition of filter paper by drips), and flammability (little ignition, and increasing fire), respectively. Common polyester polyols belong to the group of flammable materials (B3).

Disclosure of Invention

The first purpose of the invention is to provide polyester polyol for refrigerator heat insulation polyurethane foam composition, which has obviously improved flame retardant property and can be matched with other flame retardants to be used as a raw material for preparing the refrigerator heat insulation polyurethane foam composition.

In order to achieve the first object of the present invention, the following technical solutions are provided:

the polyester polyol for the refrigerator heat-insulation polyurethane foam composite material comprises the following raw material components: the polyol system comprises 1-30% of at least one monosaccharide or disaccharide and 70-99% of at least one dibasic/polybasic alcohol.

In the polyester polyol for the refrigerator heat insulation polyurethane foam composition, the polyol system at least contains 1-20% of monosaccharide or disaccharide and 80-99% of binary/polyol.

In the polyester polyol for the refrigerator heat insulation polyurethane foam composition, the molar ratio of the dibasic acid/polybasic acid to the polyol system is 1 (1.0-1.5).

In the polyester polyol for the refrigerator heat insulation polyurethane foam composition, the monosaccharide is one or a mixture of glucose, fructose and arabinose.

In the polyester polyol for the refrigerator heat insulation polyurethane foam composition, the disaccharide is one or a mixture of xylose, sucrose and maltose.

In the polyester polyol for the refrigerator insulation polyurethane foam composition, the dihydric/polyhydric alcohol includes, but is not limited to, one or more of ethylene glycol, propylene glycol, methyl propylene glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, 1, 3-butanediol, 1, 4-butanediol, pentanediol, neopentyl glycol, 1, 6-hexanediol, pentaerythritol, and the like.

In the polyester polyol for the refrigerator insulation polyurethane foam composition, the dibasic/polybasic acid is selected from aliphatic or aromatic dibasic/polybasic acids, including but not limited to one or more of succinic acid, glutaric acid, adipic acid, sebacic acid, butenedioic acid, maleic anhydride, phthalic acid, phthalate, halogenated phthalic acid, halogenated phthalate, phthalic anhydride, and the like.

The second purpose of the invention is to provide a preparation method of the polyester polyol for the refrigerator heat insulation polyurethane foam composition, which is simple and suitable for industrial production.

In order to achieve the second object of the present invention, the following technical solutions are provided:

a preparation method of polyester polyol for refrigerator heat insulation polyurethane foam composition comprises the following steps:

(1) charging a polyol system and dibasic/polybasic acid into a reactor according to the formula amount, heating and melting under the protection of nitrogen, and stirring for reaction;

(2) dehydrating when the temperature rises to 120-150 ℃, and continuously heating to 200-250 ℃ for reaction for 12-48 hours;

(3) and when the acid value is less than 0.4, cooling to finish the reaction, cooling, filtering and packaging to obtain the polyester polyol.

Compared with the prior art, the invention has the beneficial effects that:

1. according to the polyester polyol raw material for the refrigerator heat-insulation polyurethane foam composition, monosaccharide or disaccharide is partially added, the monosaccharide is the minimum hydrolysis unit of saccharide, and the disaccharide is formed by combining two monosaccharides. Monosaccharides and disaccharides are polyhydroxy compounds, which are not as flammable as other polyols, which can oxidize or burn, but generally do not burn easily. The invention takes monosaccharide or disaccharide as a part of the polyalcohol to be added into a polyalcohol system to react with the dibasic/polybasic acid to prepare the polyester polyol, thereby obviously reducing the inflammability. The flame retardant is matched with other flame retardants to be used as a raw material for preparing the refrigerator heat-insulation polyurethane foam composite material, so that the flame retardant property of the composite material is obviously improved.

2. The preparation method of the polyester polyol for the refrigerator heat insulation polyurethane foam composite material is simple, the polyester polyol is suitable for industrial production, and the obtained polyester polyol has all the properties of other polyurethane and also has remarkable flame retardant property.

Detailed Description

The technical solution of the present invention will be described in further detail with reference to the following embodiments, but the present invention is not limited thereto.