阅读说明：本技术 含金刚烷结构的聚酯多元醇树脂及制备方法 (Polyester polyol resin containing adamantane structure and preparation method thereof ) 是由 宋学礼 马晓阳 田华 韩文礼 于 2019-11-08 设计创作，主要内容包括：本发明公开了一种含金刚烷结构的聚酯多元醇树脂,其制备原料包括以下组分含量：含金刚烷结构的一元酸5-30份,二元酸或酸酐10-30份,二元醇10-30份,多元醇10-30份,催化剂0.05-0.1份,稀释剂10-30份。含金刚烷结构的聚酯多元醇的玻璃化转变温度有了显著的提高,所制备的聚氨酯涂料的表干时间、实干时间及可抛光时间显著缩短,硬度则显著提高。(The invention discloses a polyester polyol resin containing a adamantane structure, which comprises the following raw materials in percentage by weight: 5-30 parts of monoacid containing an adamantane structure, 10-30 parts of dibasic acid or anhydride, 10-30 parts of dihydric alcohol, 10-30 parts of polyhydric alcohol, 0.05-0.1 part of catalyst and 10-30 parts of diluent. The glass transition temperature of polyester polyol containing an adamantane structure is obviously improved, the surface drying time, the actual drying time and the polishing time of the prepared polyurethane coating are obviously shortened, and the hardness is obviously improved.)

1. A polyester polyol resin containing a adamantane structure is prepared from the following raw materials in parts by weight: 5-30 parts of monoacid containing an adamantane structure, 10-30 parts of dibasic acid or anhydride, 10-30 parts of dihydric alcohol, 10-30 parts of polyhydric alcohol, 0.05-0.1 part of catalyst and 10-30 parts of diluent.

2. The adamantane structure-containing polyester polyol resin of claim 1, prepared from raw materials comprising the following contents: 10-20 parts of monoacid containing an adamantane structure, 15-20 parts of dibasic acid or anhydride, 20-25 parts of dihydric alcohol, 15-20 parts of polyhydric alcohol, 0.06-0.08 part of catalyst and 20-25 parts of diluent.

3. The adamantane structure containing polyester polyol resin of claim 1 or 2, wherein the monoacid containing a adamantane structure is 1-adamantanecarboxylic acid or 1-adamantaneacetic acid.

4. The adamantane structure containing polyester polyol resin of claim 1 or 2, wherein the dibasic acid or anhydride is one or more of phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, adipic acid, glutaric acid, and succinic acid.

5. The adamantane structure containing polyester polyol resin of claim 1 or 2, wherein the diol is one or more of neopentyl glycol, ethylene glycol, diethylene glycol, methylpropanediol, 1, 4-butanediol, and 1, 6-hexanediol.

6. The adamantane structure containing polyester polyol resin of claim 1 or 2, wherein the polyol is one or more of glycerol, trimethylolpropane, pentaerythritol, and dipentaerythritol.

7. The adamantane structure containing polyester polyol resin of claim 1 or 2, where in the catalyst is dibutyl tin dilaurate, dibutyl tin oxide, or a mixture of the two.

8. The adamantane structure containing polyester polyol resin of claim 1 or 2, wherein the diluent is one or more of toluene, xylene, butyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, methyl isobutyl ketone, and methyl isoamyl ketone.

9. A method for preparing polyester polyol resin containing adamantane structure as claimed in claim 1, characterized in that, the monoacid, diacid or anhydride, diol, polyol, catalyst and other materials containing adamantane structure are put into a reaction kettle, dehydrated and condensed at high temperature of 160-230 ℃, and cooled to 150 ℃ after the acid value is reduced to below 15mgKOH/g, and then added with diluent for dilution to obtain the product.

Technical Field

The invention relates to a polyester polyol resin, in particular to a polyester polyol resin containing a adamantane structure and a preparation method thereof.

Background

The polyester polyol resin is a common polyhydroxy compound, and is widely applied in the fields of two-component polyurethane coatings, polyurethane elastomers, polyurethane foamed plastics, polyurethane pouring sealants and the like. The two-component polyurethane coating has wide application in the fields of automobile repair, engineering machinery, buses, rail transit and the like. The coating generally adopts acrylic polyol resin and polyester polyol as main film forming substances, and is matched with a polyisocyanate curing agent to form a crosslinking system. Wherein, the acrylic resin polyol has the characteristics of high drying speed, high hardness and the like, but the fullness and the distinctness of image are poor; the polyester polyol resin shows more excellent gloss and fullness, but has low glass transition temperature and slow drying speed. This also limits the use of polyester polyol resins. In the field of high-end and environment-friendly high-solid low-viscosity polyurethane coatings, the advantages and the disadvantages of polyester polyol resin are obvious. The polyester polyol resin can obtain a compound with a hyperbranched structure and high solid content and low viscosity through the design of gel points, and the characteristic is suitable for preparing high solid content, low viscosity and high performance coating with lower VOC content and more environmental protection, which is an incomparable advantage of other materials, but the disadvantages of low glass transition temperature and low drying speed greatly limit the use of the coating, and the popularization and the use of the high solid content and low viscosity coating with more environmental protection are also caused to encounter great difficulty. How to improve the hardness and drying speed of polyester polyol resin has been a problem of high performance polyurethane coating.

Disclosure of Invention

The invention aims to solve the technical problems that polyester polyol resin containing a adamantane structure and a preparation method thereof are provided, the defects of low hardness and low drying speed of the polyester polyol resin are overcome, the glass transition temperature of the polyester polyol is obviously improved after the adamantane structure is introduced, the surface drying time, the actual drying time and the polishing time of the prepared polyurethane coating are obviously shortened, and the hardness is obviously improved.

In order to solve the technical problems, the technical scheme adopted by the invention is that the raw materials for preparing the adamantane structure-containing polyester polyol resin comprise the following components in percentage by weight: 5-30 parts of monoacid containing an adamantane structure, 10-30 parts of dibasic acid or anhydride, 10-30 parts of dihydric alcohol, 10-30 parts of polyhydric alcohol, 0.05-0.1 part of catalyst and 10-30 parts of diluent.

Further, 10-20 parts of monoacid containing a adamantane structure, 15-20 parts of dibasic acid or anhydride, 20-25 parts of dihydric alcohol, 15-20 parts of polyol, 0.06-0.08 part of catalyst and 20-25 parts of diluent.

Further, the monoacid containing a adamantane structure is 1-adamantanecarboxylic acid or 1-adamantanacetic acid.

Further, the dibasic acid or anhydride is one or more of phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, adipic acid, glutaric acid and succinic acid.

Further, the dihydric alcohol is one or more of neopentyl glycol, ethylene glycol, diethylene glycol, methyl propylene glycol, 1, 4-butanediol and 1, 6-hexanediol.

Further, the polyalcohol is one or more of glycerol, trimethylolpropane, pentaerythritol and dipentaerythritol.

Further, the catalyst is dibutyl tin dilaurate, dibutyl tin oxide or a mixture of the two.

Further, the diluent is one or more of toluene, xylene, butyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, methyl isobutyl ketone and methyl isoamyl ketone.

The method for preparing the polyester polyol resin containing the adamantane structure comprises the following steps: the material containing the monoacid, the diacid or the anhydride with the adamantane structure, the dihydric alcohol, the polyalcohol, the catalyst and the like is put into a reaction kettle, and is subjected to dehydration condensation at the high temperature of 160-230 ℃ until the acid value is reduced to below 15mgKOH/g, and then the temperature is reduced to 150 ℃, and the material is added with a diluent and diluted to obtain the diamantane.

By adopting the technical scheme, the core technology of the invention is to introduce the monoacid containing the adamantane structure to prepare the polyester polyol resin, so that the glass transition temperature of the polyester polyol resin is obviously improved. Compared with conventional monobasic acid such as isooctanoic acid, isononanoic acid and the like, the 1-adamantane formic acid or 1-adamantane acetic acid has stronger rigidity due to the special adamantane ring structure, and the prepared polyester polyol has higher glass transition temperature, so that the hardness and the drying speed of the polyurethane coating are obviously improved. Due to the special cyclic structure of adamantane, the polyurethane coating prepared from the polyester polyol also shows more excellent fullness and distinctness of image, and is very suitable for preparing high-performance polyurethane coatings.

Detailed Description

The following examples are intended to illustrate the invention and should not be construed as limiting the invention in any way.

Comparative examples

12 parts of isooctanoic acid, 25 parts of hexahydrophthalic anhydride, 15 parts of neopentyl glycol, 23 parts of trimethylolpropane and 0.05 part of dibutyltin oxide are put into a polymerization reaction kettle, dehydrated and condensed at the temperature of 160-230 ℃, cooled and diluted by 25 parts of dimethylbenzene after the acid value is reduced to 15mgKOH/g, and the solid content of the obtained polyester polyol resin is 75 percent, and the viscosity is 5.5 Pa.s.