阅读说明：本技术 一种低成本高硬度聚氨酯硬挺剂浆料及其制备方法和应用 (Low-cost high-hardness polyurethane stiffening agent slurry and preparation method and application thereof ) 是由 李军 马骥 于 2020-07-15 设计创作，主要内容包括：本发明公开了一种低成本高硬度聚氨酯硬挺剂浆料及其制备方法和应用,涉及聚氨酯硬挺剂技术领域。包括如下质量份数的原料：特种聚酯多元醇树脂10～26；低聚物多元醇20～32；小分子多元醇0～5；多异氰酸酯10～16；催化剂0.01～0.02；溶剂150～300；其中,所述特种聚酯多元醇树脂为对苯二甲酸与乙二醇经酯化反应制得。解决现有聚氨酯硬挺剂浆料成本较高的情况,实现使用特种聚酯多元醇树脂使在不增加多异氰酸酯用量的情况下,提高聚氨酯硬挺剂浆料的硬度的效果。(The invention discloses low-cost high-hardness polyurethane stiffening agent slurry and a preparation method and application thereof, and relates to the technical field of polyurethane stiffening agents. The composite material comprises the following raw materials in parts by weight: 10-26 parts of special polyester polyol resin; 20-32 parts of oligomer polyol; 0-5 parts of small molecular polyol; 10-16 parts of polyisocyanate; 0.01-0.02 of a catalyst; 150-300 parts of a solvent; wherein the special polyester polyol resin is prepared by esterification reaction of terephthalic acid and ethylene glycol. The method solves the problem of higher cost of the existing polyurethane stiffening agent slurry, and realizes the effect of improving the hardness of the polyurethane stiffening agent slurry by using special polyester polyol resin without increasing the using amount of polyisocyanate.)

1. The low-cost high-hardness polyurethane stiffening agent slurry is characterized by comprising the following raw materials in parts by mass:

10-26 parts of special polyester polyol resin;

20-32 parts of oligomer polyol;

0-5 parts of small-molecule polyol;

10-16 parts of polyisocyanate;

0.01-0.02 of a catalyst;

150-300 parts of a solvent;

wherein the special polyester polyol resin is prepared by esterification reaction of terephthalic acid and ethylene glycol.

2. The low-cost high-hardness polyurethane stiffener slurry disclosed in claim 1, wherein: the molecular weight of the special polyester polyol resin is 250-1000.

3. The low-cost high-hardness polyurethane stiffener slurry disclosed in claim 1, wherein: the oligomer polyol is selected from one or two of polyester polyol or polyether polyol.

4. The low-cost high-hardness polyurethane stiffener slurry disclosed in claim 3, wherein: the polyester polyol is selected from: polyethylene glycol adipate diol, 1, 4-butanediol adipate diol, polycarbonate diol or polycaprolactone diol; the polyether polyol is selected from polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol or polytetrahydrofuran-oxypropylene copolymerized diol.

5. The low-cost high-hardness polyurethane stiffener slurry disclosed in claim 1, wherein: the micromolecular polyhydric alcohol is selected from one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 6-hexanediol, neopentyl glycol and trimethylolpropane.

6. The low-cost high-hardness polyurethane stiffener slurry disclosed in claim 1, wherein: the polyisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexyl methane diisocyanate.

7. The low-cost high-hardness polyurethane stiffener slurry disclosed in claim 1, wherein: the solvent is selected from two or more of N, N-dimethylformamide, butanone, acetone, ethyl acetate, methyl acetate, butyl acetate, dimethyl carbonate, toluene and xylene.

8. A method for preparing the low-cost high-hardness polyurethane stiffener slurry according to any one of claims 1 to 7, characterized by being prepared by the steps of:

(1) firstly, adding a solvent in a reaction device according to the mass part ratio, then adding the special polyester polyol resin, the oligomer polyol and the micromolecule polyol, and adding the polyisocyanate under the stirring condition;

(2) preparing a prepolymer, heating to 60-80 ℃ for reaction for 2-3 hours, adding a catalyst for reaction, keeping the temperature at 60-80 ℃ for reaction for 1-2 hours, and obtaining a polyurethane prepolymer;

(3) adjusting solid content, adding a solvent to adjust the prepolymer to reach the expected solid content, simultaneously cooling to below 40 ℃ to obtain the low-cost high-hardness polyurethane stiffening agent slurry, and then packaging and discharging.

9. The application of the low-cost high-hardness polyurethane stiffening agent slurry is characterized in that: the two-component polyurethane adhesive is prepared by mixing the low-cost high-hardness polyurethane stiffening agent slurry as claimed in any one of claims 1 to 7 and a polyisocyanate curing agent blocked by-NCO.

Technical Field

The invention relates to low-cost high-hardness polyurethane stiffening agent slurry and a preparation method and application thereof, belonging to the technical field of polyurethane stiffening agents.

Background

The polyurethane is a polyurethane, which is a macromolecular compound formed by polycondensation of polyisocyanate and low molecular weight polymeric diol. The polyurethane includes two types of polyester type and polyether type, and they can be made into polyurethane plastics, polyurethane fibre, polyurethane rubber and elastomer. The soft polyurethane mainly has a thermoplastic linear structure, and has better stability, chemical resistance, rebound resilience and mechanical property and smaller compression deformability than a PVC foaming material. Good heat insulation, sound insulation, shock resistance and gas defense performance. Therefore, the product is used as a packaging, sound insulation and filtering material. The hard polyurethane plastic has the advantages of light weight, excellent sound insulation and heat insulation performance, chemical resistance, good electrical property, easy processing and low water absorption rate. It is mainly used as a heat-insulating structural material in the building, automobile and aviation industries. The polyurethane elastomer has the performance between that of plastic and rubber, and has the advantages of oil resistance, wear resistance, low temperature resistance, aging resistance, high hardness and elasticity. Is mainly used in the shoe making industry and the medical industry. The polyurethane can also be used for preparing adhesives, coatings, synthetic leather and the like.

Because the polyurethane has a phase separation structure with 2 soft and hard chain segments, the polyurethane can endow the material with excellent performances of high strength, good toughness, wear resistance, oil resistance and the like through the design of the chain segments. Polyurethane products in the market improve the hardness of the products by increasing the content of hard segments, wherein the hard segments consist of polyisocyanate and micromolecular polyol. Because the production cost of the polyisocyanate product is high, the product price of the high-hardness polyurethane stiffening agent slurry is high. The research on how to produce the polyurethane stiffening agent slurry with high hardness and high performance on the premise of not increasing the using amount of polyisocyanate and reducing the production cost is the research direction of the patent.

Disclosure of Invention

The invention aims to provide a preparation method of polyurethane stiffening agent slurry, which solves the problem that the existing polyurethane stiffening agent slurry has higher cost, and realizes the effect of improving the hardness of the polyurethane stiffening agent slurry by using special polyester polyol resin without increasing the using amount of polyisocyanate.

In order to achieve the effect, the invention discloses low-cost high-hardness polyurethane stiffening agent slurry which comprises the following raw materials in parts by weight:

10-26 parts of special polyester polyol resin;

20-32 parts of oligomer polyol;

0-5 parts of small-molecule polyol;

10-16 parts of polyisocyanate;

0.01-0.02 of a catalyst;

150-300 parts of a solvent;

wherein the special polyester polyol resin is prepared by esterification reaction of terephthalic acid and ethylene glycol.

Furthermore, the molecular weight of the special polyester polyol resin is 250-1000.

Further, the oligomer polyol is selected from one or two of polyester polyol and polyether polyol.

Further, the polyester polyol is selected from: polyethylene glycol adipate diol, 1, 4-butanediol adipate diol, polycarbonate diol or polycaprolactone diol; the polyether polyol is selected from polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol or polytetrahydrofuran-oxypropylene copolymerized diol.

Further, the small molecular polyol is selected from one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 6-hexanediol, neopentyl glycol and trimethylolpropane.

Further, the polyisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.

Further, the solvent is selected from two or more of N, N-dimethylformamide, butanone, acetone, ethyl acetate, methyl acetate, butyl acetate, dimethyl carbonate, toluene and xylene.

In addition, the invention also discloses a preparation method of the low-cost high-hardness polyurethane stiffening agent slurry, which is specifically prepared by the following steps:

(1) firstly, adding a solvent in a reaction device according to the mass part ratio, then adding the special polyester polyol resin, the oligomer polyol and the micromolecule polyol, and adding the polyisocyanate under the stirring condition;

(2) preparing a prepolymer, heating to 60-80 ℃ for reaction for 2-3 hours, adding a catalyst for reaction, keeping the temperature at 60-80 ℃ for reaction for 1-2 hours, and obtaining a polyurethane prepolymer;

(3) adjusting solid content, adding a solvent to adjust the prepolymer to reach the expected solid content, simultaneously cooling to below 40 ℃ to obtain the low-cost high-hardness polyurethane stiffening agent slurry, and then packaging and discharging.

Meanwhile, the invention also discloses application of the low-cost high-hardness polyurethane stiffening agent slurry, which is characterized in that: the two-component polyurethane adhesive is prepared by mixing the low-cost high-hardness polyurethane stiffening agent slurry as claimed in any one of claims 1 to 7 and a polyisocyanate curing agent blocked by-NCO.

Compared with the prior art, the invention has the advantages of lower consumption of polyisocyanate, high product hardness and good performance, the original structural forms of the soft segment and the hard segment of polyurethane are changed by using the special polyester polyol resin, and the special polyester serves as a part of the hard segment in the polyurethane molecular chain segment, thereby improving the integral hardness of the polyurethane stiffening agent slurry.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments.