Modified polyurethane high-temperature-resistant rubber and preparation method thereof

文档序号：824153 发布日期：2021-03-30 浏览：34次中文

阅读说明：本技术 一种改性聚氨酯耐高温橡胶及其制备方法 (Modified polyurethane high-temperature-resistant rubber and preparation method thereof ) 是由付继伟王国辉张兵陈红波林三春潘旭高雅刘强于 2020-11-30 设计创作，主要内容包括：本发明涉及一种耐高温聚氨酯橡胶及其制备方法,属于聚氨酯橡胶制造领域,也属于有机合成和改性技术领域,也属于柔性热防护技术领域。通过改变扩链剂和配合剂,使得两者协同影响聚氨酯橡胶的耐热性能,使得聚氨酯橡胶的耐热性能显著提高,同时,保持聚氨酯橡胶的力学性能、耐老化性能和良好的导电性能。通常,聚氨酯橡胶的扩链剂为二元胺或二元醇等包含两个N-H键或O-H键的化合物,在本发明中,以小分子多元胺包含两个以上N-H键的化合物作为扩链剂,再添加羟基氧化铝即作为封端剂(链终止剂)也兼作配合剂使用。(The invention relates to high-temperature-resistant polyurethane rubber and a preparation method thereof, belonging to the field of polyurethane rubber manufacturing, the technical field of organic synthesis and modification and the technical field of flexible thermal protection. By changing the chain extender and the compounding agent, the chain extender and the compounding agent synergistically influence the heat resistance of the polyurethane rubber, so that the heat resistance of the polyurethane rubber is obviously improved, and meanwhile, the mechanical property, the aging resistance and the good conductivity of the polyurethane rubber are maintained. In general, the chain extender of the urethane rubber is a compound having two N-H bonds or O-H bonds, such as diamine or diol, and in the present invention, a compound having two or more N-H bonds in a small molecule polyamine is used as the chain extender, and a terminal blocking agent (chain terminator) which is obtained by adding aluminum oxyhydroxide is also used as the compounding agent.)

1. A modified polyurethane high temperature resistant rubber is characterized in that: the modified polyurethane high-temperature resistant rubber takes oligomer polyol and diisocyanate as main bodies of the polyurethane high-temperature resistant rubber, dibutyltin dilaurate as a catalyst, micromolecular polyamine 2,4, 6-triphenylcycloborazine hexaalkane as a chain extender, the molecular formula is shown as formula 1, and aluminum oxyhydroxide is taken as a capping reagent;

2. the modified polyurethane high temperature resistant rubber as claimed in claim 1, wherein: the mass portion of diisocyanate is 1 portion, the mass portion of oligomer polyol is 6 portions, the mass portion of 2,4, 6-triphenylboroazahexaalkane is 0.15-0.45 portion, the mass portion of hydroxy aluminum oxide is 0.1-2 portions, and the mass portion of dibutyltin dilaurate is 0.002 portion.

3. A preparation method of modified polyurethane high-temperature resistant rubber is characterized by comprising the following steps: and mixing oligomer polyol, diisocyanate, 2,4, 6-triphenylboroazahexaalkane, aluminum hydroxide and dibutyltin dilaurate, and reacting at 80 ℃ for 20 minutes to obtain the modified polyurethane high-temperature-resistant rubber.

4. The method for preparing the modified polyurethane high-temperature resistant rubber as claimed in claim 3, wherein the method comprises the following steps: the mass portion of diisocyanate is 1 portion, the mass portion of oligomer polyol is 6 portions, the mass portion of 2,4, 6-triphenylboroazahexaalkane is 0.15-0.45 portion, the mass portion of hydroxy aluminum oxide is 0.1-2 portions, and the mass portion of dibutyltin dilaurate is 0.002 portion.

Technical Field

The invention relates to high-temperature-resistant polyurethane rubber and a preparation method thereof, belonging to the field of polyurethane rubber manufacturing, the technical field of organic synthesis and modification and the technical field of flexible thermal protection.

Background

The polyurethane rubber is a series of elastomer materials containing more urethane groups on a polymer main chain, and is actually polyurethane rubber, which is simply referred to as polyurethane rubber or urethane rubber or polyurethane elastomer. The main body of the polyurethane rubber is composed of oligomer polyol and organic polyisocyanate, diamine or diol, micromolecule polyamine or polyol and the like contain two or more N-H bonds or O-H bonds as chain extenders, and catalysts such as dibutyltin dilaurate are vulcanized into polyurethane rubber products through reaction. The main advantages of the polyurethane rubber product are as follows: has the advantages of good mechanical property (high hardness, tearing property and tensile strength) and good aging resistance (ozone resistance and air aging resistance) which cannot be compared with common rubber. Although the polyurethane rubber has many advantages, the polyurethane rubber has the defect of poor temperature resistance, the use temperature range is about-30 ℃ to 80 ℃, compared with other rubbers, the heat resistance range of natural rubber is about 100 ℃ to 125 ℃, the temperature of styrene butadiene rubber is about 140 ℃, the temperature of chloroprene rubber is about 160 ℃, the temperature of nitrile butadiene rubber is about 175 ℃, the temperature of polyacrylate rubber is about 200 ℃, the temperature of silicon rubber and fluorine rubber is about 200 ℃ to 300 ℃, and the heat resistance range of polyurethane rubber is only about 80 ℃, so that the application range of the polyurethane rubber in a relatively high-temperature environment is obviously limited. Besides the proper selection of rubber, the compounding agent must be used reasonably, and the commonly used heat-resisting and heat-transferring compounding agents include asbestos powder, mica powder, graphite powder, carbon black, pottery clay, zinc oxide and magnesium carbonate, and under special condition, aluminium powder or lead powder can also be used. It has been empirically demonstrated that these compounding agents only slightly improve the heat resistance range of the polyurethane rubber. This is mainly because the urethane rubber main body, the chain extender and the catalyst are already shaped, and the effect of improving the heat resistance of the urethane rubber product only by adding the compounding agent is limited.

Disclosure of Invention

The invention aims to remarkably improve the high-temperature resistance of the polyurethane rubber by changing the chain extender and the compounding agent of the traditional polyurethane rubber. In the invention, the chain extender and the compounding agent are changed to cooperatively influence the heat resistance of the polyurethane rubber, so that the heat resistance of the polyurethane rubber is obviously improved, and the mechanical property, the aging resistance and the good conductivity of the polyurethane rubber are maintained. In general, the chain extender of the urethane rubber is a compound having two N-H bonds or O-H bonds, such as diamine or diol, and in the present invention, a compound having two or more N-H bonds in a small molecule polyamine is used as the chain extender, and a terminal blocking agent (chain terminator) which is obtained by adding aluminum oxyhydroxide is also used as the compounding agent.

The technical solution of the invention is as follows:

a modified polyurethane high-temperature resistant rubber takes oligomer polyol and diisocyanate as main bodies of the polyurethane high-temperature resistant rubber, dibutyltin dilaurate as a catalyst, micromolecular polyamine 2,4, 6-triphenylborazine hexaalkane (shown as a molecular formula 1) as a chain extender, and aluminum oxyhydroxide as a capping reagent (a chain terminator);

formula 1: 2,4, 6-triphenylboron nitrogen hexaalkane

In the present invention, all the ratios are mass ratios.

A preparation method of modified polyurethane high-temperature resistant rubber comprises the following steps:

firstly, preparing general polyurethane rubber;

secondly, 2,4, 6-triphenylboron nitrogen hexaalkane with different proportions is used as a chain extender to replace diamine, and hydroxy alumina with different proportions is added as a compounding agent to prepare modified polyurethane rubber;

and thirdly, testing the temperature resistance, the mechanical property and the ageing resistance of the samples in the first two steps, and comparing and analyzing the effectiveness of the invention.

The specific process steps of the invention are as follows:

firstly, preparing polyurethane rubber: taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of polyurethane rubber, taking diamine as a chain extender 0.1 part and dibutyltin dilaurate 0.002 part as a catalyst, uniformly mixing the four materials, and reacting at 80 ℃ for 20 minutes to prepare a polyurethane rubber sheet for comparison test;

secondly, taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of the polyurethane rubber, adding 2,4, 6-triphenylborazine hexaalkane in different proportions (0.15-0.45 parts) to replace diamine to serve as a chain extender, adding aluminum oxyhydroxide in different proportions (0.1-2 parts) to serve as a compounding agent, taking 0.002 part of dibutyltin dilaurate as a catalyst, uniformly mixing the five materials, and reacting at 80 ℃ for 20 minutes to prepare a polyurethane rubber sheet for comparison test;

thirdly, testing the temperature resistance, the mechanical property and the ageing resistance of the samples in the first two steps, and comparing and analyzing the effectiveness of the invention: the temperature resistance is determined by taking the highest temperature when the tensile strength begins to reduce as the upper temperature use limit, the hardness test adopts GB/T6031-1998 vulcanized rubber or thermoplastic rubber hardness, the tearing performance test adopts GB/T529-1999 vulcanized rubber or thermoplastic rubber tearing strength, GB/T528-1998 vulcanized rubber or thermoplastic rubber tensile stress strain performance, and the ozone aging resistance and air aging resistance adopt GB/T7762-2003 vulcanized rubber or thermoplastic rubber ozone crack resistance static tensile test and GB/T3512-2001 vulcanized rubber or thermoplastic rubber hot air accelerated aging and heat resistance test respectively. In the current invention, the test analysis is for comparison, so the rubber synthesized in the first step has a property of 1, and both the increase and decrease are relative percentages.

Detailed Description

The invention is further illustrated by the following examples, without restricting its application to the examples given.

Examples

The preparation method of the modified polyurethane high-temperature resistant rubber comprises the following steps:

first, preparing a conventional polyurethane rubber: taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of polyurethane rubber, taking diamine as a chain extender 0.1 part and dibutyltin dilaurate 0.002 part as a catalyst, uniformly mixing the four materials, and reacting at 80 ℃ for 20 minutes to prepare a polyurethane rubber sheet for comparison test;

secondly, taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of the polyurethane rubber, adding 2,4, 6-triphenylborazine hexaalkane in different proportions (0.15 part) to replace diamine to serve as a chain extender, adding aluminium oxyhydroxide in different proportions (0.1 part) to serve as a compounding agent, taking 0.002 part of dibutyltin dilaurate as a catalyst, uniformly mixing the five materials, and reacting at 80 ℃ for 20 minutes to obtain a polyurethane rubber sheet for comparison test;

Example 1

First, preparing a conventional polyurethane rubber: taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of polyurethane rubber, taking diamine as a chain extender 0.1 part and dibutyltin dilaurate 0.002 part as a catalyst, uniformly mixing the four materials, and reacting at 80 ℃ for 20 minutes to prepare a polyurethane rubber sheet for comparison test;

secondly, taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of the polyurethane rubber, adding 2,4, 6-triphenylborazine hexaalkane in different proportions (0.15 part) to replace diamine to serve as a chain extender, adding aluminium oxyhydroxide in different proportions (0.1 part) to serve as a compounding agent, taking 0.002 part of dibutyltin dilaurate as a catalyst, uniformly mixing the five materials, and reacting at 80 ℃ for 20 minutes to obtain a polyurethane rubber sheet for comparison test;

Example 2

secondly, taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of the polyurethane rubber, adding 2,4, 6-triphenylborazine hexaalkane in different proportions (0.45 part) to replace diamine to serve as a chain extender, adding hydroxy aluminum oxide in different proportions (2 parts) to serve as a compounding agent, taking 0.002 part of dibutyltin dilaurate as a catalyst, uniformly mixing the five materials, and reacting at 80 ℃ for 20 minutes to obtain a polyurethane rubber sheet for comparison test;

Example 3

secondly, taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of the polyurethane rubber, adding 2,4, 6-triphenylborazine hexaalkane in different proportions (0.25 part) to replace diamine to serve as a chain extender, adding aluminium oxyhydroxide in different proportions (0.5 part) to serve as a compounding agent, taking 0.002 part of dibutyltin dilaurate as a catalyst, uniformly mixing the five materials, and reacting at 80 ℃ for 20 minutes to obtain a polyurethane rubber sheet for comparison test;

Example 4:

secondly, taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of the polyurethane rubber, adding 2,4, 6-triphenylborazine hexaalkane in different proportions (0.35 part) to replace diamine to serve as a chain extender, adding hydroxy aluminum oxide in different proportions (1 part) to serve as a compounding agent, taking 0.002 part of dibutyltin dilaurate as a catalyst, uniformly mixing the five materials, and reacting at 80 ℃ for 20 minutes to obtain a polyurethane rubber sheet for comparison test;

Example 5:

secondly, taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of the polyurethane rubber, adding 2,4, 6-triphenylborazine hexaalkane in different proportions (0.40 part) to replace diamine to serve as a chain extender, adding aluminium oxyhydroxide in different proportions (1.5 parts) to serve as a compounding agent, taking 0.002 part of dibutyltin dilaurate as a catalyst, uniformly mixing the five materials, and reacting at 80 ℃ for 20 minutes to obtain a polyurethane rubber sheet for comparison test;

Example 6:

secondly, taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of the polyurethane rubber, adding 2,4, 6-triphenylborazine hexaalkane in different proportions (0.30 part) to replace diamine to serve as a chain extender, adding aluminium oxyhydroxide in different proportions (1.8 parts) to serve as a compounding agent, taking 0.002 part of dibutyltin dilaurate as a catalyst, uniformly mixing the five materials, and reacting at 80 ℃ for 20 minutes to obtain a polyurethane rubber sheet for comparison test;

Example 7:

modified rubber without adding a compounding ingredient, namely, only 2,4, 6-triphenylborazine hexaalkane with different proportions (0.15-0.45 parts) is used for replacing diamine as a chain extender, and the properties of the prepared polyurethane rubber are as follows:

secondly, taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of the polyurethane rubber, adding 2,4, 6-triphenylborazine hexaalkane in different proportions (0.15 part) to replace diamine as a chain extender, taking 0.002 part of dibutyltin dilaurate as a catalyst, uniformly mixing the five materials, and reacting at 80 ℃ for 20 minutes to obtain a polyurethane rubber sheet for comparison test;

Example 8:

secondly, taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of the polyurethane rubber, adding 2,4, 6-triphenylborazine hexaalkane in different proportions (0.30 part) to replace diamine as a chain extender, taking 0.002 part of dibutyltin dilaurate as a catalyst, uniformly mixing the five materials, and reacting at 80 ℃ for 20 minutes to obtain a polyurethane rubber sheet for comparison test;

Example 9:

secondly, taking 6 parts of oligomer polyol and 1 part of diisocyanate as main bodies of the polyurethane rubber, adding 2,4, 6-triphenylborazine hexaalkane in different proportions (0.45 part) to replace diamine as a chain extender, taking 0.002 part of dibutyltin dilaurate as a catalyst, uniformly mixing the five materials, and reacting at 80 ℃ for 20 minutes to obtain a polyurethane rubber sheet for comparison test;

Summary of the invention

As demonstrated by the first 9 examples: the hardness is improved by 0-24%, the tensile strength and the tear strength are respectively improved by 55-81% and 62-87%, the maximum use temperature is improved by 60-84 ℃, and the performances do not show linear changes along with the increase of single content, which shows that the macroscopic performances are influenced by the chain extender and the compounding agent together. In addition, 0.15-0.45 part of chain extender is independently tested, and the influence of the accessory ingredient on the performance of the polyurethane rubber is avoided, and the three examples of 7, 8 and 9 show that: the change of the chain extender causes the hardness change to be very small, the tensile strength and the tearing strength are respectively improved by about 36 percent and 47 percent, the maximum use temperature is improved by about 47 ℃, and the influence of the concentration of the chain extender on the performance is little.

In summary, the following steps: the novel chain extender can obviously improve the comprehensive performance of the polyurethane rubber, and the addition of a proper compounding agent can synergistically influence the comprehensive performance of the polyurethane rubber. In addition, the formula of the invention is simple and easy to operate, and is convenient for practical industrial production and application.

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Modified polyurethane high-temperature-resistant rubber and preparation method thereof

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