阅读说明：本技术 一种新型开孔发泡材料及其制备方法 (Novel open-cell foam material and preparation method thereof ) 是由 陈旭东 吴浪 甄智勇 于 2019-09-28 设计创作，主要内容包括：一种新型开孔发泡材料及其制备方法,包括如下重量份数的原料组分：双环戊二烯100重量份、防老化剂0.1～3重量份、紫外吸收剂剂0.1～3份、增粘剂0.2～5重量份、与双环戊二烯的摩尔比为1/100000～1/500的grubbs催化剂。制备步骤：将防老化剂室温溶解于双环戊二烯单体中；将紫外吸收剂室温溶于第一步的双环戊二烯单体中；将增粘剂室温溶解于第二步的双环戊二烯单体中；将一定比例的催化剂溶液加入双环戊二烯单体中；将所得混合液倒入模具,抽取一段时间真空保温成型后冷却、脱模即可得到开孔发泡材料。本发明所得泡沫材料具有强度高、密度低、隔热、隔音的性质；生产工艺简单,过程环保,操作方便。(The novel open-cell foam material comprises the following raw material components in parts by weight: 100 parts of dicyclopentadiene, 0.1-3 parts of anti-aging agent, 0.1-3 parts of ultraviolet absorbent, 0.2-5 parts of tackifier and grubbs catalyst with the molar ratio of the dicyclopentadiene to the dicyclopentadiene of 1/100000-1/500. The preparation method comprises the following steps: dissolving the anti-aging agent in the dicyclopentadiene monomer at room temperature; dissolving an ultraviolet absorbent in the dicyclopentadiene monomer in the first step at room temperature; dissolving tackifier in the dicyclopentadiene monomer at room temperature; adding a certain proportion of catalyst solution into dicyclopentadiene monomer; pouring the obtained mixed solution into a mould, pumping for a period of time, carrying out vacuum heat preservation molding, cooling, and demoulding to obtain the open-cell foam material. The foam material obtained by the invention has the properties of high strength, low density, heat insulation and sound insulation; the production process is simple, the process is environment-friendly, and the operation is convenient.)

1. The novel open-cell foam material is characterized by comprising the following raw material components in parts by weight: 100 parts of dicyclopentadiene, 0.1-3 parts of anti-aging agent, 0.1-3 parts of ultraviolet absorbent, 0.2-5 parts of tackifier and grubbs catalyst with the molar ratio of the dicyclopentadiene to the dicyclopentadiene of 1/100000-1/500.

2. The open-cell foam material as claimed in claim 1, wherein the aging inhibitor is one or more of bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide, 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl-p-cresol, tris (2, 4-di-tert-butylphenyl) phosphite, and pentaerythritol tetrakis (β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).

3. The novel open-cell foam material as claimed in claim 1, wherein the ultraviolet absorber is one or more of UV-326, UV-1164, UV-531, UV-327, UV-360, UV-1157 and UV-234.

4. The novel open-cell foam material as claimed in claim 1, wherein the tackifier is any one or more of styrene-butadiene rubber, ethylene-propylene-diene monomer rubber, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, styrene-butadiene block copolymer and chloroprene rubber.

5. The novel open-cell foam material of claim 1, wherein said grubbs catalyst is any one or combination of first generation and second generation grubbs catalysts.

6. A method for preparing a novel open-cell foamed material according to any one of claims 1 to 5, comprising the steps of:

the first step is as follows: dissolving the anti-aging agent in the dicyclopentadiene monomer at room temperature, and stirring for 3-5 min;

the second step is that: dissolving an ultraviolet absorbent in the dicyclopentadiene monomer in the first step at room temperature, and stirring for 3-5 min;

the third step: dissolving a tackifier in the dicyclopentadiene monomer obtained in the second step at room temperature, and stirring for 5-10 min;

the fourth step: adding a certain proportion of catalyst solution into the dicyclopentadiene monomer in the third step, and uniformly stirring for 2-3 min;

the fifth step: pouring the mixed liquid obtained in the fourth step into a mould, pumping for a period of time, carrying out vacuum heat preservation molding for 10min, cooling, and demoulding to obtain the open-cell foam material.

7. The method as claimed in claim 6, wherein the catalyst solution in the fourth step is prepared by mixing grubbs catalyst and catalyst solution solvent.

8. The method for preparing the novel open-cell foam material as claimed in claim 7, wherein the catalyst solution solvent is any one combination of dichloromethane and toluene.

9. The method for preparing the novel open-cell foam material according to claim 6, wherein the temperature of the mold in the fifth step is 35-100 ℃, and the holding time is 3-20 min.

Technical Field

The invention relates to a foamed plastic, in particular to a novel open-cell foamed material and a preparation method thereof.

Background

Currently, the concept of material weight reduction is receiving more and more attention. In the case of polymeric materials, it is common to introduce a cellular structure within the material to replace the originally solid polymeric portion with gas bubbles in order to reduce the density of the material. The polymer foam material is a microporous material based on a polymer (plastic, rubber, elastomer, or natural polymer material) and having numerous bubbles inside, and can be considered as a composite material using a gas as a filler. The polymer foaming material with the holes has wide application in the fields of biology, medical treatment, environmental engineering and the like, and can be used for tissue engineering, solvent extraction, heat preservation and insulation, sound absorption, water stopping and retention, oil absorption, controlled drug release and the like.

The foaming technology of supercritical fluid (N2, CO2, etc.) has the advantages of green, no pollution, etc., and thus has been increasingly regarded as important in preparing porous tissue engineering scaffold materials. Taking supercritical carbon dioxide foaming as an example: the supercritical CO2 is firstly diffused and dissolved into the polymer matrix, and the acceleration effect of the supercritical CO2 can reduce the glass transition temperature of the polymer and make the glass transition temperature lower than the test temperature; then, due to the fact that the system is decompressed or heated, thermodynamic instability of the system is caused, and a large number of gas nuclei are formed and grow in the polymer matrix; in the process of cell growth, a large amount of gas diffuses into cells or escapes out of a polymer foaming system, so that the driving force for cell growth is continuously reduced, and simultaneously, the rigidity of a polymer matrix is gradually improved, and the two effects can inhibit cell growth, so that the cell structure is finally fixed. However, in the conventional supercritical fluid foaming process, because a large temperature gradient exists between the surface layer and the inside of the center of the polymer material, that is, the surface layer temperature is low, and the temperature inside the material is high, CO2 gas cannot be dissolved (or less dissolved) into the surface layer of the material, so that a compact and hard skin layer is formed on the surface, and the internal porous structure is wrapped, so that the surface of the polymer foaming material is difficult to open pores or has low opening rate, which severely restricts the application range of the foaming technology, and therefore, an improved scheme is urgently needed to overcome the defect.

Polydicyclopentadiene (PDCPD) material prepared by Ring-opening metathesis polymerization (ROMP) of dicyclopentadiene monomer (DCPD) under the action of catalyst is gradually developed into novel engineering plastic due to excellent mechanical property and low cost. The DCPD has two unsaturated rings, wherein a norbornene ring is opened to form a linear PDCPD chain, and a part of cyclopentene ring is opened to form a cross-linked network structure, so that the DCPD has high modulus and high impact strength. Industrially, thermosetting crosslinked PDCPD-RIM articles are mainly prepared by Reaction Injection Molding (RIM). In order to obtain a light PDCPD-based porous material, a number of researchers have conducted related studies. The PDCPD-based porous material inherits the characteristics of the PDCPD material, generally has higher mechanical strength, and has wider application prospect and market competitiveness. The preparation methods of PDCPD-based porous materials can be mainly summarized into the following types of sol-gel combined supercritical drying method, high internal phase emulsion method, chemical induced phase separation method and chemical foaming method. The method improves the foaming multiplying power of the PDCPD and enlarges the application range of the PDCPD; however, these methods have various disadvantages, mainly including the following aspects:

1) the preparation process is complex and the price is high;

2) a large amount of solvent is needed to pollute the environment;

3) a tungsten catalyst is mostly adopted, and the requirement on test conditions is severe;

4) the prepared porous material has obvious performance reduction and cannot highlight the high-strength characteristic of the PDCPD material;

5) the prepared porous material has peculiar smell.

The prior patent applications CN 104327436A and CN 107722243A both disclose a preparation method of polydicyclopentadiene foam material, which can reduce the density of the material on the basis of ensuring the high strength of the raw material; chemical foaming agents are used, the dissolubility of the foaming agents is relatively poor, and the foaming multiplying power is not easy to adjust.

Disclosure of Invention

The invention aims to provide a novel open-cell foam material and a preparation method thereof, the open-cell foam material is prepared by a PDCPD material self-foaming process, and the obtained foam material has the properties of high strength, low density, heat insulation and sound insulation; the production process is simple, the process is environment-friendly, the operation is convenient, and the method is suitable for large-scale industrial production and solves the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: a novel open-cell foam material comprises the following raw material components in parts by weight: 100 parts of dicyclopentadiene, 0.1-3 parts of anti-aging agent, 0.1-3 parts of ultraviolet absorbent, 0.2-5 parts of tackifier and grubbs catalyst with the molar ratio of the dicyclopentadiene to the dicyclopentadiene of 1/100000-1/500.

Further, the anti-aging agent is one or a compound of more of bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide, 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl-p-cresol, tris (2, 4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).

Further, the ultraviolet absorbent is one or a compound of more of UV-326, UV-1164, UV-531, UV-327, UV-360, UV-1157 and UV-234.

Further, the tackifier is any one or combination of more of styrene butadiene rubber, ethylene propylene diene monomer, ethylene propylene copolymer, ethylene vinyl acetate copolymer, styrene-butadiene block copolymer and chloroprene rubber.

Further, the grubbs catalyst is any one or combination of a first-generation grubbs catalyst and a second-generation grubbs catalyst.

The invention provides another technical scheme as follows: a preparation method of a novel open-cell foam material comprises the following steps:

the first step is as follows: dissolving the anti-aging agent in the dicyclopentadiene monomer at room temperature, and stirring for 3-5 min;

the second step is that: dissolving an ultraviolet absorbent in the dicyclopentadiene monomer in the first step at room temperature, and stirring for 3-5 min;

the third step: dissolving a tackifier in the dicyclopentadiene monomer obtained in the second step at room temperature, and stirring for 5-10 min;

the fourth step: adding a certain proportion of catalyst solution into the dicyclopentadiene monomer in the third step, and uniformly stirring for 2-3 min;

the fifth step: pouring the mixed liquid obtained in the fourth step into a mould, pumping for a period of time, carrying out vacuum heat preservation molding for 10min, cooling, and demoulding to obtain the open-cell foam material.

And the catalyst solution in the fourth step is prepared by proportioning a grubbs catalyst and a catalyst solution solvent.

Further, the catalyst solution solvent is any one combination of dichloromethane and toluene.

And further, the temperature of the die in the fifth step is 35-100 ℃, and the heat preservation time is 3-20 min.

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

in the invention, a certain amount of anti-aging agent, ultraviolet absorbent and tackifier are dissolved in 1000mL of dicyclopentadiene monomer, and the mixture is uniformly stirred; adding a catalyst solution (dissolved in a dichloromethane or toluene solution) in a certain proportion into the monomer, and dispersing uniformly; pouring the mixture into a constant-temperature mold at a certain temperature, vacuumizing, reacting for a period of time, preserving heat in the mold for 10min, and then cooling and demolding to obtain the open-cell foamed PDCPD material, wherein the obtained PDCPD open-cell foamed material has the properties of high strength, low density, heat insulation and sound insulation; the production process is simple, the process is environment-friendly, the operation is convenient, and the method is suitable for large-scale industrial production.

Detailed Description

The following examples will explain the present invention in detail, but the present invention is not limited thereto. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.