阅读说明：本技术 一种聚甲基丙烯酰亚胺泡沫材料的制备方法 (Preparation method of polymethacrylimide foam material ) 是由 张竞 周一凡 张宏礼 张娇霞 汤继俊 于 2019-10-15 设计创作，主要内容包括：本发明公开了一种聚甲基丙烯酰亚胺泡沫材料的制备方法,首先采用Pickering乳液悬浮聚合法制备聚甲基丙烯酰亚胺热膨胀微球,微球以不饱和烯烃类单体及交联剂为外壳材料、以低沸点烷烃发泡剂为芯材,将所制得的热膨胀微球筛分得到用于生产聚甲基丙烯酰亚泡沫材料的热膨胀微球粉末,将所制得的热膨胀微球热压发泡成型,得到聚甲基丙烯酰亚胺泡沫塑料。本发明所制备的热膨胀微球颗粒经筛分可直接得到发泡原材料,省去了研磨步骤,在模具中成型可以一次性获得聚甲基丙烯酰亚泡沫塑料,具有广阔的市场应用前景。(The invention discloses a preparation method of polymethacrylimide foam material, which comprises the steps of firstly preparing polymethacrylimide thermal expansion microspheres by a Pickering emulsion suspension polymerization method, screening the prepared thermal expansion microspheres to obtain thermal expansion microsphere powder for producing polymethacrylimide foam material by using unsaturated olefin monomers and cross-linking agents as shell materials and using low-boiling-point alkane foaming agents as core materials, and carrying out hot-pressing foaming molding on the prepared thermal expansion microspheres to obtain polymethacrylimide foam plastic. The thermal expansion microsphere particles prepared by the invention can directly obtain foaming raw materials through screening, the grinding step is omitted, and the polymethacrylic subfoam can be obtained at one time by molding in a mold, so that the thermal expansion microsphere particles have wide market application prospect.)

1. A preparation method of a polymethacrylimide foam material is characterized by firstly preparing thermal expansion microspheres taking an unsaturated olefin monomer and a cross-linking agent as shell materials and taking a low-boiling-point alkane foaming agent as a core material, filtering and screening the dried thermal expansion microspheres through a 400-mesh screen, adding the filtered thermal expansion microspheres into a pressing mold preheated to 50 ℃, foaming by using a plastic hydraulic press, wherein the preferable foaming pressure of the mold is 0.5 ~ MPa, foaming in a step heating mode, heating to 140 ℃ at a heating rate of 1 ℃/min, keeping the temperature for 20 min, heating to a required foaming temperature at a heating rate of 0.5 ~ ℃/min according to the property of the microspheres, namely 200 ~ ℃, keeping the pressure for 10 ~ min according to different shapes of components, opening the mold, and carrying out thermal treatment on the taken-out components at 160 ℃ to obtain the required polymethacrylimide foam, wherein the used unsaturated olefin monomer comprises acrylonitrile, methacrylic acid, acrylamide monomer and acrylic ester monomer, wherein the acrylonitrile accounts for 3960 wt% 3885%, the methacrylic acid accounts for 10 wt%, 38730 wt%, the acrylamide monomer accounts for ~ wt%, and the acrylic ester monomer accounts for 10 wt% based on 100 wt%.

2. The method of claim 1, wherein the preparation of the thermally expandable microspheres comprises the following steps:

1) uniformly mixing unsaturated olefin monomers, a cross-linking agent, an alkane foaming agent and an oil-soluble initiator, and magnetically stirring for 5 ~ 10 min to obtain an oil phase;

2) homogenizing and emulsifying inorganic dispersant, emulsifier, inorganic salt, aqueous phase polymerization inhibitor and deionized water at 10000 rpm for 3 min to obtain aqueous phase;

3) slowly dripping the oil phase obtained in the step (1) into the water phase obtained in the step (2), and fully and uniformly mixing by mechanically stirring for 15 ~ 35 min to obtain an oil-in-water emulsion;

4) and (3) injecting the emulsion obtained in the step (3) into a high-pressure reaction kettle, heating to 55 ~ 70 ℃ under the nitrogen atmosphere, polymerizing at 0.4 ~ 0.6 MPa for 18 ~ 25 h, washing the obtained product with deionized water, filtering, and drying to obtain the thermal expansion microspheres.

3. The method of claim 1, wherein the acrylic ester comprises at least one of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and glycidyl methacrylate.

4. The method of claim 2, wherein the alkane blowing agent used in step 1 is ~ 40 wt% based on the amount of the unsaturated olefin monomer, and the alkane blowing agent is selected from alkanes having 4-4 ~ 8 carbon atoms and a boiling point higher than 20 ℃.

5. The method of claim 2, wherein the crosslinking agent used in step 1 is one or more selected from the group consisting of ethylene glycol dimethacrylate, trimethylolpropane triacrylate, 1, 6-hexanediol dimethacrylate, 1, 4-butanediol dimethacrylate, and 1, 4-butanediol vinyl diether, and the amount of the crosslinking agent is 0.01wt% to ~ 1wt% based on the amount of the unsaturated olefin monomer.

6. The method of claim 2, wherein the oil-soluble initiator used in step 1 is one or more selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide and lauroyl peroxide.

7. The process for preparing polymethacrylimide foams as claimed in claim 2, wherein the inorganic salts used in step 2 are selected from sodium chloride; the inorganic dispersant used in the step 2 is one or more of nano silicon dioxide, nano titanium dioxide, halloysite and lithium magnesium silicate; the emulsifier used in the step 2 is one or more of polyvinylpyrrolidone, polyvinyl alcohol and sodium dodecyl sulfate.

8. The method of claim 2, wherein the unsaturated olefin-based monomer used in the step 1 comprises 65 wt% ~ 80 wt% of acrylonitrile and the unsaturated olefin-based monomer used in the step 1 comprises 15wt% ~ 25 wt% of methacrylic acid.

9. The method of claim 4, wherein the alkane blowing agent is selected from the group consisting of isopentane, n-pentane, isohexane, n-hexane, and isoheptane.

10. The method of claim 5, wherein the crosslinking agent is used in an amount of 0.1 wt% ~ 0.5.5 wt% based on the amount of the unsaturated olefin monomer.

Technical Field

The invention relates to the field of polymer foam materials, in particular to a preparation method of a polymethacrylimide foam material.

Background

Polymethacrylimide (PMI) foam is a thermosetting rigid foam material, has a 100% closed cell structure, and the uniform cross-linked cell wall structure endows the foam with outstanding structural stability and excellent mechanical properties. The first generation of Polymethacrylimide (PMI) foams based on methacrylic acid (MAA) and Methacrylonitrile (MAN) as comonomers was first developed in 1966 by Rohm, Germany (now co-owned by the winning industry group) under the registered trademark ROHCELL^®The product is first successfully applied to an aircraft project to obtain a first aircraft material certificate. In recent years, with the continuous development of aerospace industry, the application of PMI foam plastics is continuously explored and researched at home and abroad.

At present, most PMI foamed plastics sold in the market are in a plate form, however, with the leap of mass production technology of carbon fibers, the market demand of PMI foamed plastics with high performance and complex shapes is continuously increased, and the single foamed plate can not meet the demand of high-performance three-dimensional components in the market.

The main factors for limiting the development of PMI foam products in China are ROHACELL foam which is expensive and has high direct purchasing cost; the main monomer Methacrylonitrile (MAN) for synthesizing PMI foam material cannot be industrially produced in China, and at present, the method mainly depends on import; the related technologies are well protected by patent layout abroad, and the technical barriers are difficult to surmount.

China researchers continuously try to explore, and provide a technical route for preparing PMI foam by replacing MAN with Acrylonitrile (AN) rich in China sources, so that technical monopoly of foreign companies is broken through from the source of AN industrial chain. Currently, a two-step method is generally adopted for preparing PMI foam by using MAA and AN as main monomers: firstly, preparing a MAA/AN copolymer foamable sheet; in the second step, the foamable copolymer sheet is foamed and cured. The MAA/AN copolymerization reaction has the remarkable characteristics that: 1. the copolymerization reaction belongs to free radical bulk polymerization, has the characteristics of slow initiation and fast growth, and is easy to release a large amount of heat instantly due to the fast growth of a C-C chain in the copolymerization process to cause sudden polymerization; if the materials are stirred, the heat transfer is accelerated, and the sudden aggregation can be effectively avoided; 2. the copolymerization reaction is a precipitation polymerization reaction, the copolymer is not dissolved in the monomer, the viscosity of the reaction system can not rise, the liquid mixture is gradually converted into a solid product formed by depositing and accumulating the copolymer, and if a foamable copolymer plate is directly obtained through the copolymerization reaction, the materials can not be stirred in the copolymerization reaction process. Thus, the main drawbacks of the two-step process are: 1. in order to prevent sudden polymerization, the copolymerization reaction can be carried out only below 60 ℃, the reaction time is more than 48 hours, and the production efficiency is low; 2. the foamable copolymer sheet formed by deposition and accumulation of the copolymer is not uniform, resulting in uneven foam sheet.

Aiming at the defects of a two-step method and the characteristics of MAA/AN copolymerization reaction, patent CN 103421206A proposes AN ultraviolet light initiation method to prepare PMI foam plastics, but the polymerization rate of ultraviolet light initiation is uncontrollable and is only suitable for small-batch copolymerization reaction; the patent CN 103232568B adopts a suspension polymerization method to prepare PMI powder, the polymerization rate of the suspension polymerization method is controllable, the product performance is uniform and stable, the copolymerization reaction time can be shortened to 4 h, and the method is suitable for large-scale copolymerization reaction.

MAA/AN copolymer particles obtained by a suspension polymerization method are hot-pressed into a foamable copolymer sheet after other auxiliary agents are added, and then foaming and curing are carried out. However, the thickness of the foamable copolymer sheet to which the MAA/AN copolymer particles are hot-pressed cannot be too thick, otherwise the copolymer sheet is not foamable. The MAA/AN copolymer can not enter a liquid state after being heated and can only enter a gel state, and when the plate is too thick, the pressure intensity can not be effectively transferred in the material, so that partial copolymer particles can not be contacted with each other to form gaps; and the adhesion between the copolymer particles is poor, and when the pressure is insufficient, even if the surfaces of the copolymer particles come into contact, a gap may be formed at the interface. During foaming, the gas generated by the foaming agent escapes from the gaps, resulting in failure of foaming. The related researchers believe that the polymer microspheres synthesized by the conventional suspension polymerization method often contain excessive surfactant, which makes the foaming of the thermally expandable microspheres difficult.

The German winning and creating industry group breaks the MAA/MAN copolymer foamable sheet and applies the sheet to the preparation of PMI foam materials with complex shapes, and the same problems are found in the preparation process. The current solution of the German winning and creating industry group is to coat a layer of adhesive on the surface of the particles, but the effect is not ideal.

Disclosure of Invention

The invention aims to solve the defects in the prior art, and the PMI thermal expansion microspheres are synthesized by a Pickering emulsion suspension polymerization method, so that the PMI thermal expansion microspheres expand after being heated, uniform internal pressure is formed in the material, the contact interfaces between the microspheres are promoted to be bonded and fused, and the PMI foam product with uniform properties is finally formed.

The technical scheme includes that the preparation method of the polymethacrylimide foam material comprises the steps of firstly preparing thermal expansion microspheres with unsaturated olefin monomers and cross-linking agents as shell materials and low-boiling-point alkane foaming agents as core materials, filtering and screening the dried thermal expansion microspheres through a 400-mesh screen, adding the filtered thermal expansion microspheres into a pressing mold preheated to 50 ℃, foaming by using a plastic hydraulic press, preferably, the foaming pressure of the mold is 0.5 ~ MPa, foaming in a step heating mode, heating to 140 ℃ at a heating rate of 1 ℃/min, keeping the temperature for 20 min, heating to a required foaming temperature at a heating rate of 0.5 ~ ℃/min according to the properties of the microspheres, namely 200 ~ ℃, keeping the pressure of the members for 10 ~ min according to different shapes of the members, opening the mold, and performing heat treatment on the taken-out members at 160 ℃ to obtain the required polymethacrylimide foam, wherein the used unsaturated olefin monomers comprise acrylonitrile, methacrylic acid, acrylamide monomers and acrylate monomers, and the unsaturated olefin monomers account for 100 wt% and comprise 60 wt% of ~%, 10 wt%, 38730%, 2 wt% of methacrylic acid, 5wt% of 2 wt%, 5wt% of the acrylamide monomers and 64 wt% of 10% and.

The preparation of the heat expansion microsphere mainly comprises the following steps:

1) uniformly mixing unsaturated olefin monomers, a cross-linking agent, an alkane foaming agent and an oil-soluble initiator, and magnetically stirring for 5 ~ 10 min to obtain an oil phase;

2) homogenizing and emulsifying inorganic dispersant, emulsifier, inorganic salt, aqueous phase polymerization inhibitor and deionized water at 10000 rpm for 3 min to obtain aqueous phase;

3) slowly dripping the oil phase obtained in the step (1) into the water phase obtained in the step (2), mechanically stirring for 15 ~ 35 min, and fully mixing uniformly to obtain an oil-in-water emulsion by suspension polymerization;

4) and (3) injecting the emulsion obtained in the step (3) into a high-pressure reaction kettle, heating to 55 ~ 70 ℃ under the nitrogen atmosphere, polymerizing at 0.4 ~ 0.6 MPa for 18 ~ 25 h, washing the obtained product with deionized water, filtering, and drying to obtain the thermal expansion microspheres.

Preferably, the unsaturated olefin monomers used in step 1 comprise 65 wt% of acrylonitrile and ~ 80 wt% of acrylonitrile.

Preferably, the unsaturated olefinic monomers used in step 1 comprise 15wt% ~ 25 wt% of methacrylic acid.

The acrylic ester includes at least one of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and glycidyl methacrylate.

The dosage of the alkane foaming agent used in the step 1 is 10 wt% ~ 40 wt% of the dosage of the unsaturated olefin monomer, and the alkane foaming agent is selected from alkanes with the carbon number of 4 ~ 8 and the boiling point of higher than 20 ℃.

Preferably, the alkane blowing agent is selected from one of isopentane, n-pentane, isohexane, n-hexane, and isoheptane.

The cross-linking agent used in the step 1 is one or more of ethylene glycol dimethacrylate, trimethylolpropane triacrylate, 1, 6-hexanediol dimethacrylate, 1, 4-butanediol dimethacrylate and 1, 4-butanediol vinyl diether, and the dosage of the cross-linking agent is ~ 1wt% of the dosage of the unsaturated olefin monomer, wherein the dosage of the cross-linking agent is 0.01 wt%.

Preferably, the amount of the crosslinking agent is 0.1 wt% ~ 0.5.5 wt% based on the amount of the unsaturated olefin monomer.

The oil-soluble initiator used in the step 1 is one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide and lauroyl peroxide.

The inorganic salt used in the step 2 is sodium chloride.

The inorganic dispersant used in the step 2 is one or more of nano silicon dioxide, nano titanium dioxide, halloysite and lithium magnesium silicate.

The emulsifier used in the step 2 is one or more of polyvinylpyrrolidone, polyvinyl alcohol and sodium dodecyl sulfate.

The invention has the beneficial effects that:

1. the prepared thermal expansion microsphere particles can directly obtain a foaming raw material by screening, so that the grinding step is omitted, and the polymethacrylic subfoam can be obtained at one time by molding in a mold;

2. the PMI thermal expansion microspheres synthesized by the invention have the shell which takes MAA/AN copolymer as a main body and the core as a foaming agent, and can complete foaming, molding and curing in a mold at one time;

3. the particle size of the polymer microspheres prepared by the Pickering emulsion suspension polymerization method is generally 5 ~ 55 mu m, which is far smaller than that of the particles of the mechanically crushed copolymer foamable sheet material, so that the specific surface area of the material is greatly increased, and the contact interface area between the microspheres is correspondingly and greatly increased;

4. the Pickering emulsion suspension polymerization method uses colloid particles, which are generally inorganic nonmetallic particles, to replace the traditional surfactant, has low toxicity and low cost, generally does not need post-treatment, and the particles are retained in the material to form a composite material, thus being environment-friendly;

5. the PMI thermal expansion microspheres synthesized by the method disclosed by the invention have wide application prospects in the aspects of preparing PMI foam thick plates and PMI foam materials with complex shapes.

Drawings

FIG. 1 is a process flow diagram of the present invention;

FIG. 2 is a graph of static thermomechanical analysis of thermally expanded microspheres prepared in example 1;

FIG. 3 is an infrared spectrum of the thermally expandable microspheres prepared in example 1.

FIG. 4 shows the properties of polymethacrylimide foams prepared in examples 1 to 4.

Detailed Description

The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.