CN110256794A - A kind of polymethacrylimide foam and preparation method thereof - Google Patents
A kind of polymethacrylimide foam and preparation method thereof Download PDFInfo
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- CN110256794A CN110256794A CN201910476841.2A CN201910476841A CN110256794A CN 110256794 A CN110256794 A CN 110256794A CN 201910476841 A CN201910476841 A CN 201910476841A CN 110256794 A CN110256794 A CN 110256794A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/142—Compounds containing oxygen but no halogen atom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
Abstract
The invention discloses a kind of polymethacrylimide foams, the raw material of the polymethacrylimide foam material include be used as the methacrylic acid and methacrylonitrile of comonomer, initiator, crosslinking agent, foaming agent, antioxidant and heat stabilizer, wherein the comonomer, the initiator, the crosslinking agent, the foaming agent, the antioxidant and the heat stabilizer weight ratio be 100:1-2:2-20:2-20:0.5-1:0.5-1；Wherein the antioxidant is selected from one of antioxidant 1010, antioxidant BHT, antioxidant DSTP or a variety of, and the invention also discloses preparation methods.The present invention effectively prevent the progress of thermal oxide, thermal decomposition, improves the compression resistant croop property of polymethacrylimide foam at high operating temperatures in the present invention, hence it is evident that improves heat distortion temperature.
Description
Technical field
The present invention relates to polymethacrylimide foam technical field, especially a kind of poly- methyl of high temperature resistant compression creep
Acrylimide foam and preparation method thereof.
Background technique
PMI foamed bulk is a kind of high-strength foam, is resistant to 130 DEG C and following temperature, 0.3MPa and following medium temperature are compound
Technique, but it is not resistant to the combination process such as 180 DEG C and temperatures above, 0.3MPa pressure above.PMI foam is in high-temperature atmosphere
In, one side strand is easily broken, and generates hydrogen-containing radicals, while hydrogen-containing radicals have can be catalyzed the disconnected of acceleration molecular chain
It splits, produces unsaturated conjugated polyene, lead to product discoloration, carbonization；On the other hand, due to being contacted with oxygen in air, low
Under temperature state, oxygen chemical energy is lower, unobvious to the oxidation effectiveness of PMI foamed bulk, when temperature reaches 130 DEG C or more
When, at especially 180 DEG C, oxygen chemical energy is improved, oxidation aggravation, to make material such as tensile property, compression performance
It reduces.
In many high end composites parts, combined temp is generally 180 DEG C, and pressure uses temperature also greater than 0.3MPa
Generally 150 DEG C or higher, PMI foam is not able to satisfy high end composites technique and requirement at present, has limited to PMI foam
Use scope and popularization and application.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome common PMI foam be not able to satisfy high end composites technique and
The problem of requirement, and provide a kind of polymethacrylimide foam and preparation method thereof.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of polymethacrylimide foam, the raw material of the polymethacrylimide foam material include as altogether
The methacrylic acid and methacrylonitrile of polycondensation monomer, initiator, crosslinking agent, foaming agent, antioxidant and heat stabilizer, wherein described
Comonomer, the initiator, the crosslinking agent, the foaming agent, the antioxidant and the heat stabilizer weight ratio be
100:1-2:2-20:2-20:0.5-1:0.5-1；
Wherein the antioxidant is selected from one of antioxidant 1010, antioxidant BHT, antioxidant DSTP or a variety of；
The heat stabilizer is selected from one of calcium laurate, sorbierite, thio-diethylene glycol amino-butenate or more
Kind.
Further, the weight ratio of the methacrylic acid and the methacrylonitrile is 1-2:1-1.6.
Preferably, the initiator be selected from benzoyl peroxide, 2,5- dimethyl -2,5 two (t-butylperoxy) hexane,
One of cumyl peroxide is a variety of.
Preferably, the crosslinking agent be selected from one of bismaleimide, Dan Malai acid imide, aluminium methacrylate or
It is a variety of.
Preferably, the foaming agent includes physical blowing agent and chemical foaming agent, and the physical blowing agent is selected from water, second
One of alcohol, tert-butyl alcohol are a variety of, and the chemical foaming agent is in azodicarbonamide, benzene sulfonyl hydrazide, Ficel CR
It is one or more.
Preferably, the raw material of the polymethacrylimide foam material further includes polymerization inhibitor, and the polymerization inhibitor is selected from
Between one or both of trinitrobenzen, m-dinitrobenzene；
Preferably, the weight ratio of the comonomer and the polymerization inhibitor is 100:0.2-0.5.
Specifically, when temperature is 130-180 DEG C and pressure is 0.3MPa-0.6Mpa, the Polymethacrylimide
Compression-creep rate≤0.13% of foamed material.
Specifically, when temperature is 230 DEG C, expansion rate≤33.48% of the polymethacrylimide foam material is inhaled
Water rate≤0.4%.
A kind of preparation method of polymethacrylimide foam, comprising the following steps:
The comonomer, the initiator, the crosslinking agent, the foaming agent, the antioxidant and the heat is steady
Determine agent to be mixed in proportion to obtain mixture；
Mixture is copolymerized within the temperature range of 20-50 DEG C in a mold, demoulding after to be solidified and entire body is transparent
Obtain first product；
The first product is foamed in 120-240 DEG C of temperature range the polymethacrylimide foam is made
Material.
Further, by the comonomer, the initiator, the crosslinking agent, the foaming agent, the antioxidant and
The heat stabilizer further be selected between one or both of trinitrobenzen, m-dinitrobenzene polymerization inhibitor mix to be mixed
Object is closed, wherein the weight ratio of the comonomer and the polymerization inhibitor is 100:0.2-0.5.
The above technical solution of the present invention has the following advantages over the prior art:
(1) it chemically reacts each stage speed and keeps almost the same, guarantee that chemical reaction equilibrium carries out, antioxidant is steady with heat
Determine agent to be equably embedded in Polymethacrylimide strand；
(2) it is effectively prevented the progress of thermal oxide, thermal decomposition, polymethacrylimide foam is in height in the raising present invention
Compression resistant croop property under temperature state, hence it is evident that improve heat distortion temperature；
(3) the polymethacrylimide foam ageing-resistant performance is good, and the service life is long, hence it is evident that improves wet-hot aging performance, expansion
Rate reduces, and water absorption rate reduces.
Detailed description of the invention
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the step flow chart in the present invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is described in further detail.
As shown in Figure 1, be the preparation method flow chart in the present invention, by comonomer, initiator, crosslinking agent, foaming agent,
Antioxidant and heat stabilizer are uniformly mixed by the weight ratio of 100:1-2:2-20:2-20:0.5-1:0.5-1 obtains mixture；
Mixture is copolymerized within the temperature range of 20-50 DEG C in a mold, demoulding after to be solidified and entire body is transparent
Obtain first product；
First product is foamed in 120-240 DEG C of temperature range so that polymethacrylimide foam material is made.
Comonomer includes methacrylic acid and methacrylonitrile, and the weight ratio of methacrylic acid and methacrylonitrile is 1-
2:1-1.6.
Antioxidant restrains or delays the oxidation and degradation of foam in material application process, and antioxidant is selected from antioxidant
1010, one of antioxidant BHT, antioxidant DSTP or a variety of.Heat stabilizer has the function of absorbing hydrogen-containing radicals, make point
Sub- chain break slows down or terminates, and heat stabilizer is in calcium laurate, sorbierite, thio-diethylene glycol amino-butenate
It is one or more.
Initiator in the reaction system, guides the polymerization of two main monomers, and initiator is selected from benzoyl peroxide, 2,5- diformazan
One of base -2,5 two (t-butylperoxy) hexane, cumyl peroxide are a variety of.
Crosslinking agent in the reaction system, plays bridge formation on polymerizable molecular chain, promotes the progress of sulfonating reaction, crosslinking
Agent is selected from one of bismaleimide, Dan Malai acid imide, aluminium methacrylate or a variety of.
Foaming agent plays a part of to generate gas in the reaction system, and foaming agent includes physical blowing agent and chemical foaming agent,
Physical blowing agent is selected from one of water, ethyl alcohol, the tert-butyl alcohol or a variety of, and chemical foaming agent is selected from azodicarbonamide, benzene sulfonyl
One of hydrazine, Ficel CR or a variety of.
The raw material of the polymethacrylimide foam material further includes polymerization inhibitor, trinitrobenzen between polymerization inhibitor is selected from,
One or both of dinitrobenzene.The weight ratio of comonomer and polymerization inhibitor is 100:0.2-0.5.Polymerization inhibitor makes to chemically react
Each stage speed is almost the same, guarantees that chemical reaction equilibrium carries out, antioxidant, heat stabilizer are equably embedded in poly- methyl-prop
In alkene acid imide strand.
Embodiment
Embodiment 1
Methacrylic acid, methacrylonitrile are used as comonomer, the polymethyl after being mixed by weight 2:1.3
The raw material of acid imide foam material includes 100 parts of comonomer, 1 part of benzoyl peroxide, 5 parts of bismaleimide, ethyl alcohol 7
Part, 3 parts of azodicarbonamide, 0.5 part of thio-diethylene glycol amino-butenate, exist after mixing by 0.5 part of antioxidant BHT
It polymerize in 40 degree of water-baths, then foams in 215 degree of ovens, it is 80Kg/m that density, which can be made,3Polymethyl acyl it is sub-
Amine foamed material.
Comparative example 1
Methacrylic acid, methacrylonitrile are used as comonomer, the polymethyl after being mixed by weight 2:1.3
The raw material of acid imide foam material includes 100 parts of comonomer, 1 part of benzoyl peroxide, 5 parts of bismaleimide, ethyl alcohol 7
Part, 3 parts of azodicarbonamide, polymerize in 40 degree of water-baths after mixing, then foam, can make in 215 degree of ovens
Obtaining density is 80Kg/m3Polymethacrylimide foam material.
Embodiment 2
Methacrylic acid, methacrylonitrile are used as comonomer, the polymethyl after being mixed by weight 2:1.3
The raw material of acid imide foam material includes 100 parts of comonomer, 2,5- dimethyl -2,5 two (t-butylperoxy) hexanes 0.3
Part, 0.7 part of cumyl peroxide, 7 parts of aluminium methacrylate, 2 parts of water, 11 parts of the tert-butyl alcohol, CR6 parts of Ficel, antioxidant
DSTP0.5 parts, 0.2 part of 0.5 part, trinitrobenzen of calcium laurate polymerize in 40 degree of water-baths after mixing, roasting at 215 degree
It foams in case, it is 42Kg/m that density, which can be made,3Polymethacrylimide foam material.
Comparative example 2
Methacrylic acid, methacrylonitrile are used as comonomer, the polymethyl after being mixed by weight 2:1.3
The raw material of acid imide foam material includes 100 parts of comonomer, 2,5- dimethyl -2,5 two (t-butylperoxy) hexanes 0.3
Part, 0.7 part of cumyl peroxide, are uniformly mixed by 7 parts of aluminium methacrylate, 2 parts of water, 11 parts of the tert-butyl alcohol, CR6 parts of Ficel
It polymerize in 40 degree of water-baths afterwards, foams in 215 degree of ovens, it is 42Kg/m that density, which can be made,3Polymethyl acyl it is sub-
Amine foamed material.
Embodiment 3
Methacrylic acid, methacrylonitrile are used as comonomer, the polymethyl after being mixed by weight 2:1.3
The raw material of acid imide foam material includes 100 parts of comonomer, 2,5- dimethyl -2,5 two (t-butylperoxy) hexanes 1.5
Part, 5 parts of Dan Malai acid imide, 3 parts of aluminium methacrylate, 3 parts of water, 2 parts of ethyl alcohol, 2 parts of the tert-butyl alcohol, 3 parts of benzene sulfonyl hydrazide, Ficel
CR3 parts, 0.5 part of antioxidant 1010,0.5 part of 0.5 part, trinitrobenzen of sorbierite polymerize in 40 degree of water-baths after mixing,
Then it foams in 215 degree of ovens, it is 25Kg/m that density, which can be made,3Polymethacrylimide foam material.
Comparative example 3
Methacrylic acid, methacrylonitrile are used as comonomer, the polymethyl after being mixed by weight 2:1.3
The raw material of acid imide foam material includes 100 parts of comonomer, 2,5- dimethyl -2,5 two (t-butylperoxy) hexanes 1.5
Part, 5 parts of Dan Malai acid imide, 3 parts of aluminium methacrylate, 3 parts of water, 2 parts of ethyl alcohol, 2 parts of the tert-butyl alcohol, 3 parts of benzene sulfonyl hydrazide, Ficel
CR3 parts, it polymerize in 40 degree of water-baths after mixing, then foams in 215 degree of ovens, it is 25Kg/ that density, which can be made,
m3Polymethacrylimide foam material.
Comparative example 4
Methacrylic acid, methacrylonitrile are used as comonomer, the polymethyl after being mixed by weight 2:1.3
The raw material of acid imide foam material includes 100 parts of comonomer, 2,5- dimethyl -2,5 two (t-butylperoxy) hexanes 1.5
Part, 5 parts of Dan Malai acid imide, 3 parts of aluminium methacrylate, 3 parts of water, 2 parts of ethyl alcohol, 2 parts of the tert-butyl alcohol, 3 parts of benzene sulfonyl hydrazide, Ficel
CR3 parts, 0.5 part of 0.5 part, trinitrobenzen of sorbierite polymerize, then in 215 degree of ovens after mixing in 40 degree of water-baths
In foam, can be made density be 25Kg/m3Polymethacrylimide foam material.
Embodiment 4
Methacrylic acid, methacrylonitrile are used as comonomer, the polymethyl after being mixed by weight 2:1.3
The raw material of acid imide foam material includes 100 parts of comonomer, 0.5 part of benzoyl peroxide, (the tertiary fourth of 2,5- dimethyl -2,5 two
Base peroxy) 0.5 part of hexane, 7 parts of bismaleimide, 10 parts of Dan Malai acid imide, 2 parts of the tert-butyl alcohol, azodicarbonamide 2
Part, 0.3 part of antioxidant BHT, DSTP0.3 parts of antioxidant, 0.3 part of sorbierite, 0.4 part of thio-diethylene glycol amino-butenate,
Between 0.2 part of trinitrobenzen, polymerize in 40 degree of water-baths after mixing, then foam, can be made close in 215 degree of ovens
Degree is 260Kg/m3Polymethacrylimide foam material.
Comparative example 5
Methacrylic acid, methacrylonitrile are used as comonomer, the polymethyl after being mixed by weight 2:1.3
The raw material of acid imide foam material includes 100 parts of comonomer, 0.5 part of benzoyl peroxide, (the tertiary fourth of 2,5- dimethyl -2,5 two
Base peroxy) 0.5 part of hexane, 7 parts of bismaleimide, 10 parts of Dan Malai acid imide, 2 parts of the tert-butyl alcohol, azodicarbonamide 2
Part, it polymerize in 40 degree of water-baths after mixing, then foams in 215 degree of ovens, it is 260Kg/m that density, which can be made,3
Polymethacrylimide foam material.
Embodiment 5
Methacrylic acid, methacrylonitrile are used as comonomer, the polymethyl after being mixed by weight 1:1.6
The raw material of acid imide foam material includes 100 parts of comonomer, 0.5 part of benzoyl peroxide, (the tertiary fourth of 2,5- dimethyl -2,5 two
Base peroxy) 0.5 part of hexane, 7 parts of bismaleimide, 10 parts of Dan Malai acid imide, 2 parts of the tert-butyl alcohol, azodicarbonamide 2
Part, 0.3 part of antioxidant BHT, DSTP0.3 parts of antioxidant, 0.3 part of sorbierite, 0.4 part of thio-diethylene glycol amino-butenate,
0.5 part of m-dinitrobenzene, it polymerize in 40 degree of water-baths after mixing, then foams, can be made close in 215 degree of ovens
Degree is 260Kg/m3Polymethacrylimide foam material.
Comparative example 6
Methacrylic acid, methacrylonitrile are used as comonomer, the polymethyl after being mixed by weight 1:1.6
The raw material of acid imide foam material includes 100 parts of comonomer, 0.5 part of benzoyl peroxide, (the tertiary fourth of 2,5- dimethyl -2,5 two
Base peroxy) 0.5 part of hexane, 7 parts of bismaleimide, 10 parts of Dan Malai acid imide, 2 parts of the tert-butyl alcohol, azodicarbonamide 2
Part, it polymerize in 40 degree of water-baths after mixing, then foams in 215 degree of ovens, it is 260Kg/m that density, which can be made,3
Polymethacrylimide foam material.
Obtained polymethacrylimide foam material is according to 20672 and of GB/T in embodiment 1-5, comparative example 1-6
Two standard of DIN53424 compares test, and data are as shown in the table:
The test result statistical form of 1 polymethacrylimide foam material of table
It can be seen that by above-mentioned data after antioxidant and heat stabilizer is added, when test temperature is 200 DEG C, test is pressed
When power is 0.6Mpa, test two hours, compression-creep rate≤0.06% of gained polymethacrylimide foam material, material
High temperature compressed croop property significantly improve, heat distortion temperature significantly improves, method of modifying it is feasible effectively.
It is added to antioxidant and heat stabilizer simultaneously in embodiment 3, has only added heat stabilizer in comparative example 4, has been not added with anti-
Oxygen agent, by embodiment 3, the test result of comparative example 4 it is found that the antioxidant in embodiment 3 can not only prevent material aging, and
In the reaction system the heat resistance of polymethacrylimide foam material can be further increased with heat stabilizer concerted reaction
Energy.
Polymethacrylimide foam material progress basic physics survey obtained in Example 4, comparative example 5
Examination, test result are as shown in table 2:
2 basic physics test result table of table
| Material number | Average thickness/μm | Density/g*cm-3 | Tg/℃ | Pore-size distribution/μm |
| Embodiment 4 | 154.6 | 0.098 | 212 | 10-20 |
| Comparative example 5 | 150.8 | 0.11 | 200 | 20-40 |
It is added to antioxidant and heat stabilizer in embodiment 4, is not added with antioxidant and heat stabilizer in comparative example 5, from table 2
As can be seen that compared with comparative example 5, the Tg of polymethacrylimide foam material obtained is obviously increased in embodiment 4, hole
Diameter is smaller, can train and cut out thinner sheet material, and polymethacrylimide foam material obtained is through soaked test in embodiment 4
It can slicing after 14 hours.
By polymethacrylimide foam material obtained in embodiment 4, comparative example 5 respectively in 85 DEG C, 85% humidity
Under the conditions of steady damp heat 48h, then heat 1min under the conditions of 200 DEG C, 230 DEG C, 250 DEG C respectively, whether test bonding fails.
After above-mentioned condition steady damp heat, 230 DEG C of expansion rate is surveyed, test result is as shown in table 3.
3 polymethacrylimide foam material composite test result table of table
In embodiment 4, comparative example 5 after polymethacrylimide foam material obtained curing, the constant temperature in 50 DEG C of water
1h, 2h are heated, and surveys Dome water absorption rate, experimental result is as shown in table 4:
The verifying of 4 polymethacrylimide foam material water absorption rate of table
| Collocation | Water absorption rate (1h) | Water absorption rate (2h) |
| Embodiment 4 | 0.4% | 0.9% |
| Comparative example 5 | 0.50% | 1.17% |
By the test result of table 3 it is found that polymethacrylimide foam material obtained is in hygrothermal environment in embodiment 4
After test, bonding failure rate is reduced, and wet-hot aging performance significantly improves, and expansion rate is also obviously reduced.It can by the test result of table 4
Know, the water absorption rate of polymethacrylimide foam material obtained is significantly reduced in embodiment 4.
Polymethacrylimide foam material prepared by the present invention can not only be effectively prevented thermal oxide, thermal decomposition into
Row improves the compression resistant croop property under the condition of high temperature, hence it is evident that improves heat distortion temperature, and in heat resistance Tg and humidity resistance
Can on be improved, compared with product before modified, the ratio of failure is decreased obviously, expansion rate reduce, water absorption rate reduce.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And thus amplify out it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of polymethacrylimide foam, it is characterised in that: the raw material of the polymethacrylimide foam material
Comprising as comonomer methacrylic acid and methacrylonitrile, initiator, crosslinking agent, foaming agent, antioxidant and thermostabilization
Agent, wherein the comonomer, the initiator, the crosslinking agent, the foaming agent, the antioxidant and the heat stabilizer
Weight ratio be 100:1-2:2-20:2-20:0.5-1:0.5-1；
Wherein the antioxidant is selected from one of antioxidant 1010, antioxidant BHT, antioxidant DSTP or a variety of；
The heat stabilizer is selected from one of calcium laurate, sorbierite, thio-diethylene glycol amino-butenate or a variety of.
2. polymethacrylimide foam according to claim 1, it is characterised in that: the methacrylic acid and described
The weight ratio of methacrylonitrile is 1-2:1-1.6.
3. polymethacrylimide foam according to claim 1 or 2, it is characterised in that: the initiator was selected from
One of Benzoyl Oxide, 2,5- dimethyl -2,5 two (t-butylperoxy) hexane, cumyl peroxide are a variety of.
4. polymethacrylimide foam according to claim 1 or 2, it is characterised in that: the crosslinking agent is selected from double
One of maleimide, Dan Malai acid imide, aluminium methacrylate are a variety of.
5. polymethacrylimide foam according to claim 1 or 2, it is characterised in that: the foaming agent inclusion
Haircut infusion and chemical foaming agent, the physical blowing agent are selected from one of water, ethyl alcohol, the tert-butyl alcohol or a variety of, the chemistry
Foaming agent is selected from one of azodicarbonamide, benzene sulfonyl hydrazide, Ficel CR or a variety of.
6. polymethacrylimide foam according to claim 1 or 2, it is characterised in that: the polymethyl acyl
The raw material of imine foam material further includes polymerization inhibitor, between the polymerization inhibitor is selected from one of trinitrobenzen, m-dinitrobenzene or
Two kinds；
The weight ratio of the comonomer and the polymerization inhibitor is 100:0.2-0.5.
7. polymethacrylimide foam described in -6 any one according to claim 1, it is characterised in that: when temperature is
When 130-180 DEG C and pressure are 0.3MPa-0.6Mpa, the compression-creep rate of the polymethacrylimide foam material≤
0.13%.
8. polymethacrylimide foam described in -6 any one according to claim 1, it is characterised in that: temperature 230
DEG C when, expansion rate≤33.48% of the polymethacrylimide foam material, water absorption rate≤0.4%.
9. a kind of preparation method of polymethacrylimide foam described in claim 1-5 any one, it is characterised in that
The following steps are included:
By the comonomer, the initiator, the crosslinking agent, the foaming agent, the antioxidant and the heat stabilizer
It is mixed in proportion to obtain mixture；
Mixture is copolymerized within the temperature range of 20-50 DEG C in a mold, demoulding obtains after to be solidified and entire body is transparent
First product；
The first product is foamed in 120-240 DEG C of temperature range so that the polymethacrylimide foam material is made
Material.
10. the preparation method of polymethacrylimide foam according to claim 9, which is characterized in that will be described total
Polycondensation monomer, the initiator, the crosslinking agent, the foaming agent, the antioxidant and the heat stabilizer further be selected from
Between the polymerization inhibitor mixing of one or both of trinitrobenzen, m-dinitrobenzene to obtain mixture, wherein the comonomer and
The weight ratio of the polymerization inhibitor is 100:0.2-0.5.
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| CN201910476841.2A CN110256794A (en) | 2019-06-03 | 2019-06-03 | A kind of polymethacrylimide foam and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708258A (en) * | 2021-01-12 | 2021-04-27 | 北京九天行歌航天科技有限公司 | Polymethacrylimide foam, preparation method and application thereof |
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| CN102858902A (en) * | 2010-03-31 | 2013-01-02 | 积水化学工业株式会社 | Thermally expandable microcapsule and process for production of thermally expandable microcapsule |
| CN103627021A (en) * | 2013-12-12 | 2014-03-12 | 扬州恒聚新材料有限责任公司 | Preparation method of polymethacrylimide foam |
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| US20020161126A1 (en) * | 2001-02-27 | 2002-10-31 | Carlos Alfonso Cruz | Processes for preparing non-gelling high polymer compositions and thermoplastic blends thereof |
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Application publication date: 20190920 |