CN107163173B - A kind of preparation method of amorphous polymer fretting map plate - Google Patents

A kind of preparation method of amorphous polymer fretting map plate Download PDF

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CN107163173B
CN107163173B CN201710338657.2A CN201710338657A CN107163173B CN 107163173 B CN107163173 B CN 107163173B CN 201710338657 A CN201710338657 A CN 201710338657A CN 107163173 B CN107163173 B CN 107163173B
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amorphous polymer
fretting map
polymerization
map plate
preparation
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CN107163173A (en
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袁新强
艾桃桃
冯小明
董金虎
盛爱香
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Shaanxi University of Technology
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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
    • C08F120/00—Homopolymers 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08J2333/04—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 esters
    • C08J2333/06—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 esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2425/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/06—Polystyrene
    • 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
    • C08J2425/00—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 at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C08J2425/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Abstract

The invention discloses a kind of preparation methods of amorphous polymer fretting map plate, comprising: 1) prepares expandable amorphous polymer: 1a using cold polymerization technique) dissolution of amorphous polymer powder；1b) cold polymerization agent is deployed；1c) mixing degassing；1d) model is cast；1e) Cryogenic air bath pre-polymerization gathers with rear；1f) fastening of model surrounding and relaxation up and down；2) the negative pressure fretting map molding of expandable amorphous polymer, is made amorphous polymer fretting map plate.Amorphous polymer fretting map plate prepared by the present invention, it can be avoided hypertonia during traditional amorphous polymer fretting map plate preparation forms, the problems such as there are surface quality, energy consumption and environmental pollutions, for a kind of pressure requirements are not high, environmental pollution is small, low energy consumption and surface quality is high, equipment investment is few and engineer application is feasible, it is particularly suitable for the preparation method of the amorphous polymer fretting map plate of high added value resource utilization waste plastic.

Description

A kind of preparation method of amorphous polymer fretting map plate
Technical field
The present invention relates to the fretting map forming technique of amorphous polymer, in particular to a kind of amorphous polymer fretting map Plate and preparation method thereof belongs to polymer fretting map field.
Background technique
Earliest in the 1950s, O.R.Mclntire and J.Lamos has found that the pore size of polymer, 20 generation It records the eighties, the Massachusetts Institute of Technology proposes the concept of polymer fretting map.Since this polymer fretting map product had both maintained The original mechanical property of polymer, and alleviate the weight of product, also effectively prevent product occur in forming process it is each Kind defect problem, forming technique exploitation are concerned with application, many leading companies such as U.S. Trexel, Japan Sekisui The practical application exploitation that the companies such as Plastics of Tokyo and Canada Eregel all have been working on the technology is pushed away with commercialization Extensively.In theory, the technology can be used all to produce polymer fretting map product, polymer fretting map material in nearly all polymer Material has been known as " 21 century new material ", and forming process is usually to mix polymer and foaming agent through being saturated, and is added Foaming agent is added to be precipitated into complex, then complex is grown up molding.In this method forming process pressure P be generally tens, it is up to a hundred even The problems such as several hundred a atmospheric pressure, pressure is very high, harsh to equipment requirement, and there are surface quality, energy consumption and environmental pollutions, industry It is limited to change application.Application is concentrated mainly on the fields such as automobile and interior material, electric equipment products, curable product at present. Therefore, it is badly in need of developing a kind of pair pressure requirements not being high, environmental pollution is small, low energy consumption and table on polymer fretting map industrialization road The high forming technique of face quality.
Summary of the invention
The purpose of the present invention is it is intended that amorphous polymer provides a kind of simple process, mild condition, low in cost, equipment Less investment and the feasible fretting map forming technique of engineer application.
The present invention is realized by following technical proposals.
A kind of preparation method of amorphous polymer fretting map plate, includes the following steps:
1) cold polymerization technique prepares expandable amorphous polymer:
1a) amorphous polymer powder dissolves: dissolving 0.05-0.2 parts of initiators, 1-5 parts with 100 parts of methyl methacrylates Azodiisobutyronitrile and 6-50 parts of amorphous polymers, be prepared into the polymer solution A of methyl methacrylate；
1b) cold polymerization agent is deployed: dissolving 20-50 parts of trimethylamines with 100 parts of methyl methacrylates, cold polymerization agent is made B；
1c) mixing degassing: by polymer solution A made from step 1a) with and step 1b) made from cold polymerization agent B according to 100:(0.1-1) mass ratio is uniformly mixed, and vacuum defoamation after filtering obtains grouting slurry C；
1d) model is cast: step 1c) slurry C obtained of being in the milk pours into chilled glass die, after being compacted, being vented It is corrected with ruler item, upper clamper；
1e) Cryogenic air bath pre-polymerization gathers with rear: model made from step 1d) is sent into the drying chamber with wind circulating system, It is taken out after pre-polymerization, is cooling；Gather after sending after compacting, exhaust, the correction of ruler item, upper clamper into the drying chamber with wind circulating system again It is taken out after continuation stage feeding polymerization, is cooling；
1f) fastening of model surrounding and relaxation up and down: the model surrounding steel bar gathered with after through Cryogenic air bath pre-polymerization is tight Gu；The correction of ruler item, release clamp；
2) the negative pressure fretting map molding of expandable amorphous polymer
Step 1f) model is placed in vacuum drying oven, is foamed under the vacuum pressures, amorphous polymer fretting map is made Plate.
Preferably, the initiator is one or both of dibenzoyl peroxide or dilauroyl peroxide Mixture pellet.
Preferably, the copolymer is polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymerization The mixture powder of one or more of object or ethylene-vinyl acetate copolymer composition.
Preferably, the trimethylamine is n,N-Dimethylaniline, N, N- dihydroxyethyl p-toluidine or N, N- It is one or more of in dihydroxypropyl para-totuidine.
Preferably, the step 1) -1e) Cryogenic air bath pre-polymerization and rear collecting process in, 40-50 DEG C band circulation It in the drying chamber of wind system, is taken out after pre-polymerization 40-60min, then rear poly- 2-4h, 40- in the 20-30 DEG C of drying chamber with wind circulating system 50 DEG C are continued to polymerize 1-2h.
Preferably, in the step 2), model is placed in 110-160 DEG C of vacuum drying oven, in 0.01-0.09MPa Pressure lower frothing 1-4h.
Compared with the existing technology, the technology of the present invention simple process, mild condition, low in cost, equipment investment be few and engineering Using feasible, it is particularly suitable for high added value resource utilization waste plastic, meets national 13 science and technology development planning requirements, Effective solution route is provided to alleviate global energy crisis.
Specific embodiment
Below with reference to embodiment, the invention will be described in further detail, but be not intended as to invention do any restrictions according to According to.
The preparation method of amorphous polymer fretting map plate of the present invention, includes the following steps:
1) cold polymerization technique prepares expandable amorphous polymer:
1a) amorphous polymer powder dissolves: dissolving 0.05-0.2 parts by diphenyl peroxide with 100 parts of methyl methacrylates One or both of formyl, dilauroyl peroxide composition mixture pellet initiator, 1-5 parts of azodiisobutyronitrile and 6-50 parts by polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer, ethylene-vinyl acetate copolymer One or more of compositions mixture powder amorphous polymers, be prepared into the polymer solution A of methyl methacrylate；
1b) cold polymerization agent is deployed: dissolving 20-50 parts by n,N-Dimethylaniline, N, N- with 100 parts of methyl methacrylates Dihydroxyethyl p-toluidine, N, the mixing trimethylamines of one or more of compositions in N- dihydroxypropyl para-totuidine are made cold poly- Mixture B；
1c) mixing degassing: by polymer solution A made from step 1a) with and step 1b) made from cold polymerization agent B according to 100:(0.1-1) mass ratio is uniformly mixed, and vacuum defoamation after filtering obtains grouting slurry C；
1d) model is cast: step 1c) slurry C obtained of being in the milk pours into chilled glass die, after being compacted, being vented It is corrected with ruler item, upper clamper；
1e) Cryogenic air bath pre-polymerization gathers with rear: model made from step 1d) is sent to 40-50 DEG C with wind circulating system It in drying chamber, is taken out after pre-polymerization 40-60min, is cooling；It send after compacting, exhaust, the correction of ruler item, upper clamper to 20-30 DEG C of band again Poly- 2-4h after in the drying chamber of wind circulating system, 40-50 DEG C is continued taking-up, cooling after polymerization 1-2h；
1f) fastening of model surrounding and relaxation up and down: the model surrounding steel bar gathered with after through Cryogenic air bath pre-polymerization is tight Gu；The correction of ruler item, release clamp；
2) the negative pressure fretting map molding of expandable amorphous polymer
Step 1f) model is placed in 110-160 DEG C of vacuum drying oven, in 0.01-0.09MPa pressure lower frothing 1-4h, system Obtain amorphous polymer fretting map plate.
Specific embodiment is given below to further illustrate the present invention.
Embodiment 1
1) cold polymerization technique prepares expandable amorphous polymer:
1a) amorphous polymer powder dissolves: dissolving 0.1 part of dibenzoyl peroxide, 3 with 100 parts of methyl methacrylates Part azodiisobutyronitrile and 30 parts of styrene-acrylonitrile copolymer, are prepared into the polymer solution A of methyl methacrylate；
1b) cold polymerization agent is deployed: dissolving 40 parts of N, N- dihydroxyethyl p-toluidine, system with 100 parts of methyl methacrylates Obtain cold polymerization agent B；
1c) mixing degassing: by polymer solution A with and cold polymerization agent B be uniformly mixed according to 100:0.5 mass ratio, process Vacuum defoamation obtains grouting slurry C after filter；
1d) model is cast: slurry C of being in the milk pours into chilled glass die, is corrected after being compacted, being vented with ruler item, on Clamper；
1e) Cryogenic air bath pre-polymerization gathers with rear: model being sent into 50 DEG C of drying chambers with wind circulating system, pre-polymerization 50min It takes out afterwards, is cooling；Gather after sending after compacting, exhaust, the correction of ruler item, upper clamper into 20 DEG C of drying chambers with wind circulating system again 4h, 45 DEG C are continued taking-up, cooling after polymerization 1h；
1f) fastening of model surrounding is with relaxation up and down: model surrounding is fastened with steel bar；The correction of ruler item, release clamp；
2) the negative pressure fretting map molding of expandable amorphous polymer:
Step 1f) model is placed in 120 DEG C of vacuum drying ovens, in 0.09MPa pressure lower frothing 3h, amorphous state polymerization is made Object fretting map plate.
Embodiment 2
1) cold polymerization technique prepares expandable amorphous polymer:
1a) amorphous polymer powder dissolves: dissolving 0.05 part by two laurel of peroxidating with 100 parts of methyl methacrylates Acyl, 5 parts of azodiisobutyronitrile and 50 parts of polymethyl methacrylates, are prepared into the polymer solution A of methyl methacrylate；
1b) cold polymerization agent is deployed: dissolving 20 parts of n,N-Dimethylaniline and N, N- bis- with 100 parts of methyl methacrylates Cold polymerization agent B is made according to the mixing trimethylamine of 1:1 volume ratio in hydroxypropyl para-totuidine；
1c) mixing degassing: polymer solution A is uniformly mixed with cold polymerization agent B according to 100:0.1 mass ratio, through filtering Vacuum defoamation obtains grouting slurry C afterwards；
1d) model is cast: slurry C of being in the milk pours into chilled glass die, is corrected after being compacted, being vented with ruler item, on Clamper；
1e) Cryogenic air bath pre-polymerization gathers with rear: model being sent into 40 DEG C of drying chambers with wind circulating system, pre-polymerization 40min It takes out afterwards, is cooling；Gather after sending after compacting, exhaust, the correction of ruler item, upper clamper into 30 DEG C of drying chambers with wind circulating system again 2h, 50 DEG C are continued taking-up, cooling after polymerization 1h；
1f) fastening of model surrounding and relaxation up and down: the model surrounding steel bar gathered with after through Cryogenic air bath pre-polymerization is tight Gu；The correction of ruler item, release clamp；
2) the negative pressure fretting map molding of expandable amorphous polymer
Step 1f) model is placed in 160 DEG C of vacuum drying ovens, in 0.01MPa pressure lower frothing 1h, amorphous state polymerization is made Object fretting map plate.
Embodiment 3
1) cold polymerization technique prepares expandable amorphous polymer:
1a) amorphous polymer powder dissolves: with 0.2 part of 100 parts of methyl methacrylates dissolution by dibenzoyl peroxide, Mixture pellet initiator, 1 part of azodiisobutyronitrile and the 6 parts of polyphenyl of one or both of dilauroyl peroxide composition The mixture powder of ethylene, ethylene-vinyl acetate copolymer is prepared into the polymer solution A of methyl methacrylate；
1b) cold polymerization agent is deployed: being dissolved 50 parts of n,N-Dimethylaniline with 100 parts of methyl methacrylates, is made cold poly- Mixture B；
1c) mixing degassing: polymer solution A is uniformly mixed with cold polymerization agent B according to 100:1 mass ratio, after filtering Vacuum defoamation obtains grouting slurry C；
1d) model is cast: slurry C of being in the milk pours into chilled glass die, is corrected after being compacted, being vented with ruler item, on Clamper；
1e) Cryogenic air bath pre-polymerization gathers with rear: model being sent into 40 DEG C of drying chambers with wind circulating system, pre-polymerization 60min It takes out afterwards, is cooling；Gather after sending after compacting, exhaust, the correction of ruler item, upper clamper into 25 DEG C of drying chambers with wind circulating system again 3h, 40 DEG C are continued taking-up, cooling after polymerization 2h；
1f) fastening of model surrounding and relaxation up and down: the model surrounding steel bar gathered with after through Cryogenic air bath pre-polymerization is tight Gu；The correction of ruler item, release clamp；
2) the negative pressure fretting map molding of expandable amorphous polymer
Step 1f) model is placed in 110 DEG C of vacuum drying ovens, in 0.09MPa pressure lower frothing 4h, amorphous state polymerization is made Object fretting map plate.
Amorphous polymer fretting map plate prepared by the present invention can be avoided traditional amorphous polymer fretting map plate preparation The problems such as hypertonia in forming process, there are surface quality, energy consumption and environmental pollutions is that a kind of pressure requirements are high, environment It pollutes that small, low energy consumption and surface quality is high, equipment investment is few and engineer application is feasible, be particularly suitable for high added value resource utilization The preparation method of the amorphous polymer fretting map plate of waste plastic.
The present invention is not limited to the above embodiments, on the basis of technical solution disclosed by the invention, the skill of this field For art personnel according to disclosed technology contents, one can be made to some of which technical characteristic by not needing creative labor A little replacements and deformation, these replacements and deformation are within the scope of the invention.

Claims (5)

1. a kind of preparation method of amorphous polymer fretting map plate, which is characterized in that include the following steps:
1) cold polymerization technique prepares expandable amorphous polymer:
1a) amorphous polymer powder dissolves: dissolving 0.05-0.2 parts of initiators, 1-5 parts of idol with 100 parts of methyl methacrylates Nitrogen bis-isobutyronitrile and 6-50 parts of amorphous polymers, are prepared into the polymer solution A of methyl methacrylate；
1b) cold polymerization agent is deployed: dissolving 20-50 parts of trimethylamines with 100 parts of methyl methacrylates, cold polymerization agent B is made；
1c) mixing degassing: by cold polymerization agent B made from polymer solution A made from step 1a) and and step 1b) according to 100: (0.1-1) mass ratio is uniformly mixed, and vacuum defoamation after filtering obtains grouting slurry C；
1d) model is cast: the obtained slurry C of being in the milk of step 1c) pours into chilled glass die, be compacted, be vented after use ruler Item correction, upper clamper；
1e) Cryogenic air bath pre-polymerization gathers with rear: model made from step 1d) being sent into the drying chamber with wind circulating system, pre-polymerization It takes out afterwards, is cooling；Again through compacting, exhaust, the correction of ruler item, send into the drying chamber with wind circulating system after upper clamper after continue point It is taken out after Duan Juhe, is cooling；
1f) fastening of model surrounding and relaxation up and down: the model surrounding gathered with after through Cryogenic air bath pre-polymerization is fastened with steel bar；Ruler Item correction, release clamp；
2) the negative pressure fretting map molding of expandable amorphous polymer
Step 1f) model is placed in vacuum drying oven, is foamed under the vacuum pressures, amorphous polymer fretting map plate is made；
The initiator is one or both of dibenzoyl peroxide or dilauroyl peroxide mixture pellet.
2. a kind of preparation method of amorphous polymer fretting map plate according to claim 1, which is characterized in that described non- Crystalline state polymer is that polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer or ethylene-vinyl acetate are total The mixture powder of one or more of polymers composition.
3. a kind of preparation method of amorphous polymer fretting map plate according to claim 1, which is characterized in that described to have Machine tertiary amine is n,N-Dimethylaniline, N, one kind or several in N- dihydroxyethyl p-toluidine or N, N- dihydroxypropyl para-totuidine Kind.
4. a kind of preparation method of amorphous polymer fretting map plate according to claim 1, which is characterized in that the step Rapid 1) -1e) Cryogenic air bath pre-polymerization and rear collecting process in, in the 40-50 DEG C of drying chamber with wind circulating system, pre-polymerization 40-60min After take out, then in the 20-30 DEG C of drying chamber with wind circulating system after poly- 2-4h, 40-50 DEG C continue polymerize 1-2h.
5. a kind of preparation method of amorphous polymer fretting map plate according to claim 1, which is characterized in that the step It is rapid 2) in, model is placed in 110-160 DEG C of vacuum drying oven, in 0.01-0.09MPa pressure lower frothing 1-4h.
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Publication number Priority date Publication date Assignee Title
CN101749521A (en) * 2008-12-12 2010-06-23 北京化工大学 Closed hole-shaped vacuum foam for heat insulation and sound insulation and method for preparing same
CN105237673A (en) * 2015-10-19 2016-01-13 陕西理工学院 Method for casting PMMA board under room temperature polymerization condition and spraying polymerization device
CN105315595A (en) * 2015-11-17 2016-02-10 陕西理工学院 Waste plastic recycling method
CN106566156A (en) * 2016-11-02 2017-04-19 武汉理工大学 Preparation method of graphene nanobelt/PMMA microcellular foam nanocomposite

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101749521A (en) * 2008-12-12 2010-06-23 北京化工大学 Closed hole-shaped vacuum foam for heat insulation and sound insulation and method for preparing same
CN105237673A (en) * 2015-10-19 2016-01-13 陕西理工学院 Method for casting PMMA board under room temperature polymerization condition and spraying polymerization device
CN105315595A (en) * 2015-11-17 2016-02-10 陕西理工学院 Waste plastic recycling method
CN106566156A (en) * 2016-11-02 2017-04-19 武汉理工大学 Preparation method of graphene nanobelt/PMMA microcellular foam nanocomposite

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