CN105037930A - Foamed polypropylene-high molecular absorbent composite material with uniform pore distribution, and preparation method thereof - Google Patents

Foamed polypropylene-high molecular absorbent composite material with uniform pore distribution, and preparation method thereof Download PDF

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Publication number
CN105037930A
CN105037930A CN201510389446.2A CN201510389446A CN105037930A CN 105037930 A CN105037930 A CN 105037930A CN 201510389446 A CN201510389446 A CN 201510389446A CN 105037930 A CN105037930 A CN 105037930A
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parts
composite material
high molecular
absorbent composite
warming
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Inventor
沈向洋
吴克
余志敏
蒋涌
吴杰
吴育兵
樊云
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ANHUI CHENGFANG NEW MATERIAL TECHNOLOGY Co Ltd
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ANHUI CHENGFANG NEW MATERIAL TECHNOLOGY Co Ltd
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Priority to CN201510389446.2A priority Critical patent/CN105037930A/en
Publication of CN105037930A publication Critical patent/CN105037930A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-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
    • C08J9/10Working-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
    • C08J9/102Azo-compounds
    • C08J9/103Azodicarbonamide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/30Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/04N2 releasing, ex azodicarbonamide or nitroso compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/06CO2, N2 or noble gases
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/14Applications used for foams
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)

Abstract

The invention discloses a foamed polypropylene-high molecular absorbent composite material with uniform pore distribution. The foamed polypropylene-high molecular absorbent composite material is prepared from, by weight, 95 to 98 parts of high melt strength polypropylene, 2 to 3 parts of low density polyethylene, 2 to 3 parts of 1% silane coupling agent kh550 aqueous solution, 3 to 5 parts of ac foaming agent, 2 to 3 parts of cocoanut active charcoal, 4 to 6 parts of china clay, 1 to 2 parts of zinc oxide, an appropriate amount of deionized water, 4 to 5 parts of methyl cellulose, 13 to 15 parts of butyl acrylate, 7.5 to 9 parts of decyl methacrylate, 0.08 to 0.1 part of N,N-methylenebisacrylamide, 0.5 to 0.6 part of azodiisobutyronitrile, 11 to 12.5 parts of ethyl acetate, and 2 to 3 parts of di(isooctyl) phosphate. The foamed polypropylene-high molecular absorbent composite material is excellent in overall oil absorptiveness; a preparation method is simple; and application prospect in water surface floating oil recycling is promising.

Description

A kind of uniform expanded polypropylene of distribution of cells and polymeric absorbent matrix material and preparation method thereof
Technical field
The present invention relates to Material Field, particularly the uniform expanded polypropylene of a kind of distribution of cells and polymeric absorbent matrix material and preparation method thereof.
Background technology
Current global waters problem of environmental pollution is on the rise, and wherein oily substance and sewage thereof, waste liquid and the water resource pollution problem such as river, ocean that causes as oil carrier or tank leak because of various accident are on the rise, urgently effectively containment and solving.
Oil absorption material mainly can be divided into three major types, i.e. inorganic oil absorption material, organic synthesis oil absorption material and organic natural oil absorption material.Expanded polypropylene foam is a kind of high crystallization composite material of performance brilliance, compared with other TPO, polypropylene has higher rigidity, excellent mechanical property, good thermotolerance and chemical stability are the excellent materials for industrial uses such as filtering separation, not only recyclable recycling, and can natural degradation, can not white pollution be caused, thus be called as " green " foam.Polypropylene foam, due to its good mechanical property, excellent resistance toheat and the character being beneficial to environment protection, is the foam materials of new generation after traditional polystyrene foam, polyurethane foam and polyethylene, has a wide range of applications.But this material is as sorbing material, have some shortcomings, such as there is gravity, to protect oily rate lower, after absorbing, extruding is leaked again, and due to vesicular structure, specific surface area is large, the volatility of absorbed high volatile volatile liquid cannot be suppressed, undesirable etc. to poisonous explosive chemical treatments effect.Methyl acrylic ester high oil absorbing resin is one of the study hotspot in oil absorption material field in recent years, methyl acrylic ester high oil absorbing resin is the function that Van der Waals force by producing between the oleophilic group in molecular chain and oil molecule realizes oil suction, oil product difficult drop-off after resin material oil suction, protect oily rate high, the advantage of oil-absorbing resin with expanded polypropylene foam combines by imagination, propose in expandable polypropylene resin process, polyacrylic resin to be cross-linked wherein, in order to improve material Oil keeping energy, novel material has just possessed the two-fold advantage of physical adsorption and chemical absorption.
Summary of the invention
The object of this invention is to provide the uniform expanded polypropylene of a kind of distribution of cells and polymeric absorbent matrix material and preparation method thereof.The present invention add appropriate Low Density Polyethylene and high melt strength, propylene blended, after crosslinked with the melting of polyacrylic acid polymer resin microspheres, by chemistry, physics is composite foamed, macromolecule resin is evenly distributed on the hole wall of expanded polypropylene, obtains uniform foam cell, oil suction is quick, oil suction multiplying power is high, protect the high novel material of oily rate.
In order to realize object of the present invention, the present invention is by following scheme implementation:
A kind of uniform expanded polypropylene of distribution of cells and polymeric absorbent matrix material, be made up of the raw material of following weight part: high melt strength, propylene 95-98, Low Density Polyethylene 2-3,1% the silane coupling agent kh550 aqueous solution 2-3, ac whipping agent 3-5, cocoanut active charcoal 2-3, potter's clay 4-6, zinc oxide 1-2, deionized water appropriate, methylcellulose gum 4-5, butyl acrylate 13-15, lauryl methacrylate 7.5-9, N, N ,-methylene-bisacrylamide 0.08-0.1, Diisopropyl azodicarboxylate 0.5-0.6, ethyl acetate 11-12.5, di (isooctyl) phosphate 2-3;
The uniform expanded polypropylene of a kind of distribution of cells of the present invention and polymeric absorbent matrix material, be made up of following concrete steps:
(1) methylcellulose gum is added in the deionized water of 30 times amount, be heated to while stirring dissolve completely, after being cooled to room temperature, add ethyl acetate, N, N slowly successively under nitrogen protection ,-methylene-bisacrylamide, Diisopropyl azodicarboxylate, butyl acrylate, lauryl methacrylate, di (isooctyl) phosphate, controlling stirring velocity is 1000 revs/min, then 40 DEG C are slowly warming up to, stirring reaction is after 10 minutes, continue to be warming up to 70 DEG C, stirring reaction is after 20 minutes, continue to be warming up to 80 DEG C, with the speed stirring reaction 1 hour of 400 revs/min, obtain microspheres with solid, reaction system is down to room temperature, the microspheres with solid obtained is filtered, with 80 DEG C of deionized water wash 3 times, the finally dry subtree lipoid microsphere that namely secures satisfactory grades for 24 hours at 50 DEG C;
(2) potter's clay is put into stirrer with after the silane coupling agent kh550 aqueous solution of 1%, baking oven is put into dry after filtering after stirring 30 minutes with the speed of 300 revs/min, cocoanut active charcoal is ground into after 100 order powder with process after potter's clay, ball mill is put into after ac whipping agent mixes, take out after 15-20 minute with the temperature ball milling of 60-70 DEG C, with Low Density Polyethylene, zinc oxide is put into high-speed mixer and is mixed, then modified particles is obtained by forcing machine extruding pelletization, controlling forcing machine extrusion temperature is 100-120 DEG C, screw speed is 300-400 rev/min,
(3) put in the hopper of Bitruder after polymer resin microspheres mixing high melt strength, propylene, foaming modification particle and step (1) obtained, extruding machine starts screw rod knob after being warming up to 180-200 DEG C, plastify mixing 120-150 minute, carry out first time foaming; After cylindrical shell interruption mixture has melted plasticizing evenly, carbon dioxide (add-on being controlled carbonic acid gas by flowrate control valve is 10% of melting materials capable quality) is injected under 10-15MPa condition, keep after 40-50 minute, then be down to normal pressure, then foam; By the melt extrusion plastified, the temperature controlling extruder head is 200-210 DEG C, can obtain sidewall and be covered with microporous foam pipe, can prepare the particle of expanded polypropylene and macromolecule resin compound after air natural cooling with special dicing machine pelletizing.
The invention has the beneficial effects as follows: first the present invention prepares polymer resin microspheres, then by a series of technique by ac whipping agent, potter's clay, cocoanut active charcoals etc. activate, reduce the decomposition temperature of whipping agent, do not affect gas forming amount simultaneously, enable to be decomposed to form abscess smoothly and faster in injection moulding process, foam structure is stablized, then with polypropylene, polymer resin microspheres puts into extruding machine fusing plasticizing jointly, pass through chemical foaming, pass into the matrix material that the physical blowings such as carbonic acid gas make open cell type, there is larger specific surface area, improve absorption property.
The present invention and the expanded polypropylene foam after polymeric absorbent compound are compared with common expanded polypropylene foam, have more good treatment effect, there is good absorption multiplying power and evenly fine and closely woven abscess, reason adds the appropriate composition such as potter's clay, cocoanut active charcoal inherently to have good absorption property, the structure of modified expanded polypropylene there occurs some changes, thus enhances absorption property.The overall oil absorptiveness of the present invention is better, preparation method simple, in the recycling of oil slick, have great application prospect.
Specific embodiments
Below by specific examples, the present invention is described in detail.
A kind of uniform expanded polypropylene of distribution of cells and polymeric absorbent matrix material, be made up of the raw material of following weight part (kilogram): the silane coupling agent kh550 aqueous solution 2 of high melt strength, propylene 95, Low Density Polyethylene 2,1%, ac whipping agent 3, cocoanut active charcoal 2, potter's clay 4, zinc oxide 1, deionized water are appropriate, methylcellulose gum 4, butyl acrylate 13, lauryl methacrylate 7.5, N, N ,-methylene-bisacrylamide 0.08, Diisopropyl azodicarboxylate 0.5, ethyl acetate 11, di (isooctyl) phosphate 2;
The uniform expanded polypropylene of a kind of distribution of cells of the present invention and polymeric absorbent matrix material, be made up of following concrete steps:
(1) methylcellulose gum is added in the deionized water of 30 times amount, be heated to while stirring dissolve completely, after being cooled to room temperature, add ethyl acetate, N, N slowly successively under nitrogen protection ,-methylene-bisacrylamide, Diisopropyl azodicarboxylate, butyl acrylate, lauryl methacrylate, di (isooctyl) phosphate, controlling stirring velocity is 1000 revs/min, then 40 DEG C are slowly warming up to, stirring reaction is after 10 minutes, continue to be warming up to 70 DEG C, stirring reaction is after 20 minutes, continue to be warming up to 80 DEG C, with the speed stirring reaction 1 hour of 400 revs/min, obtain microspheres with solid, reaction system is down to room temperature, the microspheres with solid obtained is filtered, with 80 DEG C of deionized water wash 3 times, the finally dry subtree lipoid microsphere that namely secures satisfactory grades for 24 hours at 50 DEG C;
(2) potter's clay is put into stirrer with after the silane coupling agent kh550 aqueous solution of 1%, baking oven is put into dry after filtering after stirring 30 minutes with the speed of 300 revs/min, cocoanut active charcoal is ground into after 100 order powder with process after potter's clay, ball mill is put into after ac whipping agent mixes, take out after 15 minutes with the temperature ball milling of 60-70 DEG C, with Low Density Polyethylene, zinc oxide is put into high-speed mixer and is mixed, then modified particles is obtained by forcing machine extruding pelletization, controlling forcing machine extrusion temperature is 100-120 DEG C, screw speed is 300 revs/min,
(3) put in the hopper of Bitruder after polymer resin microspheres mixing high melt strength, propylene, foaming modification particle and step (1) obtained, extruding machine starts screw rod knob after being warming up to 180-200 DEG C, plastify mixing 120 minutes, carry out first time foaming; After cylindrical shell interruption mixture has melted plasticizing evenly, under 10MPa condition, inject carbon dioxide (add-on being controlled carbonic acid gas by flowrate control valve is 10% of melting materials capable quality), keep after 40 minutes, then be down to normal pressure, then foam; By the melt extrusion plastified, the temperature controlling extruder head is 200-210 DEG C, can obtain sidewall and be covered with microporous foam pipe, can prepare the particle of expanded polypropylene and macromolecule resin compound after air natural cooling with special dicing machine pelletizing.
Detect matrix material of the present invention, result is specific absorption (0# diesel oil) 91.0%, specific absorption (trichloroethane) 89.9%; Protect oily rate (0# diesel oil) 85.6%, protect oily rate (trichloroethane) 82.7%, be far longer than inspecting standard.

Claims (2)

1. the uniform expanded polypropylene of distribution of cells and polymeric absorbent matrix material, it is characterized in that, be made up of the raw material of following weight part: high melt strength, propylene 95-98, Low Density Polyethylene 2-3,1% the silane coupling agent kh550 aqueous solution 2-3, ac whipping agent 3-5, cocoanut active charcoal 2-3, potter's clay 4-6, zinc oxide 1-2, deionized water appropriate, methylcellulose gum 4-5, butyl acrylate 13-15, lauryl methacrylate 7.5-9, N, N ,-methylene-bisacrylamide 0.08-0.1, Diisopropyl azodicarboxylate 0.5-0.6, ethyl acetate 11-12.5, di (isooctyl) phosphate 2-3.
2. the uniform expanded polypropylene of a kind of distribution of cells and polymeric absorbent matrix material according to claim 1, is characterized in that, be made up of following concrete steps:
(1) methylcellulose gum is added in the deionized water of 30 times amount, be heated to while stirring dissolve completely, after being cooled to room temperature, add ethyl acetate, N, N slowly successively under nitrogen protection ,-methylene-bisacrylamide, Diisopropyl azodicarboxylate, butyl acrylate, lauryl methacrylate, di (isooctyl) phosphate, controlling stirring velocity is 1000 revs/min, then 40 DEG C are slowly warming up to, stirring reaction is after 10 minutes, continue to be warming up to 70 DEG C, stirring reaction is after 20 minutes, continue to be warming up to 80 DEG C, with the speed stirring reaction 1 hour of 400 revs/min, obtain microspheres with solid, reaction system is down to room temperature, the microspheres with solid obtained is filtered, with 80 DEG C of deionized water wash 3 times, the finally dry subtree lipoid microsphere that namely secures satisfactory grades for 24 hours at 50 DEG C;
(2) potter's clay is put into stirrer with after the silane coupling agent kh550 aqueous solution of 1%, baking oven is put into dry after filtering after stirring 30 minutes with the speed of 300 revs/min, cocoanut active charcoal is ground into after 100 order powder with process after potter's clay, ball mill is put into after ac whipping agent mixes, take out after 15-20 minute with the temperature ball milling of 60-70 DEG C, with Low Density Polyethylene, zinc oxide is put into high-speed mixer and is mixed, then modified particles is obtained by forcing machine extruding pelletization, controlling forcing machine extrusion temperature is 100-120 DEG C, screw speed is 300-400 rev/min,
(3) put in the hopper of Bitruder after polymer resin microspheres mixing high melt strength, propylene, foaming modification particle and step (1) obtained, extruding machine starts screw rod knob after being warming up to 180-200 DEG C, plastify mixing 120-150 minute, carry out first time foaming; After cylindrical shell interruption mixture has melted plasticizing evenly, carbon dioxide (add-on being controlled carbonic acid gas by flowrate control valve is 10% of melting materials capable quality) is injected under 10-15MPa condition, keep after 40-50 minute, then be down to normal pressure, then foam; By the melt extrusion plastified, the temperature controlling extruder head is 200-210 DEG C, can obtain sidewall and be covered with microporous foam pipe, can prepare the particle of expanded polypropylene and macromolecule resin compound after air natural cooling with special dicing machine pelletizing.
CN201510389446.2A 2015-07-06 2015-07-06 Foamed polypropylene-high molecular absorbent composite material with uniform pore distribution, and preparation method thereof Pending CN105037930A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106380693A (en) * 2016-09-21 2017-02-08 苏州佰思科节能环保科技有限公司 Glass-fiber-added composite absorbing material and preparation method thereof
CN106378107A (en) * 2016-09-21 2017-02-08 苏州佰思科节能环保科技有限公司 Composite material for rapidly absorbing petroleum pollutant and preparation method thereof
CN106633583A (en) * 2016-09-21 2017-05-10 苏州佰思科节能环保科技有限公司 Compound oil absorption material with excellent degradation property and preparation method thereof
CN106674739A (en) * 2016-12-22 2017-05-17 阜阳市三郁包装材料有限公司 Hybridized PAN silica aerogel modified flame-retardant polypropylene foaming plate and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101092500A (en) * 2007-07-20 2007-12-26 唐山市福恩特防腐电气控制设备有限公司 Polypropylene material with high bath strength and preparation method
CN102702560A (en) * 2012-06-26 2012-10-03 重庆鸿岱科技有限公司 Compound foaming manufacturing method for polypropylene foaming material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101092500A (en) * 2007-07-20 2007-12-26 唐山市福恩特防腐电气控制设备有限公司 Polypropylene material with high bath strength and preparation method
CN102702560A (en) * 2012-06-26 2012-10-03 重庆鸿岱科技有限公司 Compound foaming manufacturing method for polypropylene foaming material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106380693A (en) * 2016-09-21 2017-02-08 苏州佰思科节能环保科技有限公司 Glass-fiber-added composite absorbing material and preparation method thereof
CN106378107A (en) * 2016-09-21 2017-02-08 苏州佰思科节能环保科技有限公司 Composite material for rapidly absorbing petroleum pollutant and preparation method thereof
CN106633583A (en) * 2016-09-21 2017-05-10 苏州佰思科节能环保科技有限公司 Compound oil absorption material with excellent degradation property and preparation method thereof
CN106674739A (en) * 2016-12-22 2017-05-17 阜阳市三郁包装材料有限公司 Hybridized PAN silica aerogel modified flame-retardant polypropylene foaming plate and preparation method thereof

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