CN105732860B - The expandable polystyrene bead and preparation method of inflatable few layer graphene - Google Patents
The expandable polystyrene bead and preparation method of inflatable few layer graphene Download PDFInfo
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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
- C08F112/00—Homopolymers 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
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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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
- C08J9/16—Making expandable particles
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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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
- C08J2325/00—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
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to the expandable polystyrene beads and preparation method of a kind of inflatable few layer graphene, electrochemical intercalation is carried out to natural flake graphite with the concentrated sulfuric acid, obtain the compound between graphite layers that interlamellar spacing becomes larger, few layer graphene is obtained by ultrasonic vibration delamination, secondary intercalation, washing, drying are carried out to it by chemical method, inflatable few layer graphene is made, few layer graphene and polystyrene monomers suspension polymerisation will be may expand again, the expandable polystyrene bead of inflatable layer graphene less is made.Expandable few layer graphene is introduced expandable polystyrene by the present invention, expansible graphite alkene high uniformity in expandable polystyrene bead disperses, to guarantee the infrared reflective in the cavity inner height of expandable polystyrene, heat-proof quality is good, the flame retardant effect that inflatable few layer graphene can show asphyxia flame again, completely cut off heat radiation.B1 grades are reached by the flame retardant rating of foam board produced by the present invention, heat conductivity value is 0.028~0.032W/ (mK).
Description
Technical field
The present invention relates to a kind of polystyrene foamed material, especially high fire-retardance, low thermally conductive containing may expand few layer graphite
The expandable polystyrene bead and preparation method of alkene.
Background technique
Polystyrene foamed material be by the expandable polystyrene bead containing volatile fluid foaming agent, it is heated pre-
It sends out.Because it is with good properties of heat preservation and energy saving, therefore it is widely used in the fields such as building materials, packaging.
In order to obtain better fire-retardant, heat insulating effect:
CN104231461A disclose a kind of " graphite EPS bead and its production technology " by granules of polystyrene, foaming agent,
The modified graphite powder in surface and fire retardant are mixed and made into graphite EPS bead.Since the graphite mixed is common graphite, number of plies mistake
More, dispersibility is bad, easily assembles, and causing it to reflect, the level of infrared ray is insufficient, and heat insulation and preservation effect is not ideal enough.
CN103788397A discloses " a kind of preparation method of the fire-retardant expandable polystyrene spherolite of the graphite containing leafing "
It is characterized in that using expansible graphite meet high temperature when graphite layers sharply expansion open, thus reach asphyxia flame, every
The purpose of insulation radiation.But mixed expansible graphite granularity is excessive (generally all in tens microns), dispersibility is bad,
Cause anti-flaming thermal-insulation effect not satisfactory.It is to solve and prepares the easy group of graphitiferous particle expandable polystyrene suspension polymerisation
Poly-, the dispersion of graphite particle in polystyrene is unevenly and the technology of the anti-flaming thermal-insulation performance difference of expandable polystyrene is asked
Topic.The preparation method comprises the following steps: one, in parts by weight claim raw material；Two, the first mixture is prepared；Three, the second mixture is prepared；Four, will
Second mixture is added under stiring into the first mixture, and after reaction, emulsifier is added, and the reaction was continued, and pentane is then added,
Nitrogen is poured in a kettle, heat up and is reacted, and after the reaction was completed, by reaction kettle natural cooling, being slowly deflated to pressure is zero
When discharge, the dry fire-retardant expandable polystyrene spherolite to get the graphite containing leafing of washing
CN103819597A disclose a kind of " preparation method of the expandable polystyrene polymer of containing graphene " due to
Graphene majority made from Hummers method belongs to mono-layer graphite, and no longer extruding (interlayer opening) when meeting high temperature does not have asphyxia
The effects of flame, isolation heat radiation and contact with oxygen, so anti-flaming thermal-insulation performance is still unsatisfactory.Solve existing graphite
The preparation method of alkene poly styrene composite material is using graphene as raw material, high, complex process and discomfort so as to cause preparation cost
The problem of closing large-scale industrial production.
Summary of the invention
The object of the invention is that in view of the above shortcomings of the prior art, provide a kind of high fire-retardance, it is low it is thermally conductive can be swollen
The expandable polystyrene bead of swollen few layer graphene；
It is a further object of the present invention to provide a kind of preparations of the expandable polystyrene bead of inflatable few layer graphene
Method.
The purpose of the present invention is what is be achieved through the following technical solutions:
The expandable polystyrene bead of inflatable few layer graphene, be prepared by mass percentage by following substance and
At:
Wherein, inflatable few layer graphene is prepared by the following steps:
A, the preparation of compound between graphite layers: using the natural flake graphite that average grain diameter is 1000-5000 mesh as anode, gold
Belong to titanium sheet as cathode, the concentrated sulfuric acid for being 98% using concentration carries out electrochemical intercalation as intercalator under 1.8V voltage, when intercalation
Between be 0.5-2.0 hour, obtained compound between graphite layers；
B, the preparation of few layer graphene: above-mentioned compound between graphite layers in the concentrated sulfuric acid solution that concentration is 98%, in
Implement ultrasonic vibration under 1000W power to remove 0.5-1.5 hours, few layer graphene is made；
C, it may expand the preparation of few layer graphene: using the concentrated sulfuric acid of concentration 98% as intercalator, the peroxidating of concentration 30%
Hydrogen is oxidant, lacks layer graphene to above-mentioned gained at room temperature and carries out chemical method secondary intercalation, the time is 30 minutes；So
Afterwards, the product after intercalation is washed to pH value 4-6 and is dried 2 hours at 100 DEG C again, obtain inflatable few layer graphene.
The preparation method of the expandable polystyrene bead of inflatable few layer graphene, comprising the following steps:
A, the preparation of compound between graphite layers: using the natural flake graphite that average grain diameter is 1000-5000 mesh as anode, gold
Belong to titanium sheet as cathode, the concentrated sulfuric acid for being 98% using concentration carries out electrochemical intercalation as intercalator under 1.8V voltage, when intercalation
Between be 0.5-2.0 hour, obtained compound between graphite layers；
B, the preparation of few layer graphene: above-mentioned compound between graphite layers in the concentrated sulfuric acid solution that concentration is 98%, in
Implement ultrasonic vibration under 1000W power to remove 05-1.5 hours, few layer graphene is made；
C, it may expand the preparation of few layer graphene: using the concentrated sulfuric acid of concentration 98% as intercalator, the peroxidating of concentration 30%
Hydrogen is oxidant, lacks layer graphene to above-mentioned gained at room temperature and carries out chemical method secondary intercalation, the time is 30 minutes；So
Afterwards, the product after intercalation is washed to pH value 4-6 and is dried 2 hours at 100 DEG C again, obtain inflatable few layer graphene；
D, the preparation of the expandable polystyrene bead of containing graphene: by 13.8-17.3% styrene of mass percent,
In 3.5-5.5% inflatable few layer graphene and 76-77% deionized water investment reaction kettle, mechanical stirring 30min, stirring speed
Degree is kept for 210~300 revs/min；Put into 0.52-1.1% inorganic dispersant calcium hydroxy phosphate and 0.03-0.05% organic dispersion
Agent polyvinyl alcohol, 0.3-4.0% benzoyl peroxide, when the temperature of charge in reaction kettle rises to 87~90 DEG C, in this temperature
Lower polymerization reaction 6~11 hours；0.2~0.8% calcium hydroxy phosphate and 0.35-0.55% foaming agent are added, is continued to reaction
Kettle heating；When the temperature of charge in reaction kettle rises to 110~135 DEG C, constant temperature is kept for 3~5 hours；By the material in reaction kettle
It takes out and is filtered, obtain granular material；It is 1-3 hours dry by 30~50 DEG C of pneumatic drier, obtain containing graphene
Polystyrene bead.
The utility model has the advantages that be that will may expand few layer of graphene to be introduced into the synthesis of expandable polystyrene, the nanoscale of preparation
Expansible graphite alkene can disperse high uniformity in expandable polystyrene bead, to guarantee in expandable polystyrene
The infrared reflective of cavity inner height obtains good heat-proof quality, while inflatable few layer graphene can show to suffocate again
The flame retardant effect that flame, isolation radiate.
The polystyrene bead of containing graphene prepared by the present invention is subjected to foaming processing, obtains foam board.It adopts
Flame retardant rating test is carried out with standard GB/T 8624-2006, thermal conductivity test is carried out using national military standard GJB1875-94.By
The flame retardant rating of foam board produced by the present invention reaches B1 grades, and heat conductivity value is 0.028~0.032W/ (mk)
Detailed description of the invention:
Fig. 1 is the shape appearance figure of multilayer expansible graphite alkene.
Specific embodiment
It is described in further detail with reference to the accompanying drawings and examples
The expandable polystyrene bead of inflatable few layer graphene, be prepared by mass percentage by following substance and
At:
The preparation method of the expandable polystyrene bead of inflatable few layer graphene, comprising the following steps:
A, the preparation of compound between graphite layers: using the natural flake graphite that average grain diameter is 1000-5000 mesh as anode, gold
Belong to titanium sheet as cathode, the concentrated sulfuric acid for being 98% using concentration carries out electrochemical intercalation as intercalator under 1.8V voltage, when intercalation
Between be 0.5-2.0 hour, obtained compound between graphite layers；
B, the preparation of few layer graphene: above-mentioned compound between graphite layers in the concentrated sulfuric acid solution that concentration is 98%, in
Implement ultrasonic vibration under 1000W power to remove 0.5-1.5 hours, few layer graphene is made；
C, it may expand the preparation of few layer graphene: using the concentrated sulfuric acid of concentration 98% as intercalator, the peroxidating of concentration 30%
Hydrogen is oxidant, lacks layer graphene to above-mentioned gained at room temperature and carries out chemical method secondary intercalation, the time is 30 minutes.So
Afterwards, the product after intercalation is washed to pH value 4-6 and is dried 2 hours at 100 DEG C again, obtain inflatable few layer graphene；
D, the preparation of the expandable polystyrene bead of containing graphene: by 13.8-17.3% styrene of mass percent,
In 0.3-4.0% benzoyl peroxide and 3.5-5.5% inflatable few layer graphene investment reaction kettle, mechanical stirring 30min,
Mixing speed is kept for 210~300 revs/min；Investment 0.52-1.1% inorganic dispersant calcium hydroxy phosphate and 0.03-0.05% has
Machine polyethylene of dispersing agent alcohol, when the temperature of charge in reaction kettle rises to 87~90 DEG C, polymerization reaction 6~11 is small at this temperature
When；0.2~0.8% calcium hydroxy phosphate and 0.35-0.55% foaming agent are added, continues to heat reaction kettle；When in reaction kettle
When temperature of charge rises to 110~135 DEG C, constant temperature is kept for 3~5 hours；Material in reaction kettle is taken out and is filtered, is obtained
To granular material；It is 1-3 hours dry by 30~50 DEG C of pneumatic drier, obtain the polystyrene bead of containing graphene.
Embodiment 1
A, the preparation of compound between graphite layers: using the natural flake graphite that average grain diameter is 1000 mesh as anode, Titanium
For piece as cathode, the concentrated sulfuric acid for being 98% using concentration carries out electrochemical intercalation as intercalator under 1.8V voltage, and the intercalation time is
2.0 hours, compound between graphite layers are made.
B, the preparation of few layer graphene: above-mentioned compound between graphite layers in the concentrated sulfuric acid solution that concentration is 98%, in
Implement ultrasonic vibration under 1000W power to remove 1.5 hours, few layer graphene is made.
C, it may expand the preparation of few layer graphene: using the concentrated sulfuric acid of concentration 98% as intercalator, the peroxide of concentration 30%
Change hydrogen as oxidant, layer graphene is lacked to above-mentioned gained at room temperature and carries out chemical method secondary intercalation, the time is 30 points
Clock.Then, the product after intercalation is washed to pH value 6 and is dried 2 hours at 100 DEG C again, obtain inflatable few layer graphite
Alkene.
D, the molten of 10 grams of styrene monomers the preparation of the polystyrene bead of containing graphene: is sequentially added in four-hole bottle
Liquid, the inflatable few layer graphene of 2g, 45 milliliters of deionized water, mechanical stirring 30min, mixing speed is kept for 210 revs/min.Investment
0.25g inorganic dispersant calcium hydroxy phosphate and 0.025 gram of organic dispersing agent polyvinyl alcohol and benzoyl peroxide 0.17g.When anti-
When the temperature of charge in kettle being answered to rise to 90 DEG C, polymerization reaction 6 hours at this temperature；0.2g calcium hydroxy phosphate and 0.2g are added again
Foaming agent continues to heat reaction kettle；When the temperature of charge in reaction kettle rises to 110~135 DEG C, constant temperature holding 3~5 is small
When；Material in reaction kettle is taken out and is filtered, granular material is obtained；By the drying 3 hours of 30 DEG C of pneumatic drier, obtain
To the polystyrene bead of containing graphene.
Embodiment 2
A, the preparation of compound between graphite layers: using the natural flake graphite that average grain diameter is 3000 mesh as anode, Titanium
For piece as cathode, the concentrated sulfuric acid for being 98% using concentration carries out electrochemical intercalation as intercalator under 1.8V voltage, and the intercalation time is
1.0 hours, compound between graphite layers are made.
B, the preparation of few layer graphene: above-mentioned compound between graphite layers in the concentrated sulfuric acid solution that concentration is 98%, in
Implement ultrasonic vibration under 1000W power to remove 1.0 hours, few layer graphene is made.
C, it may expand the preparation of few layer graphene: using the concentrated sulfuric acid of concentration 98% as intercalator, the peroxide of concentration 30%
Change hydrogen as oxidant, layer graphene is lacked to above-mentioned gained at room temperature and carries out chemical method secondary intercalation, the time is 30 points
Clock.Then, the product after intercalation is washed to pH value 5 and is dried 2 hours at 100 DEG C again, obtain inflatable few layer graphite
Alkene.
D, the molten of 10 grams of styrene monomers the preparation of the polystyrene bead of containing graphene: is sequentially added in four-hole bottle
Liquid, the inflatable few layer graphene of 3g, 50 milliliters of deionized water, mechanical stirring 30min, mixing speed is kept for 250 revs/min.Investment
0.35g inorganic dispersant calcium hydroxy phosphate and 0.025 gram of organic dispersing agent polyvinyl alcohol and benzoyl peroxide 2.0g.Work as reaction
When temperature of charge in kettle rises to 90 DEG C, polymerization reaction 7 hours at this temperature；0.2g calcium hydroxy phosphate and 0.3g hair are added again
Infusion continues to heat reaction kettle；When the temperature of charge in reaction kettle rises to 115 DEG C, constant temperature is kept for 4 hours；By reaction kettle
Interior material takes out and is filtered, and obtains granular material；By the drying 2 hours of 40 DEG C of pneumatic drier, containing graphene is obtained
Polystyrene bead.
Embodiment 3
A, the preparation of compound between graphite layers: using the natural flake graphite that average grain diameter is 5000 mesh as anode, Titanium
For piece as cathode, the concentrated sulfuric acid for being 98% using concentration carries out electrochemical intercalation as intercalator under 1.8V voltage, and the intercalation time is
0.5 hour, compound between graphite layers are made.
B, that lacks layer graphene prepares above-mentioned compound between graphite layers in the concentrated sulfuric acid solution that concentration is 98%, in
Implement ultrasonic vibration under 1000W power to remove 0.5 hour, few layer graphene is made.
C, it may expand the preparation of few layer graphene: using the concentrated sulfuric acid of concentration 98% as intercalator, the peroxide of concentration 30%
Change hydrogen as oxidant, layer graphene is lacked to above-mentioned gained at room temperature and carries out chemical method secondary intercalation, the time is 30 points
Clock.Then, the product after intercalation is washed to pH value 4 and is dried 2 hours at 100 DEG C again, obtain inflatable few layer graphite
Alkene.
D, the molten of 10 grams of styrene monomers the preparation of the polystyrene bead of containing graphene: is sequentially added in four-hole bottle
Liquid, the inflatable few layer graphene of 4g, 55 milliliters of deionized water, mechanical stirring 30min, mixing speed is kept for 280 revs/min.Investment
0.4g inorganic dispersant calcium hydroxy phosphate and 0.03 gram of organic dispersing agent polyvinyl alcohol and benzoyl peroxide 2.3g.Work as reaction kettle
When interior temperature of charge rises to 90 DEG C, polymerization reaction 7 hours at this temperature；0.2g calcium hydroxy phosphate and 0.4g foaming are added again
Agent continues to heat reaction kettle；When the temperature of charge in reaction kettle rises to 115 DEG C, constant temperature is kept for 4 hours；It will be in reaction kettle
Material take out and be filtered, obtain granular material；By the drying 1 hour of 50 DEG C of pneumatic drier, containing graphene is obtained
Polystyrene bead.
Claims (2)
1. a kind of expandable polystyrene bead of inflatable few layer graphene, which is characterized in that be by following substance by quality
Percentage is prepared:
Wherein, inflatable few layer graphene is prepared by the following steps:
A, the preparation of compound between graphite layers: using the natural flake graphite that average grain diameter is 1000-5000 mesh as anode, Titanium
For piece as cathode, the concentrated sulfuric acid for being 98% using concentration carries out electrochemical intercalation as intercalator under 1.8V voltage, and the intercalation time is
0.5-2.0 hours, compound between graphite layers are made；
B, the preparation of few layer graphene: above-mentioned compound between graphite layers are in the concentrated sulfuric acid solution that concentration is 98%, in 1000W function
Implement ultrasonic vibration under rate to remove 0.5-1.5 hours, few layer graphene is made；
C, may expand the preparation of few layer graphene: using the concentrated sulfuric acid of concentration 98% as intercalator, the hydrogen peroxide of concentration 30% is
Oxidant lacks layer graphene to above-mentioned gained at room temperature and carries out chemical method secondary intercalation, and the time is 30 minutes；Then,
Product after intercalation is washed to pH value 4-6 and is dried 2 hours at 100 DEG C again, inflatable few layer graphene is obtained.
2. a kind of preparation method of the expandable polystyrene bead of inflatable few layer graphene, which is characterized in that including following
Step:
A, the preparation of compound between graphite layers: using the natural flake graphite that average grain diameter is 1000-5000 mesh as anode, Titanium
For piece as cathode, the concentrated sulfuric acid for being 98% using concentration carries out electrochemical intercalation as intercalator under 1.8V voltage, and the intercalation time is
0.5-2.0 hours, compound between graphite layers are made；
B, the preparation of few layer graphene: above-mentioned compound between graphite layers are in the concentrated sulfuric acid solution that concentration is 98%, in 1000W function
Implement ultrasonic vibration under rate to remove 0.5-1.5 hours, few layer graphene is made；
C, may expand the preparation of few layer graphene: using the concentrated sulfuric acid of concentration 98% as intercalator, the hydrogen peroxide of concentration 30% is
Oxidant lacks layer graphene to above-mentioned gained at room temperature and carries out chemical method secondary intercalation, and the time is 30 minutes；Then,
Product after intercalation is washed to pH value 4-6 and is dried 2 hours at 100 DEG C again, inflatable few layer graphene is obtained；
D, the preparation of the expandable polystyrene bead of containing graphene: by 13.8-17.3% styrene of mass percent, 3.5-
In 5.5% inflatable few layer graphene and 76-77% deionized water investment reaction kettle, mechanical stirring 30min, mixing speed is kept
210~300 revs/min；Put into 0.52-1.1% inorganic dispersant calcium hydroxy phosphate and the poly- second of 0.03-0.05% organic dispersing agent
Enol, 0.3-4.0% benzoyl peroxide polymerize at this temperature when the temperature of charge in reaction kettle rises to 87~90 DEG C
Reaction 6~11 hours；0.2~0.8% calcium hydroxy phosphate and 0.35-0.55% foaming agent are added, continues to heat reaction kettle；
When the temperature of charge in reaction kettle rises to 110~135 DEG C, constant temperature is kept for 3~5 hours；Material in reaction kettle is taken out simultaneously
It is filtered, obtains granular material；It is 1-3 hours dry by 30~50 DEG C of pneumatic drier, obtain the polyphenyl second of containing graphene
Alkene bead.
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| CN106543475B (en) * | 2016-10-31 | 2018-10-19 | 无锡云亭石墨烯技术有限公司 | A kind of preparation of modified graphene and its application in expandable polystyrene |
| CN106519300B (en) * | 2016-10-31 | 2018-10-02 | 无锡云亭石墨烯技术有限公司 | A kind of preparation of watersoluble modified graphene slurry and application process |
| CN106519091B (en) * | 2016-10-31 | 2018-10-19 | 无锡云亭石墨烯技术有限公司 | A kind of oiliness modified graphene slurry and application thereof |
| CN106752116A (en) * | 2016-11-15 | 2017-05-31 | 吉林省云亭节能技术有限公司 | The preparation method and modified graphene oxide EPS of modified graphene oxide mold the preparation method of styrofoam |
| CN106674783A (en) * | 2016-12-29 | 2017-05-17 | 吉林省云亭节能技术有限公司 | Preparation method of high-strength graphene expandable polystyrene board |
| CN106633458B (en) * | 2016-12-29 | 2019-04-23 | 吉林云亭石墨烯技术股份有限公司 | A kind of preparation method of low thermally conductive nonflammable graphene expandable polystyrene plate |
| CN107337750B (en) * | 2017-05-17 | 2019-09-17 | 无锡兴达泡塑新材料股份有限公司 | A kind of expandable poly-styrene and preparation method thereof |
| CN107442775B (en) * | 2017-07-14 | 2019-03-22 | 成都新柯力化工科技有限公司 | A kind of grapheme foam aluminum composite metal material and preparation method |
| CN107987410B (en) * | 2017-11-29 | 2020-05-22 | 吉林云亭石墨烯技术股份有限公司 | Preparation of graphene EPS master batch and EPS compounding method |
| CN109082018A (en) * | 2018-07-25 | 2018-12-25 | 无锡云亭石墨烯技术有限公司 | A kind of elastic graphite alkene EPS and preparation method thereof |
| CN109942883A (en) * | 2019-04-03 | 2019-06-28 | 西南交通大学 | Utilize interlayer in-situ polymerization graphene/foam of polymers batch preparation |
| CN114957875A (en) * | 2022-07-26 | 2022-08-30 | 江苏舜昶新型建材有限公司 | Polystyrene-graphene composite material and preparation method and application thereof |
| CN115351866A (en) * | 2022-09-09 | 2022-11-18 | 三门峡速达交通节能科技股份有限公司 | Negative oxygen ion pine needle indoor decorative plate and preparation process thereof |
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| WO2014111628A2 (en) * | 2013-01-18 | 2014-07-24 | Styrochem Finland Oy | Method of producing polystyrene beads having low moisture content |
| CN103788397B (en) * | 2014-02-19 | 2016-08-17 | 哈尔滨工业大学 | A kind of preparation method of the fire-retardant expandable polystyrene spherolite containing leafing graphite |
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