CN109082018A - A kind of elastic graphite alkene EPS and preparation method thereof - Google Patents
A kind of elastic graphite alkene EPS and preparation method thereof Download PDFInfo
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- CN109082018A CN109082018A CN201810824746.2A CN201810824746A CN109082018A CN 109082018 A CN109082018 A CN 109082018A CN 201810824746 A CN201810824746 A CN 201810824746A CN 109082018 A CN109082018 A CN 109082018A
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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
- C08J9/12—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
- C08J9/141—Hydrocarbons
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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
- C08J9/0014—Use of organic additives
- C08J9/0033—Use of organic additives 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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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
- C08J9/0066—Use of inorganic compounding ingredients
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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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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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
- 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
- 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
- C08J2423/06—Polyethene
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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
- C08J2429/00—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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The present invention relates to the preparations and application of a kind of elastic graphite alkene EPS, specifically, first by after elastomer ball mill grinding, carry out blending and modifying with graphene, then extruding pelletization, is made graphene elastomer master batch；Then graphene elastomer master batch is added in the EPS system being made of styrene, calcium hydroxy phosphate, surfactant, stabilizer, BPO (dibenzoyl peroxide), foaming agent and deionized water and carries out polymerization reaction, to prepare elastic graphite alkene EPS product.EPS product prepared by the present invention is compared with existing product, ability with certain flexible deformation, furthermore, the EPS is cheap, pass through addition elastomer and graphene, the elastomeric fine quality of EPS high-strength light is assigned, therefore brings huge potential benefit for the application of EPS product, has wide prospect.
Description
Technical field
The present invention relates to the technical fields of the preparation of high molecular polymer and application, and in particular to a kind of to utilize graphene system
The method of standby elastic graphite alkene EPS.
Background technique
Polystyrene foam (Expanded Polystyrene abbreviation EPS) is a kind of light polymer, it is
Foaming agent is added using polystyrene resin, while heating is softened, and is generated gas, is formed a kind of bubble of rigid closed cell structure
Foam plastics.EPS is due to excellent lasting heat insulation property, unique buffering shock resistance, ageing resistance and anti-deionized water
Property, thus be widely used in many fields such as daily life, agricultural, transportation, war industry.
However, contain phenyl ring in EPS, and molecular structure is asymmetric, so that eps foam plastics are integrally in certain rigidity and crisp
Property, do not have elastically-deformable ability, therefore the general resilience of existing EPS is poor, limits EPS to a certain extent one
A little particular needs shock resistances need to have application in certain screen resilience field, such as particular packing industry, such as precision instrument, military
Packaging material, inside gadget, bumper in automobile industry.
Currently, graphene EPS material is mainly to improve the indexs such as intensity and the thermal insulation property of this traditional material of EPS, also
It is not involved with the promotion of EPS other performance especially elasticity aspect.Such as " a kind of oiliness modified graphene slurry and its use
250%-280%, thermal conductivity ratio can be improved than national standard intensity in the graphene EPS molding styrofoam prepared in patent on the way "
032 grade of national standard reduces 13%-16%；Modified graphene in " a kind of graphene deionization aqueous slurry and preparation method thereof "
EPS molds styrofoam intensity and improves 200-230% than national standard, and 032 grade of national standard of thermal conductivity ratio reduces 10-13%.
In summary, how to develop the EPS product that a kind of elasticity is stronger, best in quality is that this field is badly in need of solving at present
Technical problem.
Summary of the invention
The purpose of the present invention is to above-mentioned deficiency in the prior art, provide that a kind of elasticity is good, matter by modified
Excellent EPS product is measured, particular content is as follows:
Present invention firstly provides a kind of elastic graphite alkene EPS, the weight percent of each raw material are as follows:
Elastomer: 0.05%-0.5%；
Graphene 0.1%-1%；
Styrene: 20%-50%；
Calcium hydroxy phosphate: 0.5%-1%；
Surfactant: 0.02%-0.05%；
Stabilizer: 0.02%-0.05%；
BPO (dibenzoyl peroxide): 0.5%-3%；
Foaming agent: 1%-5%；
Deionized water: 30%-75%；
Each raw material total amount is 100%.
Preferably, above-mentioned elastomer is polyurethane elastomeric fiber and/or elastic rubber；
Preferably, above-mentioned graphene is the graphene obtained using chemical method production, and the number of plies is at 10 layers or less；The chemistry
The general chemical method that method is grasped by those skilled in the art, such as: chemical vapour deposition technique, epitaxial growth method and oxidation
Graphite reduction method etc. can carry out polymerization reaction with EPS since the graphene surface of chemical method preparation has various groups；
Preferably, above-mentioned surfactant is polyvinyl alcohol, neopelex, polyethylene wax, hydroxy ethyl fiber
One or more of element；
Preferably, above stabilizer is sodium sulphate and/or sodium hydrogensulfite；
Preferably, above-mentioned foaming agent is pentane.
The present invention also provides the preparation methods of above-mentioned elastic graphite alkene EPS, and steps are as follows:
(1) each raw material is weighed according to weight percent, it is spare；
(2) elastomer is taken, by its ball mill grinding to 1-10 μm；
(3) step (2) treated elastomer and graphene are subjected to blending and modifying；
(4) the mixture extruding pelletization obtained to step (3), is made graphene elastomer master batch；
(5) graphene elastomer master batch made from step (4) is added to by styrene, calcium hydroxy phosphate, surface-active
In the EPS system that agent, stabilizer, BPO (dibenzoyl peroxide), foaming agent and deionized water combine, polymerization reaction is carried out, from
And be made can elastic graphite alkene EPS product.
Specific step is as follows for above-mentioned steps (5) polymerization reaction:
1. styrene, deionized water and graphene elastomer master batch are put into reaction kettle and stirred, time 10-
30min, speed are to keep 100~300r/min；
2. calcium hydroxy phosphate, surfactant, stabilizer, BPO (dibenzoyl peroxide) is added, it is warming up in reaction kettle
Temperature of charge rise to 85~95 DEG C, polymerization reaction 6~12 hours；
3. foaming agent is added to continue to heat, when temperature rises to 115~130 DEG C, constant temperature is kept for 3~8 hours；
4. taking out and being filtered the material in reaction kettle, granular material is obtained；
5. washing is dry to get elastic graphite alkene EPS bead.
The present invention include it is following the utility model has the advantages that
Elastic graphite alkene EPS provided by the present invention, is utilized the characteristic of graphene high-specific surface area, is wrapped up by absorption
A certain amount of elastomer, is then polymerize with EPS, makes graphene elastomer graft on EPS strand, and it is stronger to assign EPS
Elastically-deformable ability；The addition of graphene can be improved the mechanical strength and thermal insulation property index of EPS, avoid elastomer straight
It connects and polymerize with EPS and occur to tie kettle phenomenon.
To sum up, elastic graphite alkene EPS product provided by the present invention compared with existing product there is certain elasticity to become
The ability of shape, furthermore the EPS is cheap, and by the addition of elastomer and graphene, it is elastomeric to assign EPS high-strength light
Performance, therefore huge potential benefit is brought for the application of EPS product, have wide prospect.
Specific embodiment
Below by several embodiments specific embodiment that the present invention will be described in detail, but not to claim of the invention
Do any restriction.
Embodiment 1
(1) each raw material is weighed according to weight percent, spare, concrete component is as follows:
Polyurethane elastomeric fiber: 0.05%；
Graphene 0.1%；
Styrene: 37.81%；
Calcium hydroxy phosphate: 0.5%；
Polyvinyl alcohol: 0.01%；
Neopelex: 0.01%；
Sodium sulphate: 0.02%；
BPO (dibenzoyl peroxide): 0.5%；
Pentane: 1%；
Deionized water: 60%；
(2) take polyurethane elastomeric fiber by its ball mill grinding to 10 μm；
(3) step (2) treated polyurethane elastomeric fiber and graphene are subjected to blending and modifying；
(4) the mixture extruding pelletization obtained to step (3), is made graphene elastomer master batch；
(5) polymerization reaction:
It is stirred 1. graphene elastomer master batch made from styrene, deionized water and step (4) is put into reaction kettle,
Time is 10min, and speed is to keep 300r/min；
2. calcium hydroxy phosphate, polyvinyl alcohol, neopelex, sodium sulphate, BPO (diphenyl peroxide first is added
Acyl), the temperature of charge being warming up in reaction kettle rises to 85 DEG C, polymerization reaction 12 hours；
3. pentane is added to continue to heat, when temperature rises to 115 DEG C, constant temperature is kept for 8 hours；
4. taking out and being filtered the material in reaction kettle, granular material is obtained；
5. washing is dry to get elastic graphite alkene EPS bead.
Embodiment 2
(1) each raw material is weighed according to weight percent, spare, concrete component is as follows:
Elastic rubber: 0.5%；
Graphene 1%；
Styrene: 50%；
Calcium hydroxy phosphate: 1%；
Polyethylene wax: 0.02%；
Hydroxyethyl cellulose: 0.03%；
Sodium hydrogensulfite: 0.05%；
BPO (dibenzoyl peroxide): 3%；
Pentane: 5%；
Deionized water: 39.4%；
(2) take elastic rubber by its ball mill grinding to 1 μm；
(3) step (2) treated elastic rubber and graphene are subjected to blending and modifying；
(4) the mixture extruding pelletization obtained to step (3), is made graphene elastomer master batch；
(5) polymerization reaction:
It is stirred 1. graphene elastomer master batch made from styrene, deionized water and step (4) is put into reaction kettle,
Time is 30min, and speed is to keep 100r/min；
2. calcium hydroxy phosphate, polyethylene wax, hydroxyethyl cellulose, sodium hydrogensulfite, BPO (diphenyl peroxide first is added
Acyl), the temperature of charge being warming up in reaction kettle rises to 95 DEG C, polymerization reaction 6 hours；
3. pentane is added to continue to heat, when temperature rises to 130 DEG C, constant temperature is kept for 3 hours；
4. taking out and being filtered the material in reaction kettle, granular material is obtained；
5. washing is dry to get elastic graphite alkene EPS bead.
Embodiment 3
(1) each raw material is weighed according to weight percent, spare, concrete component is as follows:
Polyurethane elastomeric fiber: 0.14%；
Elastic rubber: 0.15%；
Graphene 0.7%；
Styrene: 20%；
Calcium hydroxy phosphate: 0.75%；
Polyvinyl alcohol: 0.01%；
Neopelex: 0.01%；
Polyethylene wax: 0.01%；
Hydroxyethyl cellulose: 0.01%
Sodium sulphate: 0.02%；
BPO (dibenzoyl peroxide): 2%；
Pentane: 1.2%；
Deionized water: 75%；
(2) take polyurethane elastomeric fiber and elastic rubber by its ball mill grinding to 5 μm；
(3) step (2) treated polyurethane elastomeric fiber and elastic rubber and graphene are subjected to blending and modifying；
(4) the mixture extruding pelletization obtained to step (3), is made graphene elastomer master batch；
(5) polymerization reaction:
It is stirred 1. graphene elastomer master batch made from styrene, deionized water and step (4) is put into reaction kettle,
Time is 20min, and speed is to keep 200r/min；
2. calcium hydroxy phosphate, polyvinyl alcohol, neopelex, polyethylene wax, hydroxyethyl cellulose, sulfuric acid is added
Sodium, BPO (dibenzoyl peroxide), the temperature of charge being warming up in reaction kettle rise to 90 DEG C, polymerization reaction 9 hours；
3. pentane is added to continue to heat, when temperature rises to 125 DEG C, constant temperature is kept for 5 hours；
4. taking out and being filtered the material in reaction kettle, granular material is obtained；
5. washing is dry to get elastic graphite alkene EPS bead.
Embodiment provided above is better embodiment of the invention, only is used to facilitate to illustrate the present invention, not to this hair
It is bright to make any form of restriction, any those of ordinary skill in the art, if not departing from the proposed skill of the present invention
In the range of art feature, using the equivalent embodiment locally changed or modified made by disclosed technology contents, and
Without departing from technical feature content of the invention, in the range of still falling within the technology of the present invention feature.
Claims (9)
1. a kind of elastic graphite alkene EPS, which is characterized in that the weight percent of each raw material are as follows:
Elastomer: 0.05%-0.5%；
Graphene 0.1%-1%；
Styrene: 20%-50%；
Calcium hydroxy phosphate: 0.5%-1%；
Surfactant: 0.02%-0.05%；
Stabilizer: 0.02%-0.05%；
BPO (dibenzoyl peroxide): 0.5%-3%；
Foaming agent: 1%-5%；
Deionized water: 30%-75%；
Each raw material total amount is 100%.
2. elastic graphite alkene EPS according to claim 1, which is characterized in that the weight percent of each raw material are as follows:
Elastomer: 0.1%-0.4%；
Graphene 0.3%-0.8%；
Styrene: 30%-40%；
Calcium hydroxy phosphate: 0.6%-0.8%；
Surfactant: 0.02%-0.05%；
Stabilizer: 0.02%-0.05%；
BPO (dibenzoyl peroxide): 1%-2%；
Foaming agent: 1%-5%；
Deionized water: 40%-60%；
Each raw material total amount is 100%.
3. elastic graphite alkene EPS according to claim 1 or 2, which is characterized in that the elastomer is polyurethane elastomer
Fiber and/or elastic rubber.
4. elastic graphite alkene EPS according to claim 1 or 2, which is characterized in that the graphene is raw using chemical method
The graphene obtained is produced, the number of plies is at 10 layers or less.
5. elastic graphite alkene EPS according to claim 1 or 2, which is characterized in that the surfactant is polyethylene
One or more of alcohol, neopelex, polyethylene wax, hydroxyethyl cellulose.
6. elastic graphite alkene EPS according to claim 1 or 2, which is characterized in that the stabilizer be sodium sulphate and/or
Sodium hydrogensulfite.
7. the preparation method of elastic graphite alkene EPS described in a kind of any of the above-described claim, which is characterized in that step is such as
Under:
(1) each raw material is weighed according to weight percent, it is spare；
(2) elastomer is taken, by its ball mill grinding；
(3) step (2) treated elastomer and graphene are subjected to blending and modifying；
(4) the mixture extruding pelletization obtained to step (3), is made graphene elastomer master batch；
(5) graphene elastomer master batch made from step (4) is added to by styrene, calcium hydroxy phosphate, surfactant, steady
In the EPS system for determining agent, BPO (dibenzoyl peroxide), foaming agent and deionized water combination, polymerization reaction is carried out, to make
At elastic graphite alkene EPS product.
8. preparation method according to claim 7, which is characterized in that ball mill grinding is to 1-10 μm in the step (2).
9. preparation method according to claim 7, which is characterized in that the specific steps of polymerization reaction in the step (5)
Are as follows:
1. styrene, deionized water and graphene elastomer master batch are put into reaction kettle and stirred, time 10-30min, speed
Degree is 100~300r/min；
2. calcium hydroxy phosphate, surfactant, stabilizer, BPO (dibenzoyl peroxide), the object being warming up in reaction kettle is added
Material temperature degree rises to 85~95 DEG C, polymerization reaction 6~12 hours；
3. foaming agent is added to continue to heat, when temperature rises to 115~130 DEG C, constant temperature is kept for 3~8 hours；
4. taking out and being filtered the material in reaction kettle, granular material is obtained；
5. washing is dry to get elastic graphite alkene EPS bead.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995430A (en) * | 2020-09-02 | 2020-11-27 | 江苏筑立建筑科技有限公司 | Graphene modified silicalite insulation board and manufacturing method thereof |
| CN113416340A (en) * | 2021-07-29 | 2021-09-21 | 重庆中科建筑科技(集团)有限公司 | Preparation method of modified graphene EPS (expandable polystyrene) particles and mortar and modified graphene EPS mortar |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348665A (en) * | 2015-12-11 | 2016-02-24 | 绍兴文理学院元培学院 | Composite TPU and EPS expandable resin and preparing method thereof |
| CN105732860A (en) * | 2016-02-04 | 2016-07-06 | 吉林省云亭节能技术有限公司 | Expandable polystyrene beads prepared from expandable few-layer graphene and preparing method of expandable polystyrene beads |
| CN108164853A (en) * | 2018-01-29 | 2018-06-15 | 厦门派探特环保科技有限公司 | A kind of novel environment friendly expanded material and preparation method thereof and foam process |
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2018
- 2018-07-25 CN CN201810824746.2A patent/CN109082018A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348665A (en) * | 2015-12-11 | 2016-02-24 | 绍兴文理学院元培学院 | Composite TPU and EPS expandable resin and preparing method thereof |
| CN105732860A (en) * | 2016-02-04 | 2016-07-06 | 吉林省云亭节能技术有限公司 | Expandable polystyrene beads prepared from expandable few-layer graphene and preparing method of expandable polystyrene beads |
| CN108164853A (en) * | 2018-01-29 | 2018-06-15 | 厦门派探特环保科技有限公司 | A kind of novel environment friendly expanded material and preparation method thereof and foam process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995430A (en) * | 2020-09-02 | 2020-11-27 | 江苏筑立建筑科技有限公司 | Graphene modified silicalite insulation board and manufacturing method thereof |
| CN113416340A (en) * | 2021-07-29 | 2021-09-21 | 重庆中科建筑科技(集团)有限公司 | Preparation method of modified graphene EPS (expandable polystyrene) particles and mortar and modified graphene EPS mortar |
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Application publication date: 20181225 |