CN108299752A - A kind of halogen-free flameproof PE/PS alloy materials and preparation method thereof - Google Patents
A kind of halogen-free flameproof PE/PS alloy materials and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/22—Halogen free composition
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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Abstract
The invention discloses a kind of halogen-free flameproof PE/PS alloy materials and preparation method thereof.A kind of halogen-free flameproof PE/PS alloy materials, include following components by mass fraction：Polyethylene 20~40%；Polystyrene 30~50%；Compound bulking agent 5~10%；Halogen-free flame retardants 15~30%；Siliceous inorganic particle 2~10%；Processing aid 0.5~3%.Also disclose a kind of preparation method of halogen-free flameproof PE/PS alloy materials.The PE/PS alloy materials of the present invention have the characteristic of halogen-free flameproof, excellent comprehensive performance and good appearance, and preparation method is simple to operation, industrialization continuous production easy to implement.
Description
Technical field
The present invention relates to a kind of halogen-free flameproof PE/PS alloy materials and preparation method thereof.
Background technology
Polyethylene (PE) and polystyrene (PS) are all the big kind general-purpose plastics that yield tops the list.Polystyrene leads to other
With plastic compared to having the advantages that good moldability, rigidity is good, electrical insulation capability is good, agent of low hygroscopicity, easy dyeing and cheap.Cause
And it is widely used in industries such as packaging, electronics, building, automobile, household electrical appliances, daily necessities.But the shock resistance of PS, resistance to ring
Border stress cracking and solvent nature are poor, and heat distortion temperature is relatively low (70~98 DEG C), limits its application.And PE have it is good
Good toughness, solvent resistance, but rigidity is low, not easy dyeing.In order to obtain the material of high comprehensive performance, people to PS, PE into
Study on the modification is gone, it is expected that obtaining a kind of composite material having both PS, PE excellent performance.
PS/PE is typical Immiscible Polymer Blends, and interfacial tension is big, and simple physical mechanical blending is difficult to disperse component,
Therefore the adhesiveness for solving the compatibility and interface of PS, PE, is the key that prepare excellent performance PS/PE alloy materials.It is right at present
The method of PE/PS alloy material component compatibility Resolving probiems is that bulking agent is added.It is compatible that bulking agent is broadly divided into non-reactive
Agent and response type compatilizer, two kinds respectively have advantage and disadvantage, and non-reactive compatilizer is predominantly grafted or one analog copolymer of block, work
Skill is simple, but additive amount is big, declines to material modulus and tensile strength apparent；Another kind of reactive compatibilizer additive amount is small,
Compatibilization effect is apparent, but since its more difficult dispersion causes its controllability poor, complex process.Two kinds of bulking agents are combined simultaneously
With keeping reactive compatibilizer pre-dispersed and make reactive extrusion in non-reactive bulking agent, dispersion effect is good, while can subtract
Few bulking agent dosage, is a kind of ideal increase-volume mode.
But as the development of plastics industry keeps people higher and higher to the various performance requirements of plastic product, to plastics system
More stringent requirements are proposed for the fire safety of product, be especially in electric material and indoor building material etc., not only requires resistance
Combustion also requires Halogen and nuisanceless.For PE/PS alloy materials because having excellent comprehensive performance, applying has bright prospects, but
It is that PE/PS alloy material flammable properties limit its application range, therefore develop a kind of high-performance halogen-free flame retardant PE/PS alloy materials
Material has important practical significance.
Invention content
The purpose of the present invention is to provide a kind of halogen-free flameproof PE/PS alloy materials, the alloy material have halogen-free flameproof,
The characteristic of excellent comprehensive performance and good appearance.
Another object of the present invention provides the preparation method of above-mentioned halogen-free flameproof PE/PS alloy materials, and this method is to make instead
Answer type bulking agent is pre-dispersed to make reactive extrusion in non-reactive bulking agent, dispersion effect is good, reduces bulking agent dosage,
PE/PS alloy materials to be had excellent performance.
It is still another object of the present invention to provide a kind of method of halogen-free flameproof modified PE/PS alloy materials, this method is
Halogen-free flame retardants and siliceous inorganic particle are compounded, a kind of synergistic flame-retardant system is formed, is added into alloy system, is hindered
Fire the halogen-free flameproof PE/PS alloy materials haveing excellent performance.
The technical solution used in the present invention is：
A kind of halogen-free flameproof PE/PS alloy materials, include following components by mass fraction：
Bulking agent is compounded by the non-reactive bulking agent of grafting or block copolymer to be increased with the response type for causing function
Hold agent composition, wherein non-reactive bulking agent is Styrene-Butadiene-Styrene Block Copolymer, hydrogenated styrene-butadiene
Block copolymer, nitrile rubber, ethylene-methyl acrylate-methacrylic acid glycerin ether terpolymer, maleic anhydride grafting are poly-
At least one of ethylene, maleic anhydride inoculated polypropylene；Reactive compatibilizer is cumyl peroxide, bis 25 vulcanizing agent
At least one of.
Polyethylene is at least one of HDPE, LDPE, LLDPE.
Polystyrene is at least one of HIPS, GPPS.
The mass ratio of non-reactive bulking agent and reactive compatibilizer is (5~30)：1.
Halogen-free flame retardants is at least one of ammonium polyphosphate flame retardant, piperazine pyrophosphate fire retardant.
Siliceous inorganic particle is at least one of talcum powder, montmorillonite, kaolin, wollastonite in powder, white carbon.
Processing aid is at least one of antioxidant, lubricant.
Antioxidant is at least one of Hinered phenols, hindered amines, phosphoric acid ester, thioester antioxidant.
Above-mentioned lubricant is at least one of hydro carbons, fatty acid, metal soap, silicone oil.
A kind of preparation method of halogen-free flameproof PE/PS alloy materials is first by polyethylene, polystyrene and compounding bulking agent
Mixing adds halogen-free flame retardants, siliceous inorganic particle and processing aid mixing, then melts, squeeze out, be granulated, obtain Halogen
Fire-retardant PE/PS alloy materials.
The beneficial effects of the invention are as follows：
The PE/PS alloy materials of the present invention have the characteristic of halogen-free flameproof, excellent comprehensive performance and good appearance, preparation method
It is simple to operation, industrialization continuous production easy to implement.
It is specific as follows：
1, the present invention is because taking compounding bulking agent to carry out alloy capacity increasing modifying, and compatibility is good between making its component, to
The alloy property arrived is excellent, with high intensity, high tenacity, low-density, lower shrinkage and resistant to chemical etching excellent and with pearly-lustre
The good appearance of color and luster.
2, the present invention compounds siliceous inorganic particle synergistic flame-retardant system using halogen-free flame retardants, and superior flame retardant property reaches
To UL94V-0 0.8mm V-0 ranks, meet environmental requirement, green material, technique extension PE/PS conjunctions can be used as
The use scope of golden material.
3, raw material needed for halogen-free flameproof PE/PS alloy materials of the present invention have market sale, are easier to obtain, preparation side
Method is simple to operation, industrialization continuous production easy to implement.
Specific implementation mode
A kind of halogen-free flameproof PE/PS alloy materials, include following components by mass fraction：
Bulking agent is compounded by the non-reactive bulking agent of grafting or block copolymer to be increased with the response type for causing function
Hold agent composition, wherein non-reactive bulking agent is Styrene-Butadiene-Styrene Block Copolymer (SBS), hydrogenated styrene-
Butadiene block copolymer (SEBS), nitrile rubber (NBR), ethylene-methyl acrylate-methacrylic acid glycerin ether ternary polymerization
At least one of object (EMA), maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene；Reactive compatibilizer is peroxide
Change at least one of diisopropylbenzene (DIPB) (DCP), bis 25 vulcanizing agent.
Preferably, polyethylene is HDPE (high density polyethylene (HDPE)), LDPE (low density polyethylene (LDPE)), LLDPE (linea low densities
At least one of polyethylene).
Preferably, polystyrene is at least one in HIPS (high-impact polystyrene), GPPS (common polystyrene)
Kind.
Preferably, compounding bulking agent is to be stirred by non-reactive bulking agent, reactive compatibilizer and mix lubricant and made
；The mass ratio of non-reactive bulking agent and reactive compatibilizer is (5~30)：1, the addition of lubricant increases for non-reactive
Hold the 0.5~2% of agent and reactive compatibilizer gross mass.
Preferably, halogen-free flame retardants is at least one of ammonium polyphosphate flame retardant (APP), piperazine pyrophosphate fire retardant.
Preferably, siliceous inorganic particle is at least one in talcum powder, montmorillonite, kaolin, wollastonite in powder, white carbon
Kind.
Preferably, processing aid is at least one of antioxidant, lubricant.
Preferably, antioxidant is at least one of Hinered phenols, hindered amines, phosphoric acid ester, thioester antioxidant；
It is further preferred that antioxidant is irgasfos 168,1010, at least one of 1076.
Further, the dosage of antioxidant accounts for the 0.1~1% of halogen-free flameproof PE/PS alloy material gross masses.
Preferably, lubricant is at least one of hydro carbons, fatty acid, metal soap, silicone oil；It is further preferred that
Lubricant is at least one of paraffin oil, fatty acid calcium, PE waxes, EBS.
Further, the dosage of lubricant accounts for the 0.5~3% of halogen-free flameproof PE/PS alloy material gross masses.
A kind of preparation method of halogen-free flameproof PE/PS alloy materials is first by polyethylene, polystyrene and compounding bulking agent
Mixing adds halogen-free flame retardants, siliceous inorganic particle and processing aid mixing, then melts, squeeze out, be granulated, obtain Halogen
Fire-retardant PE/PS alloy materials.
Preferably, it squeezes out and is machined in twin-screw extrusion, processing temperature is 175~200 DEG C.
Present disclosure is described in further detail below by way of specific embodiment, but the embodiment party of the present invention
Formula is without being limited thereto.The preparation method that bulking agent is compounded in embodiment is that non-reactive bulking agent and reactive compatibilizer are added
1wt% paraffin oils, then 3~5min of high-speed stirred is added in homogenizer, obtains compounding bulking agent.
Embodiment 1：
A kind of PE/PS alloys of halogen-free flameproof prepare raw material by following mass fraction at being grouped as：
HDPE 20%
HIPS 40%
Compound compatilizer (SEBS:DCP=10:1) 5%
Halogen-free flame retardants 30%
Kaolin 4%
Antioxidant (1010:168=1:1) 0.4%
CaSt 0.6%
Preparation method is：High-speed mixer is added after HDPE, HIPS, compounding bulking agent are weighed in mass ratio and mixes 2
~6min, then the halogen-free flame retardants weighed in mass ratio, kaolin, 3~6min of processing aid addition kneading machine mixing is equal
It is even to be mixed to get premix, double screw extruder is added in premix, melting extrusion is granulated to obtain halogen-free flameproof PE/PS alloys,
Processing temperature control is 175~200 DEG C, which is shown in Table 1.
Embodiment 2：
HDPE 10%
LDPE 15%
GPPS 35%
Compound compatilizer (SBS:Double 2 5=20:1) 8%
Halogen-free flame retardants 22%
Talcum powder 8%
Antioxidant (1076:168=2:3) 0.5%
PE waxes 1.5%
Preparation method is：High-speed mixer is added after HDPE, LDPE, GPPS are weighed in mass ratio with compounding bulking agent
Mix 2~6min, then by the halogen-free flame retardants weighed in mass ratio, talcum powder, processing aid be added kneading machine mixing 3~
6min is uniformly mixed to get premix, double screw extruder is added in premix, melting extrusion is granulated to obtain halogen-free flameproof PE/PS
Alloy, processing temperature control is 175~200 DEG C, which is shown in Table 1.
Embodiment 3：
HDPE 23%
LDPE 12%
LLDPE 10%
HIPS 15%
GPPS 20%
Compound compatilizer (NBR:Double 2 5=25:1) 6%
Halogen-free flame retardants 20%
Wollastonite in powder 3%
Antioxidant (1076:168=2:3) 0.5%
EBS 0.5%
Preparation method is：Add after HDPE, LDPE, LLDPE, HIPS, GPPS are weighed in mass ratio with compounding bulking agent
Enter high-speed mixer and mix 2~6min, then the halogen-free flame retardants weighed in mass ratio, wollastonite in powder, processing aid are added
Kneading machine mixes 3~6min and is uniformly mixed to get premix, double screw extruder is added in premix, melting extrusion is granulated to obtain
Halogen-free flameproof PE/PS alloys, processing temperature control is 175~200 DEG C, which is shown in Table 1.
Embodiment 4：
HDPE 11%
LLDPE 10%
HIPS 25%
GPPS 25%
Compound compatilizer (SEBS:DCP=30:1) 10%
Halogen-free flame retardants 15%
Montmorillonite 3%
Antioxidant (1076:168=2:3) 0.5%
EBS 0.2%
CaSt 0.3%
Preparation method is：High speed is added after HDPE, LLDPE, HIPS, GPPS are weighed in mass ratio with compounding bulking agent
Mixing machine mixes 2~6min, then the halogen-free flame retardants weighed in mass ratio, montmorillonite, processing aid are added kneading machine and are mixed
It closes 3~6min and is uniformly mixed to get premix, double screw extruder is added in premix, melting extrusion is granulated to obtain halogen-free flameproof
PE/PS alloys, processing temperature control is 175~200 DEG C, which is shown in Table 1.
Embodiment 5：
HDPE 10%
LLDPE 17%
HIPS 45%
Compound compatilizer (EMA:Double 2 5=25:1) 8%
Halogen-free flame retardants 17%
White carbon 3%
Antioxidant (1076:168=2:3) 0.5%
EBS 0.2%
CaSt 0.3%
Preparation method is：Mixed at high speed is added after HDPE, LLDPE, HIPS are weighed in mass ratio with compounding bulking agent
Machine mix 2~6min, then by the halogen-free flame retardants weighed in mass ratio, white carbon, processing aid be added kneading machine mixing 3~
6min is uniformly mixed to get premix, double screw extruder is added in premix, melting extrusion is granulated to obtain halogen-free flameproof PE/PS
Alloy, processing temperature control is 175~200 DEG C, which is shown in Table 1.
Embodiment 6：
HDPE 21%
LDPE 13%
GPPS 30%
Compound compatilizer (EMA:DCP=20:1) 7%
Halogen-free flame retardants 20%
Talcum powder 8%
Antioxidant (1076:168=2:3) 0.5%
PE waxes 1.5%
Preparation method is：High-speed mixer is added after HDPE, LDPE, GPPS are weighed in mass ratio with compounding bulking agent
Mix 2~6min, then by the halogen-free flame retardants weighed in mass ratio, talcum powder, processing aid be added kneading machine mixing 3~
6min is uniformly mixed to get premix, double screw extruder is added in premix, melting extrusion is granulated to obtain halogen-free flameproof PE/PS
Alloy, processing temperature control is 175~200 DEG C, which is shown in Table 1.
The alloy property of 1 embodiment of table
Comparative example 1：
HDPE 21%
LDPE 13%
GPPS 30%
Compatilizer EMA 7%
Halogen-free flame retardants 20%
Talcum powder 8%
Antioxidant (1076:168=2:3) 0.5%
PE waxes 1.5%
Preparation method is：Be added after HDPE, LDPE, GPPS are weighed in mass ratio with EMA high-speed mixer mix 2~
6min, then the halogen-free flame retardants weighed in mass ratio, talcum powder, 3~6min of processing aid addition kneading machine mixing is uniform
It is mixed to get premix, double screw extruder is added in premix, melting extrusion is granulated to obtain halogen-free flameproof PE/PS alloys, add
The control of work temperature is 175~200 DEG C, which is shown in Table 2.
Comparative example 2：
HDPE 21%
LDPE 13%
GPPS 37%
Bulking agent DCP 0.35%
Halogen-free flame retardants 20%
Talcum powder 8%
Antioxidant (1076:168=2:3) 0.5%
PE waxes 1.5%
Preparation method is：Be added after HDPE, LDPE, GPPS are weighed in mass ratio with DCP high-speed mixer mix 2~
6min, then the halogen-free flame retardants weighed in mass ratio, talcum powder, 3~6min of processing aid addition kneading machine mixing is uniform
It is mixed to get premix, double screw extruder is added in premix, melting extrusion is granulated to obtain halogen-free flameproof PE/PS alloys, add
The control of work temperature is 175~200 DEG C, which is shown in Table 2.
2 embodiment of table and comparative example alloy material performance
By table 2 it is found that being higher than single compatibilization system alloy material using the alloy material performance of compounding compatilizer increase-volume
Performance.
Claims (10)
1. a kind of halogen-free flameproof PE/PS alloy materials, it is characterised in that：Include following components by mass fraction：
Polyethylene 20~40%；
Polystyrene 30~50%；
Compound bulking agent 5~10%；
Halogen-free flame retardants 15~30%；
Siliceous inorganic particle 2~10%；
Processing aid 0.5~3%；
Bulking agent is compounded by the non-reactive bulking agent of grafting or block copolymer and the reactive compatibilizer with initiation function
Composition, wherein non-reactive bulking agent are Styrene-Butadiene-Styrene Block Copolymer, hydrogenated styrene-butadiene block
Copolymer, nitrile rubber, ethylene-methyl acrylate-methacrylic acid glycerin ether terpolymer, maleic anhydride are grafted poly- second
At least one of alkene, maleic anhydride inoculated polypropylene；Reactive compatibilizer is in cumyl peroxide, bis 25 vulcanizing agent
At least one.
2. a kind of halogen-free flameproof PE/PS alloy materials according to claim 1, it is characterised in that：Polyethylene be HDPE,
At least one of LDPE, LLDPE.
3. a kind of halogen-free flameproof PE/PS alloy materials according to claim 1, it is characterised in that：Polystyrene be HIPS,
At least one of GPPS.
4. a kind of halogen-free flameproof PE/PS alloy materials according to claim 1, it is characterised in that：Non-reactive bulking agent
Mass ratio with reactive compatibilizer is (5~30)：1.
5. a kind of halogen-free flameproof PE/PS alloy materials according to claim 1, it is characterised in that：Halogen-free flame retardants is poly-
At least one of ammonium phosphate fire retardant, piperazine pyrophosphate fire retardant.
6. a kind of halogen-free flameproof PE/PS alloy materials according to claim 1, it is characterised in that：Siliceous inorganic particle is
At least one of talcum powder, montmorillonite, kaolin, wollastonite in powder, white carbon.
7. a kind of halogen-free flameproof PE/PS alloy materials according to claim 1, it is characterised in that：Processing aid is antioxygen
At least one of agent, lubricant.
8. a kind of halogen-free flameproof PE/PS alloy materials according to claim 7, it is characterised in that：Antioxidant is hindered phenol
At least one of class, hindered amines, phosphoric acid ester, thioester antioxidant.
9. a kind of halogen-free flameproof PE/PS alloy materials according to claim 7, it is characterised in that：Lubricant is hydro carbons, fat
At least one of fat acids, metal soap, silicone oil.
10. a kind of preparation method of halogen-free flameproof PE/PS alloy materials described in claim 1, it is characterised in that：First by poly- second
Alkene, polystyrene and compounding bulking agent mixing, add halogen-free flame retardants, siliceous inorganic particle and processing aid mixing, then
Melting squeezes out, and is granulated, obtains halogen-free flameproof PE/PS alloy materials.
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| CN109553872A (en) * | 2018-12-18 | 2019-04-02 | 苏州马培德办公用品制造有限公司 | A kind of composite material and preparation method and application of plastic penholder |
| CN115490973A (en) * | 2022-08-30 | 2022-12-20 | 武汉金发科技有限公司 | Polystyrene-polyethylene alloy composite material and preparation method and application thereof |
| CN115612238A (en) * | 2022-11-08 | 2023-01-17 | 武汉金发科技有限公司 | Polystyrene-polyethylene alloy material and preparation method and application thereof |
| CN116218127A (en) * | 2023-05-08 | 2023-06-06 | 广东美的制冷设备有限公司 | Compatilizer and preparation method thereof, alloy material and preparation method thereof, and refrigerator liner |
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| CN102643484A (en) * | 2012-04-25 | 2012-08-22 | 金发科技股份有限公司 | In-situ compatibilization polyolefin/polystyrene alloy and preparation method and application thereof |
| CN103849076A (en) * | 2012-12-04 | 2014-06-11 | 青岛三利中德美水设备有限公司 | Nanoscale antiflaming reinforced PS/PE (poly styrene/polyethylene) alloy material and preparation method thereof |
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| CN1197815A (en) * | 1997-07-15 | 1998-11-04 | 华南理工大学 | Preparation of lightly crosslinking-bulked PS/PE mixture |
| CN102643484A (en) * | 2012-04-25 | 2012-08-22 | 金发科技股份有限公司 | In-situ compatibilization polyolefin/polystyrene alloy and preparation method and application thereof |
| CN103849076A (en) * | 2012-12-04 | 2014-06-11 | 青岛三利中德美水设备有限公司 | Nanoscale antiflaming reinforced PS/PE (poly styrene/polyethylene) alloy material and preparation method thereof |
Cited By (7)
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| CN109370082A (en) * | 2018-10-24 | 2019-02-22 | 山东创伟外墙保温材料集团有限公司 | One kind receives plastic insulation board and its manufacturing method |
| CN109553872A (en) * | 2018-12-18 | 2019-04-02 | 苏州马培德办公用品制造有限公司 | A kind of composite material and preparation method and application of plastic penholder |
| CN115490973A (en) * | 2022-08-30 | 2022-12-20 | 武汉金发科技有限公司 | Polystyrene-polyethylene alloy composite material and preparation method and application thereof |
| CN115612238A (en) * | 2022-11-08 | 2023-01-17 | 武汉金发科技有限公司 | Polystyrene-polyethylene alloy material and preparation method and application thereof |
| CN115612238B (en) * | 2022-11-08 | 2023-08-29 | 武汉金发科技有限公司 | Polystyrene-polyethylene alloy material and preparation method and application thereof |
| CN116285068A (en) * | 2023-04-20 | 2023-06-23 | 东莞市塘厦鸿联吸塑厂 | High-elasticity toughened PE modified material and preparation method thereof |
| CN116218127A (en) * | 2023-05-08 | 2023-06-06 | 广东美的制冷设备有限公司 | Compatilizer and preparation method thereof, alloy material and preparation method thereof, and refrigerator liner |
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