CN109971107A - A kind of poly styrene composite material and preparation method thereof - Google Patents
A kind of poly styrene composite material and preparation method thereof Download PDFInfo
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- CN109971107A CN109971107A CN201811610235.7A CN201811610235A CN109971107A CN 109971107 A CN109971107 A CN 109971107A CN 201811610235 A CN201811610235 A CN 201811610235A CN 109971107 A CN109971107 A CN 109971107A
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention discloses a kind of poly styrene composite materials, which is characterized in that by weight, including following components: 100 parts of polystyrene-polybutadiene graft copolymer；5-70 parts of polyacrylate polymers；1-15 parts of cinnamic acrylic ester analog copolymer.Poly styrene composite material of the invention has the advantages that wilful good, good appearance.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of poly styrene composite material and its preparation side
Method.
Background technique
Polystyrene refers to the polymer by styrene monomer free radical addition polymerization.Polystyrene includes common
Polystyrene, expanded polystyrene (EPS), high impact polystyrene and syndiotactic polytyrene etc..High impact polystyrene (abbreviation HIPS) is
The graft copolymer of styrene and polybutadiene rubber.Polybutadiene improves impact strength, keeps HIPS same as rubber toughened
When intensity with higher and good toughness.It is widely used in household electrical appliances, electronic apparatus and packaging industry.
But contain the rubber of big size composition in high impact polystyrene, so that material surface is softened.When for sheathing material
When, product can inevitably collide with hard object during preparation, transport and use, rub, and surface is made easily to occur significantly drawing
Trace influences surface aesthetics, hinders its application.
General way is damage resistant agent to be added to increase scratch resistant performance, but damage resistant agent is added merely, can only be subtracted
Slight scratch it is clear, can not improve material surface resist sharp objects generate scratch.Also, excessive addition damage resistant agent,
Increase the risk being precipitated when use, durability decline.
Way also is mass filler to be added to increase scratch resistant performance, but filler can seriously reduce the surface of material
Glossiness influences the beauty of product.And also there is reduction effect to the toughness of material.
Summary of the invention
It is an object of the present invention to overcome the above technological deficiency, a kind of poly styrene composite material is provided, with toughness
The advantages of good, good appearance.
Another object of the present invention is to provide the preparation methods of above-mentioned poly styrene composite material.
The present invention is achieved by the following technical solutions:
A kind of poly styrene composite material, by weight, including following components:
100 parts of polystyrene-polybutadiene graft copolymer (HIPS)；
5-70 parts of polyacrylate polymers；
1-15 parts of cinnamic acrylic ester analog copolymer.
The addition of polyacrylate polymers can make HIPS promote surface hardness, and then improve scratch resistant performance.
But the compatibility of HIPS and polyacrylate polymers is very poor, can coagulate after more polyacrylate polymers are added
Knot forms small group, does not only result in declining to a great extent for toughness, there is also " dark line " and glossiness declines, there are also pearls on surface
Light influences appearance.Existing common compatilizer cannot make the two compatible (6 graft copolymer of styrene-nylon, benzene second well
The compatibility of alkene-ethylene/propene diblock copolymer and HIPS are preferable, but with polyacrylate polymers poor compatibility, nothing
Method plays good compatibilization to polyacrylate polymers；SBS or SEBS is preferable with the compatibility of HIPS, but with it is poly-
Acrylic polymer poor compatibility, while can have a significant impact to glossiness).It is a discovery of the invention that cinnamic acrylic ester
Analog copolymer can effectively promote the compatibility of HIPS and polyacrylate as compatilizer, and then improve dark line phenomenon, pearl
Optical phenomenon improves surface gloss, ensure that the toughness of composite material while improving surface hardness.
The polyacrylate polymers are selected from polymethyl acrylate quasi polymer, polyethyl acrylate Type of Collective
Object, polyacrylic acid propyl ester quasi polymer, butyl polyacrylate quasi polymer, at least one in polyacrylic acid pentyl ester quasi polymer
Kind；
Preferably, the polyacrylate polymers are selected from polymethyl acrylate quasi polymer, polyethyl acrylate is birdsed of the same feather flock together
Close at least one of object.
Poly styrene composite material of the present invention can be adjusted according to the polyacrylate polymers of different substituents
Hardness, glossiness, above-mentioned two classes polyacrylate polymers, hardness and glossiness all synthesis are higher, less in additional amount
In the case of can meet hardness under common situation, the demand that glossiness is promoted.
The polyacrylate polymers weight average molecular weight Mw is 80000g/mol-300000 g/mol；
Using the comprehensive performance of the hardness of poly styrene composite material and processing performance as preferential index, it is preferred that described is poly-
Acrylic polymer weight average molecular weight Mw is 140000g/mol-190000 g/mol.
The weight average molecular weight of polyacrylate polymers is bigger, and hardness is relatively also bigger, to poly styrene composite material
Hardness promoted it is preferable.But the molecular weight of polyacrylate polymers is too big, will lead to too hard and increases difficulty of processing.
The cinnamic acrylic ester analog copolymer is selected from copolymer in cinnamic acrylic ester, styrene-butadiene-
At least one of acrylate copolymer.
In general, cinnamic acrylic ester analog copolymer is generally used for being prepared into core-shell structure, it to be used for toughening.Specifically,
Styrene-butadiene-acrylic acid esters co-polymer is generally used for being prepared into the MBS of core-shell structure, the toughening for PVC.Benzene second
Alkene-acrylate copolymer can be prepared into emulsion form, be used for coating.So far do not report that it is used for HIPS and polyacrylate
The increase-volume application of quasi polymer, and cinnamic acrylic ester analog copolymer has certain glossiness, can further be promoted
The glossiness of poly styrene composite material achievees the effect that the good appearance of high gloss.
Preferably, in the cinnamic acrylic ester analog copolymer content of acrylate within the scope of 20-60%.
The content of acrylate is within the scope of 20-60%, and cinnamic acrylic ester analog copolymer is for HIPS and polypropylene
The compatibility of acid esters quasi polymer is preferable.
Preferably, the weight average molecular weight Mw of the polystyrene-polybutadiene graft copolymer be 80000g/mol extremely
180000g/mol, with polystyrene-polybutadiene graft copolymer segment total weight, polybutadiene content is 10% to 40%.
The parameter of polystyrene-polybutadiene graft copolymer within the above range, can make material obtain preferable comprehensive mechanical property
And good processing performance, meet practical application request.
The test result of the weight average molecular weight of general polymerization object is " the inverted U song of the similar normal distribution of a wide scope
Line " has a peak, as long as peak falls into protection scope of the present invention in claimed range of the invention.
It by weight, can also include 0-3 parts of damage resistant agent；The damage resistant agent is selected from stearate damage resistant
At least one of agent, silicone damage resistant agent.
It by weight, further include 0.1-10 parts of auxiliary agent；The auxiliary agent is selected from fire retardant, heat stabilizer, antioxidant, resistance
Fire at least one of synergist, anti-dripping agent, light stabilizer, plasticizer, filler and colorant.
The lubricant is Metallic stearates series lubricant agent, allcyl stearate series lubricant agent, stearic acid pentaerythrite
Ester lubricant, paraffin or lignite wax.
The heat stabilizer is organic phosphite, preferably triphenyl phosphite, phosphorous acid three-(2,6- dimethyl benzenes
Base) ester, three-nonyl of phosphorous acid phenylester, dimethylbenene phosphonate or trimethyl phosphate.
The antioxidant is the alkyl of organic phosphite, alkylated monohydric phenol or polyphenol, polyphenol and diene
Change reaction product, butylation product, the alkylated hydroquinones, hydroxylated thio two of paracresol or bicyclopentadiene
Phenyl ethers, alkylidene-bis-phenol, benzyl compounds or polyol ester kind antioxidant.
The retardant synergist be siliceous compound or fluorine-containing compound, preferably siloxanes, dimethyl siloxane,
Phenyl siloxane, methoxy radical siloxane, polytetrafluoroethylene (PTFE), acrylonitrile-butadiene copolymer SAN cladding polytetrafluoroethyl-ne
Polytetrafluoroethylene (PTFE), emulsion polymerized poly or the perfluorinated sulfonate of alkene, polycarbonate cladding.
The light stabilizer is at least one of benzotriazole light stabilizer or benzophenone light stabilizer.
The plasticizer is phthalic acid ester.
The colorant is pigments or dyes.
The preparation method of above-mentioned poly styrene composite material, comprising the following steps:
Weigh raw material according to the proportion, then by polystyrene-polybutadiene graft copolymer, polyacrylate, Styrene And Chloroalkyl Acrylates
Lipin polymer, auxiliary agent mixed at high speed are uniform, and melting extrusion is granulated to obtain poly styrene composite material, screw rod in host is added
Temperature is 210-230 DEG C.
The present invention has the advantages that
The present invention is improved compound by the way that polyacrylate is added in polystyrene-polybutadiene graft copolymer (HIPS)
The hardness of material, then by the way that special compatilizer cinnamic acrylic ester analog copolymer is added, improve polystyrene-poly fourth
The compatibility of diene graft copolymer and polyacrylate, ensure that the toughness of material, also further improve hardness (damage resistant
Performance is good, can save good appearance for a long time), dark line, pearly-lustre are eliminated, and improve surface gloss.To sum up, of the invention
Poly styrene composite material has the advantages that high tenacity, good appearance.
Specific embodiment
The present invention further illustrates the present invention by following embodiment, but the present invention is not limited by the following examples.
The raw materials used in the present invention derives from commercial product.
Polystyrene-polybutadiene graft copolymer: weight average molecular weight is about 140000g/mol, and polybutadiene content is about
It is 33%；
Copolymer in cinnamic acrylic ester A: the content of acrylate is about 46%；
Copolymer in cinnamic acrylic ester B: the content of acrylate is about 76%；
Polymethyl methacrylate A(hereinafter abbreviation PMMA-A): weight average molecular weight peak is about 161000g/mol；
Polymethyl methacrylate B(hereinafter abbreviation PMMA-B): weight average molecular weight peak is about 129000g/mol；
Poly- ethyl propylene acid butyl ester (PEBA): weight average molecular weight peak is about 154000g/mol；
Polybutyl methacrylate (PMBA): weight average molecular weight peak is about 189000g/mol；
Poly- butyl methacrylate (PBMA): weight average molecular weight peak is about 146000g/mol；
Other compatilizers A: styrene-ethylene/propylene diblock copolymer；
Other compatilizers B:SEBS；
Antioxidant: pentaerythritol ester kind antioxidant, phosphite ester antioxidant；
Lubricant: ethylene bis stearamide.
The preparation method of embodiment and comparative example poly styrene composite material: weighing raw material according to the proportion, then by polyphenyl second
Alkene-polybutadiene graft copolymer, polyacrylate, cinnamic acrylic ester analog copolymer (or other compatilizers), auxiliary agent
Mixed at high speed is uniform, and melting extrusion is granulated to obtain poly styrene composite material, extruder temperature 210-230 in host is added
℃。
Properties test method:
(1) impact strength: according to GB1843-1996 " plastics izodtest method " standard testing, pendulum energy
2.75J, room temperature test.
(2) hardness: Rockwell hardness is tested by GB230.1-2004 " Rockwell hardness experimental method ", and test sample is 6mm thick
The disk of diameter；Pencil hardness is by GB/T 6739-2006 " paint and varnish pencil method measures hardness of paint film " test.
(3) hundred lattice: it is molded by 100 × 100mm band dermatoglyph square plate, by " stroke of GB9286-1998 paint and varnish paint film
Lattice test " it carries out drawing hundred lattice, observation scratch △ L, △ L is the smaller the better under the microscope later.
(4) glossiness: by " GB/T 8807-1988 plastics bright luster test method " with 60 ° of angle measurement glossiness.
(5) dark line: being molded the rectangular slab of long 200mm, width 50mm, thickness 2mm, visually observes surface dark line.
Table 1: embodiment poly styrene composite material each group distribution ratio (parts by weight) and its properties test result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| HIPS | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| PMMA-A | 12 | - | - | - | - | 25 | 50 | 12 |
| PMMA-B | - | 12 | - | - | - | - | - | - |
| PEBA | - | - | 12 | - | - | - | - | - |
| PMBA | - | - | - | 12 | - | - | - | - |
| PBMA | - | - | - | - | 12 | - | - | - |
| Copolymer in cinnamic acrylic ester A | 6 | 6 | 6 | 6 | 6 | 10 | 15 | - |
| Copolymer in cinnamic acrylic ester B | - | - | - | - | - | - | - | 6 |
| Impact strength, kJ/m2 | 8.8 | 8.5 | 9.2 | 8.6 | 7.9 | 7.1 | 6.6 | 8.3 |
| Rockwell hardness | 107 | 104 | 105 | 108 | 105 | 110 | 114 | 105 |
| △ L after hundred lattice | 0.48 | 0.75 | 0.53 | 0.42 | 0.58 | 0.38 | 0.21 | 0.67 |
| Glossiness | 82 | 78 | 74 | 73 | 81 | 85 | 91 | 80 |
| Dark line | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing |
Table 2: comparative example poly styrene composite material each group distribution ratio (parts by weight) and its properties test result
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| HIPS | 100 | 100 | 100 |
| PMMA-A | 12 | 12 | 12 |
| Styrene-ethylene/propylene diblock copolymer | - | 6 | - |
| SEBS | - | - | 6 |
| Impact strength, kJ/m2 | 4.6 | 4.9 | 5.3 |
| Rockwell hardness | 102 | 97 | 94 |
| △ L after hundred lattice | 0.92 | 1.16 | 1.32 |
| Glossiness | 67 | 58 | 47 |
| Dark line | Have | Have | Have |
From comparative example and embodiment can be seen that be added cinnamic acrylic ester analog copolymer as compatilizer, being capable of maximum limit
Guarantee the toughness of composite material on degree, and obtains good presentation quality.
It can be seen that cinnamic acrylic ester analog copolymer as compatilizer for HIPS from comparative example 2-3 and embodiment
It is best with the compatibilization of polyacrylate polymers, and can significantly promote glossiness.
From embodiment 1-5 can be seen that addition polymethyl acrylate quasi polymer product hardness and glossiness it is comprehensive compared with
It is high.
From embodiment 1 and embodiment 2 as can be seen that with the comprehensive of the hardness of poly styrene composite material and processing performance
When can be used as preferential index, preferably polyacrylate polymers weight average molecular weight Mw is 140000g/mol-190000 g/
mol。
From embodiment 1 and embodiment 8 as can be seen that copolymer in cinnamic acrylic ester is in preferred range, Ge Xiangxing
Preferably there can be preferable holding especially for notch impact strength.
Claims (9)
1. a kind of poly styrene composite material, which is characterized in that by weight, including following components:
100 parts of polystyrene-polybutadiene graft copolymer；
5-70 parts of polyacrylate polymers；
1-15 parts of cinnamic acrylic ester analog copolymer.
2. poly styrene composite material according to claim 1, which is characterized in that the polyacrylate polymers
Selected from polymethyl acrylate quasi polymer, polyethyl acrylate quasi polymer, polyacrylic acid propyl ester quasi polymer, polyacrylic acid fourth
At least one of esters polymer, polyacrylic acid pentyl ester quasi polymer；Preferably, selected from polymethyl acrylate quasi polymer,
At least one of polyethyl acrylate quasi polymer.
3. poly styrene composite material according to claim 1 or 2, which is characterized in that the polyacrylate is birdsed of the same feather flock together
Conjunction object weight average molecular weight Mw is 80000g/mol-300000 g/mol；Preferably, polyacrylate polymers weight is equal
Molecular weight Mw is 140000g/mol-190000 g/mol.
4. poly styrene composite material according to claim 1, which is characterized in that the cinnamic acrylic ester class
Copolymer is selected from least one of copolymer in cinnamic acrylic ester, styrene-butadiene-acrylate copolymer.
5. poly styrene composite material according to claim 1 or 4, which is characterized in that the cinnamic acrylic ester
The content of acrylate is within the scope of 20-60% in analog copolymer.
6. poly styrene composite material according to claim 1, which is characterized in that the polystyrene-polybutadiene
The weight average molecular weight Mw of graft copolymer is 80000g/mol to 180000g/mol, with polystyrene-polybutadiene graft copolymerization
Object segment total weight, polybutadiene content is 10% to 40%.
7. poly styrene composite material according to claim 1, which is characterized in that further include 0-3 parts by weight
Damage resistant agent；The damage resistant agent is selected from least one of the agent of stearate damage resistant, silicone damage resistant agent.
8. poly styrene composite material according to claim 1, which is characterized in that further include 0.1-10 by weight
The auxiliary agent of part；The auxiliary agent is selected from fire retardant, heat stabilizer, antioxidant, retardant synergist, anti-dripping agent, light stabilizer, plasticising
At least one of agent, filler, colorant.
9. the preparation method of poly styrene composite material according to any one of claims 8, which comprises the following steps:
Weigh raw material according to the proportion, then by polystyrene-polybutadiene graft copolymer, polyacrylate, Styrene And Chloroalkyl Acrylates
Lipin polymer, auxiliary agent mixed at high speed are uniform, and melting extrusion is granulated to obtain poly styrene composite material, screw rod in host is added
Temperature is 210-230 DEG C.
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| CN201811610235.7A CN109971107A (en) | 2018-12-27 | 2018-12-27 | A kind of poly styrene composite material and preparation method thereof |
| PCT/CN2019/121732 WO2020134844A1 (en) | 2018-12-27 | 2019-11-28 | Polystyrene composite material and preparation method therefor |
| AU2020101213A AU2020101213A4 (en) | 2018-12-27 | 2020-07-01 | Polystyrene composite material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111073251A (en) * | 2019-12-23 | 2020-04-28 | 宁波帅特龙集团有限公司 | High-yield high-strength electroplating PC/ABS alloy and preparation method thereof |
| WO2020134844A1 (en) * | 2018-12-27 | 2020-07-02 | 金发科技股份有限公司 | Polystyrene composite material and preparation method therefor |
| CN112708208A (en) * | 2020-12-23 | 2021-04-27 | 成都金发科技新材料有限公司 | Polypropylene composite material and preparation method thereof |
| CN114957874A (en) * | 2022-07-07 | 2022-08-30 | 青岛海纳新材料有限公司 | High-hardness scratch-resistant polystyrene composite material and preparation method and application thereof |
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| CN115246932B (en) * | 2021-04-26 | 2023-08-15 | 合肥杰事杰新材料股份有限公司 | Compatilizer PS-g-POP and preparation method and application thereof |
| CN114479297B (en) * | 2021-12-29 | 2023-06-09 | 上海金发科技发展有限公司 | High-impact-resistance wear-resistant transparent polystyrene composition and preparation method and application thereof |
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| AU2020101213A4 (en) | 2020-08-06 |
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