CN101007887A - Toughened polystyrene composition and its preparation method - Google Patents
Toughened polystyrene composition and its preparation method Download PDFInfo
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Abstract
The invention provides a novle toughened polystyrene compound, which is the nanometer rubber particle with average grain size being 20- 300 dispersed in polyphenylacetylene base material. Said rubber particle takes rubber unit with cross-linking structure as core, and is covered with polyphenylacetylene, and the rubber particle content in compound is 1- 40 wt%. The compatability between rubber particle and polyphenylacetylene is increased, and the dispersing condition of rubber particle in polyphenylacetylene is improved. So the flexibility of polyphenylacetylene compound is dramatically improved even the rubber particle content is very low, and the strength, rigidity and other mechanical performance are still maintained.
Description
Technical field
The present invention relates to a kind of toughened polystyrene composite and preparation method thereof, more particularly, relate to a kind of composition and method of making the same that median size is the rubber particle of 20-300 nanometer that is dispersed with in polystyrene substrate, this resin combination has good toughness.
Background technology
Polystyrene (PS) because of its abundant raw material, low price, be easy to forming process, water absorbability is little and transparent advantage such as good, have in industry and civilian every field and to use widely, is the very big a kind of general-purpose plastics of consumption.But polystyrene resin has determined shortcoming on its mechanical property as insufficient strength height, poor toughness etc., especially to show brittle behaviour because of the immanent structure of its molecular chain.This makes its range of application be restricted to a great extent, has particularly limited its application aspect the high-impact goods.In order to improve the toughness of polystyrene, the method for normal at present employing polymerization or blend is mixed rubber components in polystyrene.Usually polymerization is to add rubber components in cinnamic polymerization process, as cis-1,4-polybutadiene rubber is dissolved in the styrene monomer, adopts the polymeric method finally to make the polystyrene resin that contains the cis-1,4-polybutadiene rubber particulate.Blending method is the method that adopts rubber components and the blend of polystyrene resin component melts, obtains blend composition as styrene-butadiene rubber(SBR) and polystyrene mechanical blending.
No matter be polymerization or blending method, select the optimum grain-diameter scope of rubber particles, and rubber particles is evenly dispersed in the polystyrene is the key that reaches best toughening effect.At present, found to adopt than small particle size, particularly nano level rubber particles comes the enhancing touthness of polyphenylethylene by adding resin can reach effect preferably, CN1159379C discloses a kind of enhancing touthness of polyphenylethylene by adding and preparation method thereof as Chinese patent, it adopts polystyrene and the median size with crosslinking structure is that the rubber grain blend of 0.02 μ m-0.5 μ m makes, but because blend method is difficult to the dispersion state of rubber particles in polystyrene substrate effectively controlled, consistency between rubber particles and polystyrene substrate is relatively poor, particularly the size when rubber particles is very little, when surface energy is big, easily self reunites, can not be dispersed in the polymkeric substance well, thereby reduce the toughening effect of rubber particles.
Summary of the invention
The invention provides a kind of composition of new enhancing touthness of polyphenylethylene by adding, its rubber particle with nucleocapsid structure by a kind of small particle size swells in and carries out polymerization on the throne in the styrene monomer and obtain.In the polyphenylacetylene combination of gained, improved the consistency between rubber particles and polystyrene substrate effectively, the dispersion state of rubber particles in polystyrene substrate is improved.Even thereby in the presence of less rubber particles, the toughness of polyphenylacetylene combination all is significantly improved, and still can keep other mechanical properties such as its intensity, rigidity.
A kind of toughened polystyrene composite, it is to be dispersed with the rubber particle that median size is the 20-300 nanometer in polystyrene substrate, the content of rubber particle is 1wt%～40wt% in described composition, is preferably 3wt%～30wt%, more preferably 5wt%～25wt%.Described rubber particle is to be nuclear with a kind of rubber components with crosslinking structure, is coated with polystyrene.Wherein the weight ratio of the polystyrene of rubber components and coating is 1: 2.00～1: 0.01, is preferably 1: 0.60～1: 1.30, more preferably 1: 0.1～1: 1.0.8.
Rubber components in the rubber particle is selected from least a or multiple in sulfurized natural rubber, styrene-butadiene rubber(SBR), carboxylic styrene-butadiene rubber, paracril, carboxy nitrile rubber, polyhutadiene, chloroprene rubber, esters of acrylic acid rubber and the ethylene-propylene rubber(EPR).In order to obtain toughening effect preferably, the crosslinking degree of general requirement rubber components is higher, and the present invention adopts the method for known its gel content of mensuration of the industry to characterize the crosslinking degree of rubber.The gel content of described rubber components generally is not less than 60wt%, preferably is not less than 80wt%.
Comparatively preferred scheme of toughened polystyrene composite of the present invention is: said composition is to be dispersed with the rubber particle that median size is the 20-300 nanometer in polystyrene substrate, described rubber particle is to be nuclear with a kind of rubber components with crosslinking structure, and being coated with polystyrene is shell.The weight ratio of the rubber components in rubber particle and the polystyrene of coating is 1: 0.60～1: 1.30, rubber components is selected from least a in sulfurized natural rubber, styrene-butadiene rubber(SBR) and the ethylene-propylene rubber(EPR), its gel content is not less than 80wt%, and the content of rubber particle is 5wt%～25wt% in described composition.
Rubber particle of the present invention should be thought a kind of material with nucleocapsid structure, is nuclear with a kind of rubber components with crosslinking structure wherein, and the outer polystyrene that coats is a shell.In the prior art, common this rubber particle need obtain by the polymeric method, can adopt the known polymerization process of the industry, and rubber particle and the common polymerization of styrene monomer are obtained.
A specific embodiments for preparing described rubber particle can comprise following preparation process: (1) causes radical polymerization with the respective emulsion of described rubber components and the mixture of styrene monomer in the presence of emulsifying agent; (2) after the latex that (1) step is obtained adds the linking agent mixing, adopt the high energy gamma source x ray irradiation x, make rubber components crosslinked, obtain rubber particle after the drying.
Wherein the polymerization temperature in the step (1) is 60 ℃～100 ℃, the polymerization regular hour, be generally 2～8 hours, and the weight ratio of rubber components and styrene monomer is controlled to be made as 1: 0.01～1: 2,1: 0.60～1: 1.30.Described emulsifying agent is selected from least a in sodium lauryl sulphate, sodium stearate or the Sodium pentadecanecarboxylate, preferably sodium dodecyl sulfate.The emulsifying agent consumption is 0.1～0.01wt%.The initiator that causes radical polymerization can be selected from persulphate compounds such as Potassium Persulphate or ammonium persulphate, also can select peroxide compound such as hydrogen phosphide cumene, benzoyl peroxide etc., the preferred vitriolate of tartar that adopts, the consumption of initiator is 0.1～2wt% of monomer total amount.
Wherein the linking agent that adds in the step (2) is selected from (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, a kind of in Diethylene Glycol (methyl) acrylate, Vinylstyrene, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, preferential (methyl) Isooctyl acrylate monomer of selecting.The consumption of described linking agent is counted the 0.1-0.5 gram with every gram rubber components.Carry out the high energy gamma source ray that irradiation adopted and to comprise cobalt source, X-ray, ultraviolet ray and high-energy electron accelerator.Preferentially select for use the cobalt source to carry out irradiation, dosage can be 2.5Mrad, and dose rate can be 50Gy/min.Latex behind the irradiation is by the spray-dryer spraying drying, and the inlet temperature of spray-dryer is 100 ℃～2000 ℃, and temperature out is 20 ℃～80 ℃, collects dried rubber particle with nucleocapsid structure of certain gel content in cyclonic separator.
The composition of enhancing touthness of polyphenylethylene by adding of the present invention is to swell in by the above-mentioned rubber particle with nucleocapsid structure to carry out polymerization on the throne in the styrene monomer and obtain.Particularly, can obtain by following component polymerization:
Above-mentioned rubber particle parts by weight 5～25
Styrene monomer parts by weight 75～95
Described polyreaction preferably adopts radical polymerization, and initiating method can adopt thermal initiation or initiator to cause.Initiator is selected from least a in Potassium Persulphate, dicumyl peroxide, hydrogen phosphide cumene, benzoyl peroxide or the peroxide di-t-butyl, preferably adopts hydrogen phosphide cumene.The consumption of initiator is 0.1～2wt% of styrene monomer total amount, is preferably 0.2-0.5wt%.
Above-mentioned radical polymerization randomly adds organic solvent, and described organic solvent preferably adopts aromatic hydrocarbons, as toluene, dimethylbenzene or ethylbenzene etc.The consumption of organic solvent is generally 0～60wt% of styrene monomer total amount, is preferably 10～30wt%.Styrene monomer and rubber particle are dissolved in the organic solvent, are adding an amount of initiator initiated polymerization then.
In above-mentioned radical polymerization process, also can adopt the known some other auxiliary agent of the industry in addition, as anti-aging agent, oxidation inhibitor etc., concrete as: 2,2,4-trimethylammonium-1,2-dihydroquinoline polymer (RD); Four [3-(3,5-di-t-butyl-4-hydroxyl) phenylpropionic acid] pentaerythritol ester (1010); Three (2, the 4-di-t-butyl) phenyl phosphites (168); Distearyl pentaerythritol diphosphite (618); N-cyclohexyl-N '-phenyl paraphenylenediamine (4010); 2,2 '-methylene-bis (4-methyl-6-tert butyl) phenol (2246) etc., can add also that the industry is known to can be used for toughness reinforcing rubber components.
In above-mentioned polyreaction, polymerization can be carried out under 100～170 ℃ of temperature, and pressure is normal pressure.Because polymeric reaction temperature is bigger to the molecular weight influence of resulting polymers, so the controlled polymerization temperature is important.Can be by the telo merization temperature to control the polystyrene viscosity-average molecular weight in (weight-average molecular weight is between 10～400,000) between 5～100,000.In the present invention,, can preferably adopt the form of stage feeding polymerization, promptly be chosen in the corresponding time of polymerization under the different polymeric temperature of reaction for controlling polymers molecular weight and raising monomer conversion.Comparatively embodiment preferred is, polymerization temperature and corresponding time may be selected to be: 100 ℃～130 ℃ following 1 hour, 130 ℃～140 ℃ the reaction 2 hours, 140 ℃～170 ℃ the reaction 3 hours.Polyreaction is earlier carried out prepolymerization under 100 ℃～130 ℃, not only control the active centre number, suitable controlled polymerization rate of heat release simultaneously, when transformation efficiency reaches 30～35%, just be the autoacceleration effect after, improve temperature of reaction to 170 ℃ more gradually, make to react completely.
Usually need conventional devolatilization, drying and other steps by the polyphenylacetylene combination that obtains after the polyreaction.
It is worthy of note in the above-mentioned toughened polystyrene composite of the present invention, owing to adopted a kind of rubber particle with special construction, in rubber particle, be nuclear with the rubber components, its skin is coated with the shell of one deck polystyrene, make the surface hard, when therefore this rubber particle being mixed with vinylbenzene, be difficult for reuniting, and has good wetting property with vinylbenzene, improved the consistency between rubber particle and polystyrene substrate after common polymerization, the dispersion state of rubber particles in polystyrene substrate is improved.Even thereby in the presence of less rubber particles, the toughness of polyphenylacetylene combination all is significantly improved, and still can keep other mechanical properties such as its intensity, rigidity.
Above-mentioned polyphenylacetylene combination not only have pure polystyrene insulation, be easy to advantages such as forming process, water absorbability be little, and polymerization technique is simple, erosion-resisting characteristics is better.Can be widely used in fields such as household electrical appliances, electronic apparatus industry and equipment industry, all occupy the very big market as meter case, lampshade, instrument part, telecommunication part, auto parts and medical facilities aspect.
Embodiment
The invention is further illustrated by the following examples, to deepen the understanding of the present invention.Below given embodiment be for better the explanation rather than the restriction the present invention.
Description of drawings
Fig. 1 is the SEM photo testing method under embodiment 1 gained polyphenylacetylene combination stretching section amplifies 40000 times:
1, Izod notched Izod impact strength (J/m): measure Emhorn shock strength (23 ℃) according to ASTM D-256-03
2, tensile yield strength (Mpa): test according to ASTM D-638-03.
3, gel content: press the GB/t18474-2001 test.
[embodiment 1]
1, the preparation of rubber particle: with styrene-butadiene latex (7030 latex, from the Shanghai Gaoqiao chemical plant, solids content 35%) 2300g, deionized water 650g, styrene 315g add in the still, with nitrogen with air displacement in the still, mix and blend 2 hours and absorb 8 hours under the 170rpm mixing speed, add initiator potassium persulfate (with 50 ml deionized water dissolving 0.6g) after fully disperseing, add again emulsifier sodium lauryl sulfate 0.1g, mixed 30 minutes, be warming up to 85 ℃, reacted 5 hours, and namely got the core-shell particle emulsion. With gained latex, add the crosslinking agent Isooctyl acrylate monomer and stirred one hour, adopt afterwards the cobalt source to carry out irradiation, dosage is 2.5Mrad, close rate is 50Gy/min. The core-shell particle powder that spray-dried (inlet temperature of spray dryer is controlled at 140 ℃～160 ℃, and outlet temperature is controlled at 40 ℃～60 ℃) obtains having full vulcanization type, gel content is 76wt%. Average grain diameter is 150nm. Weight ratio between the nucleocapsid is 1: 0.39.
2, the preparation of polyphenylacetylene combination: the above-mentioned nucleocapsid structure sample powder 130g that obtains, vinylbenzene (Yanshan Petrochemical production) 1600g and ethylbenzene 410g are added in the still, stir, swelling 4 hours adds antioxidant 1681g again, dispersion agent mineral oil 18g.With nitrogen with air displacement in the still.Adopt the method polymerization of free radical mass polymerization, initiating method adopts thermal initiation.Polymeric kettle heats up under the 170rpm stir speed (S.S.), 100 ℃ of following polymerizations one hour, 130 ℃ of following polymerizations two hours, continues to heat up, 145 ℃ of following polymerizations three hours.Because system viscosity is bigger, suitably reduce stir speed (S.S.) to 100rpm in the polymerization process, finish polymerization process, the thickness body of polymerization gained is discharged in the devolatilizer that enters 185 ℃, flash distillation rapidly removes unreacted monomer and solvent ethylbenzene under vacuum state.After the devolatilization polymkeric substance 1310g, the styrene conversion rate is 74%, the weight ratio of core-shell particle and polystyrene is 10: 90, promptly gets sample through cooling, granulation, sample preparation, and rerum natura is measured.Mechanical test results is that tensile yield strength is 38.9MPa, and cantilever beam impact strength is 57.7J/m.
Fig. 1 is the SEM figure (U.S. FEI Co. produces XL-30 type field launch environment scanning electron microscope) under embodiment 1 stretching section amplifies 40000 times.From photo as seen, the rubber particle component is than in homodisperse and the polystyrene substrate, median size is at 200nm, basically can think the agglomeration that rubber particle does not take place, and crackle does not appear between particulate and the base material, improved the consistency between rubber particles and polystyrene substrate effectively.
[comparative example 1]
Ethylbenzene 335g, vinylbenzene 2325g does not add rubber particle component of the present invention, the preparation styrene homopolymers.All the other conditions are identical with embodiment 1.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 38MPa, and cantilever beam impact strength is 19.6J/m.The cantilever beam impact strength of embodiment 1 sample is 2.94 times of comparative example 1.
[comparative example 2]
The core-shell particle latex of gained among the embodiment 1 is directly carried out spraying drying without radiation crosslinking, gained nucleocapsid structure rubber particle replaces the rubber particle of the nucleocapsid structure among the embodiment 1, all the other conditions are identical with embodiment 1, and discharging 1370g, core-shell particle weight percent are 10%.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 41.6MPa, and cantilever beam impact strength is 21.7J/m.
[embodiment 2]
After the rubber particle of the nucleocapsid structure of embodiment 1 milled, make nucleocapsid structure sample particle thinner (median size is 100nm), carry out toughening polystyrene, other conditions are identical with embodiment 1.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 42.4MPa, and cantilever beam impact strength is 31.1J/m.
[embodiment 3]
Improve nucleocapsid structure rubber particle consumption to 200g, the ethylbenzene consumption is 630g, anti-aging agent 10106.5g, and all the other conditions are identical with embodiment 1, and discharging 1290g, core-shell particle weight percent are 15%.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 39.5MPa, and cantilever beam impact strength is 33.9J/m.
The Mechanics Performance Testing result of table 1 polymer composition
| Embodiment | Rubber particle content wt% | Tensile yield strength MPa | Cantilever beam impact strength J/m |
| Embodiment 1 | 10％ | 38.9 | 57.7 |
| Comparative example 1 | 0 | 38.0 | 19.6 |
| Comparative example 2 | 10％ | 41.6 | 21.7 |
| Embodiment 2 | 10％ | 42.4 | 31.1 |
| Embodiment 3 | 15％ | 39.5 | 33.9 |
Claims (11)
1, a kind of toughened polystyrene composite, said composition is to be dispersed with the rubber particle that median size is the 20-300 nanometer in polystyrene substrate, and the content of rubber particle is 1wt%～40wt% in composition, described rubber particle is to be nuclear with a kind of rubber components with crosslinking structure, and being coated with polystyrene is shell.
2, toughened polystyrene composite according to claim 1, the weight ratio of the rubber components in the wherein said rubber particle and the polystyrene of coating is 1: 0.60～1: 1.30.
3, toughened polystyrene composite according to claim 1, the weight ratio of the rubber components in the wherein said rubber particle and the polystyrene of coating is 1: 0.1～1: 1.0.8.
4, toughened polystyrene composite according to claim 1, the rubber components in the wherein said rubber particle are selected from least a in sulfurized natural rubber, styrene-butadiene rubber(SBR), carboxylic styrene-butadiene rubber, paracril, carboxy nitrile rubber, polyhutadiene, chloroprene rubber, esters of acrylic acid rubber and the ethylene-propylene rubber(EPR).
5, toughened polystyrene composite according to claim 3, the gel content of wherein said rubber components is not less than 60wt%.
6, toughened polystyrene composite according to claim 1, wherein the content of rubber particle is 5wt%～25wt% in described composition.
7, toughened polystyrene composite according to claim 1, wherein said rubber particle is by comprising the method preparation of following steps: (1) is in the presence of emulsifying agent, with the respective emulsion of described rubber components and the mixture initiated polymerization of styrene monomer; (2) after the latex that step (1) is obtained adds the linking agent mixing, adopt the high energy gamma source x ray irradiation x, make rubber components crosslinked, obtain rubber particle after the drying.
8, toughened polystyrene composite according to claim 7, wherein said emulsifying agent are selected from a kind of and arbitrary combination in sodium lauryl sulphate, sodium stearate or the Sodium pentadecanecarboxylate.
9, toughened polystyrene composite according to claim 7, wherein said linking agent is selected from: (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, a kind of and arbitrary combination in Diethylene Glycol (methyl) acrylate, Vinylstyrene, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate.
10, toughened polystyrene composite according to claim 1, the weight ratio of the rubber components in the wherein said rubber particle and the polystyrene of coating is 1: 0.60～1: 1.30, this rubber components is selected from least a in sulfurized natural rubber, styrene-butadiene rubber(SBR) and the ethylene-propylene rubber(EPR), its gel content is not less than 80wt%, and the content of rubber particle is 5wt%～25wt% in described composition.
11, the preparation method of the described toughened polystyrene composite of a kind of claim 1, be by with described be nuclear with rubber components with crosslinking structure, the rubber particle that is coated with polystyrene and is shell swells in the styrene monomer, cause by thermal initiation or initiator, carrying out radical polymerization on the throne obtains, wherein the parts by weight of rubber particle are 5～25, the parts by weight 75～95 of styrene monomer.
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| CN103804810A (en) * | 2014-01-20 | 2014-05-21 | 苏州新区华士达工程塑胶有限公司 | Polystyrene brittle modified plastic |
| CN104479236A (en) * | 2014-11-20 | 2015-04-01 | 苏州新区佳合塑胶有限公司 | Liner material of refrigerator |
| CN106479069A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of polystyrene microsphere composite for laser sintering and moulding and preparation method thereof |
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| MX168323B (en) * | 1986-10-21 | 1993-05-18 | Rohm & Haas | COVERED NUCLEUS IMPACT MODIFIERS FOR STYRENE RESINS |
| CN1063187C (en) * | 1997-04-03 | 2001-03-14 | 中国石油化工总公司 | Process for preparing core-shell particle toughened polystyrene material |
| CN1152082C (en) * | 1999-12-03 | 2004-06-02 | 中国石油化工集团公司 | Full vulcanized powdered rubber with controllable particle diameter, preparing method thereof |
| CN1145662C (en) * | 2000-11-03 | 2004-04-14 | 中国石油化工股份有限公司 | Cross-linked powdered rubber and its preparing process and usage |
| CN1160405C (en) * | 2001-04-18 | 2004-08-04 | 中国石油化工股份有限公司 | Full-sulfurized thermoplastic polystyrene elastomer and its preparing process |
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| CN103804810A (en) * | 2014-01-20 | 2014-05-21 | 苏州新区华士达工程塑胶有限公司 | Polystyrene brittle modified plastic |
| CN104479236A (en) * | 2014-11-20 | 2015-04-01 | 苏州新区佳合塑胶有限公司 | Liner material of refrigerator |
| CN106479069A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of polystyrene microsphere composite for laser sintering and moulding and preparation method thereof |
| CN108314858A (en) * | 2018-03-21 | 2018-07-24 | 安徽江淮汽车集团股份有限公司 | A kind of PP-PS composite material and preparation methods |
| CN111375359A (en) * | 2018-12-27 | 2020-07-07 | 上海元颉新材料科技有限公司 | Monodisperse core-shell structure organic-inorganic composite nano rubber particle and preparation method and application thereof |
| CN113493582A (en) * | 2020-03-18 | 2021-10-12 | 中国石油化工股份有限公司 | Toughening agent composition and application thereof, HIPS (high impact polystyrene) resin, ABS (acrylonitrile-butadiene-styrene) resin and preparation method thereof |
| CN113493582B (en) * | 2020-03-18 | 2023-01-31 | 中国石油化工股份有限公司 | Toughening agent composition and application thereof, HIPS (high impact polystyrene) resin and ABS (acrylonitrile-butadiene-styrene) resin and preparation method thereof |
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| CN112552459A (en) * | 2020-12-04 | 2021-03-26 | 山纳合成橡胶有限责任公司 | Chloroprene rubber latex with core-shell structure colloidal particles and preparation method thereof |
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