CN101139456B - Toughened polystyrene composition and method of making the same - Google Patents
Toughened polystyrene composition and method of making the same Download PDFInfo
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Abstract
The invention provides a polystyrene combination and a preparing method for the combination, which comprises rubber particles distributed in a polystyrene substrate. The content of the rubber particles is 1-40wt%, preferably 3-30wt%, and best 5wt%-25wt%. The rubber particles comprise butadiene rubber particles and nanometer rubber particles by weight 1:0.01-1:1. The gel content in the nanometer rubber particles shall not be less than 60wt%. The combination is obtained by polymerizing two different types of rubber particles of different diameters with styrene, which comprises the graft polymerization of the butadiene rubber particles solved in the styrene, and in-situ dispersed polymerization of nanometer rubber particles melting in the styrene. The polystyrene combination is of higher stiffness while maintaining other mechanical properties such as strength and rigidity, etc.
Description
Technical field
The present invention relates to a kind of toughened polystyrene composite and preparation method thereof, in particular, the present invention relates to a kind of polystyrene resin composite that comprises cis-1,4-polybutadiene rubber particulate and nano-rubber particulate, it has the effect of sized particles coordination plasticizing.
Background technology
Polystyrene (PS) has characteristics such as matter is hard, transparent, rigidity, electrical insulating property, agent of low hygroscopicity, cheap, easy dyeing, easy processing because of it, have application widely in industry and civilian every field, has become one of current four big general-purpose plastics.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, at present methods that adopt rubber toughened polystyrene more.
To the system of rubber toughened polystyrene, generally accept multiple crazingization-shear zone toughening mechanism now.The introducing that it has been generally acknowledged that the micron order rubber grain helps to cause the expansion that plastic substrate produces a large amount of crazings and control crazing; The nano level rubber grain then helps to cause matrix and produces a large amount of shear zones, and the ability of this shear zone control crazing expansion is more effective.The initiation of crazing initiation and termination and shear zone and increase process can consume lot of energy, and interaction of Cun Zaiing between the two and synergy contribute for the toughness that improves material.
The method of traditional rubber toughened polystyrene, many employing cis-1,4-polybutadiene rubbers are dissolved in and carry out graft polymerization in the styrene monomer, as patent publication No. is the styrene resin that contains rubber of CN 1254722A and the method for preparation, this method for toughening is because the restriction of polymerizing condition, rubber grain footpath size in the gained matrix of materials all more than 1 μ m, is unfavorable for the formation of shear zone.Though this method has improved the shock strength of material, the add-on of rubber is extremely important, and having added influences rigidity; Add fewly, rigidity satisfies, but shock strength is not enough again.The inventor is through discovering, if introduce a kind of nano level rubber particle simultaneously again and swell in and carry out the original position dispersion polymerization in the vinylbenzene adding cis-1,4-polybutadiene rubber, not only help the formation of shear zone, the expansion of control crazing, improve the toughness of material, and effectively kept the intensity and the rigidity of material.
Summary of the invention
The purpose of this invention is to provide a kind of polyphenylacetylene combination, described composition is a dispersion rubber particulate in polystyrene substrate, and the content of rubber particle is 1～40wt% in described composition, is preferably 3～30wt%, more preferably 5～25wt%, most preferably 5～10wt%.Described rubber particle comprises cis-1,4-polybutadiene rubber particulate and nano-rubber particulate, and the weight ratio of cis-1,4-polybutadiene rubber particulate and nano-rubber particulate is 1: 0.01～1: 1, is preferably 1: 0.05～1: 0.5, more preferably 1: 0.05～1: 0.2.Described nano-rubber particulate is selected at least a in the following material for use: nanometer butadiene-styrene-vinyl rubber particle, nanotube-natural rubber particulate or nanometer divinyl rubber particulate, preferentially select the nanometer butadiene-styrene-vinyl rubber particle.
Described cis-1,4-polybutadiene rubber comprises high-cis divinyl rubber and low cis divinyl rubber, preferentially selects the high-cis divinyl rubber.
The epigranular of described nano-rubber particulate, its particle diameter is generally 20～500nm, is preferably 30～400nm, and more excellent is 50～300nm.Be characterized in that crosslinking degree is higher, the present invention adopts the method for the known mensuration gel content of the industry to characterize the crosslinking degree of rubber.The gel content of described nano-rubber particulate generally is not less than 60wt%, preferably is not less than 70wt%, more preferably is not less than 90wt%.The swelling index of described nano-rubber particulate is not more than 15, preferably is not more than 13.Each particulate in this nano-rubber particulate all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, divides the phenomenon that equates uneven phase.It need not to add separant and gets final product unrestricted flow.
Kind for the nano-rubber particulate does not have any restriction, it comprises at least a in nanometer butadiene-styrene-vinyl rubber particle, nanotube-natural rubber particulate and the nanometer divinyl rubber particulate, preferentially select the nanometer butadiene-styrene-vinyl rubber particle for use, this rubber particle and preparation method thereof is disclosed among the applicant's the Chinese patent CN1152082C, and its full content is introduced the present invention as a reference.
A specific embodiment for preparing nano-rubber particulate of the present invention is:
With the synthesizing butadiene styrene rubber emulsion is raw material, adds linking agent and stirs one hour, adopts the high energy gamma source x ray irradiation x afterwards, makes rubber components crosslinked, gets cross-linking type butylbenzene rubber latex, and the gel content of emulsion should be not less than 60wt%, and swelling index should be not more than 15.Obtain nanometer powder styrene-butadiene rubber(SBR) particulate after spray-dried.
The linking agent that adds can be 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.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 is 2.5Mrad, and dose rate is 50Gy/min.Drying process can adopt spray-drying process or precipitation desiccating method, the preferably spray drying method, the inlet temperature of spray-dryer is 100 ℃～200 ℃, and temperature out is 20 ℃～80 ℃, collects dried nano-rubber particulate with certain gel content in cyclonic separator.
Another object of the present invention provides a kind of preparation of compositions method of new impact-resistant polystyrene, and rubber and styrene polymerization by two kinds of particle diameters of size obtain.In the polyphenylacetylene combination of gained, formed the effect of the rubber particle coordination plasticizing polystyrene of two kinds of particle diameters of size, this method for toughening helps the formation of shear zone in the matrix and the termination of crazing, under the synergy of multiple crazing and shear zone, improve the toughness of material, and still can keep other mechanical properties such as its intensity, rigidity.
Polymerization process of the present invention, comprise: the method that described nano-rubber particulate, cis-1,4-polybutadiene rubber, vinylbenzene adopt free radical to cause is carried out mass polymerization, described polymerization process comprises that described nano-rubber particulate swells in cinnamic original position dispersion polymerization and described cis-1,4-polybutadiene rubber is dissolved in cinnamic graft polymerization, after described polymerization process finishes, remove unnecessary monomer and solvent, obtain the polystyrene resin of high impact strength.
The radical polymerization initiating method adopts thermal initiation or initiator to cause.Initiator can be 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 the 0.1wt%～2wt% of styrene monomer total amount.
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 organic solvent, and then carry out thermal initiation or add an amount of initiator initiated polymerization.
In addition, the known some other auxiliary agent of the also available industry in above-mentioned radical polymerization process, as anti-aging agent, antioxidant, 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), CPPD N cyclohexyl N (4010), 2,2 '-methylene-bis (4-methyl-6-tert butyl) phenol (2246), 3,5-di-t-butyl-4 hydroxy phenyl propionic acid octadecanol ester (1076) etc.; Thermo-stabilizer, concrete as: Zinic stearas, lead stearate, cadmium stearate etc.
The molecular weight of polystyrene is very big to its performance impact, and weight-average molecular weight is lower than 100,000, and then physical strength is very low, and weight-average molecular weight is higher than 400,000, and processing characteristics is very poor.Polymeric reaction temperature is the principal element of impact polymer molecular weight, and temperature of reaction is higher, the active centre of formation the more, speed of reaction is fast more, polymericular weight is low more, 10 ℃～20 ℃ of the every risings of temperature of reaction, molecular weight descends at double.So necessary telo merization temperature is to control the polystyrene weight-average molecular weight between 10～400,000.Being aggregated under 100～170 ℃ of temperature that this patent carried out carried out, and pressure is normal pressure.
For controlling polymers molecular weight and raising monomer conversion, can adopt the form of stage feeding polymerization, promptly be chosen in the corresponding time of polymerization under the different polymeric temperature of reaction, being chosen as of this patent polymerization temperature and corresponding time: 100 ℃～130 ℃ following 4 hours, 130 ℃～140 ℃ were reacted 2 hours, and 140 ℃～170 ℃ were reacted 1 hour.
Usually need conventional devolatilization, drying and other steps by the poly styrene polymer that obtains after the polyreaction.
In the impact-resistant polystyrene composition of the present invention, owing to not only adopted cis-1,4-polybutadiene rubber to be dissolved in cinnamic graft polymerization but also adopted the nano-rubber particulate to swell in cinnamic original position dispersion polymerization dual mode, in polystyrene substrate, formed the particulate of two kinds of particle diameters of size, when causing the crazing generation, also cause matrix and produce a large amount of shear zones, control the expansion of crazing, thereby reach the effect of coordination plasticizing polystyrene.Acting in conjunction of this big or small two kinds of particle diameter particulates and synergy have effectively improved the toughness of polystyrene material, 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 its polymerization technique is simple, and has good erosion-resisting characteristics.Can be widely used in fields such as household electrical appliances, electronic apparatus industry and equipment industry, as all occupying the very big market aspect meter case, lampshade, instrument part, telecommunication part, auto parts and the medical facilities.
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
The transmission electron microscope photo TEM figure of Fig. 1 embodiment 4 gained polyphenylacetylene combinations
The transmission electron microscope photo TEM figure of Fig. 2 comparative example 5 gained polyphenylacetylene combinations
Adopt the form of transmission electron microscope observing sample, transmission electron microscope model: TECNAI 20, Dutch FEI Co. produces. Ultramicrotome is adopted in sample preparation, and model: LEICAEMFCS observes after osmium tetroxide dyeing at-55 ℃ of book sheets that cut about 100nm.
Physical property measurement
1, socle girder notched Izod impact strength (kJ/m
2): test according to GB/T1843-1996.
2, tensile yield strength (MPa): test according to GB/T1040-1992.
3, the mensuration of gel content: test according to GB/T 18474-2001.
4, the mensuration of swelling index: test according to GB/T 7763-1987.
Embodiment 1
Preparation nano-rubber particulate---nanometer butadiene-styrene-vinyl rubber particle:
With the commercially available styrene-butadiene latex of solid content 45wt% (orchidization production, the trade mark: butylbenzene-50) 5kg places a container, under agitation the different monooctyl ester 67.5g of dropwise addition of acrylic acid, after being added dropwise to complete, continue to stir 1 hour, use cobalt-60 radiosterilize afterwards, dosage is 2.5Mrad, and dose rate is 50Gy/min.Latex behind the irradiation is by the spray-dryer spraying drying, and the inlet temperature of spray-dryer is 140 ℃～160 ℃, and temperature out is 40 ℃～60 ℃, collects in cyclonic separator and obtains free flowable full sulfuration nanometer butadiene-styrene-vinyl rubber particle.The particle diameter that records the nanometer butadiene-styrene-vinyl rubber particle is about 50～150nm, and gel content is 90.0wt%, and swelling index is 12.9.
The preparation polyphenylacetylene combination:
Nanometer butadiene-styrene-vinyl rubber particle 13g, high-cis cis-1,4-polybutadiene rubber 1 (BR-9004 that embodiment 1 is obtained, Yanshan Petrochemical production) 112g, vinylbenzene (Yanshan Petrochemical production) 1600g and ethylbenzene 420g add in the still, stir, swelling 72 hours adds anti-aging agent 1076 1.6g again.
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.), 120 ℃ of following polymerizations 4 hours, 130 ℃ of following polymerizations 2 hours, 160 ℃ of following polymerizations 1 hour.Excessive in the polymerization process owing to system viscosity, suitably reduce stir speed (S.S.) to 100rpm, finish polymerization process, the thickness body of polymerization gained is escaped and enter in 185 ℃ the devolatilizer, flash distillation rapidly removes unreacted monomer and solvent ethylbenzene under vacuum state.Obtain polymkeric substance 1310g after the devolatilization, the styrene conversion rate is 74%, and the rubber particle weight percent is 10%, promptly gets sample through cooling, granulation, sample preparation, and rerum natura is measured.Mechanical test results is that tensile yield strength is 30.7MPa, and cantilever beam impact strength is 16.4kJ/m
2
Comparative example 1
Do not add the nanometer butadiene-styrene-vinyl rubber particle, only add high-cis cis-1,4-polybutadiene rubber 1 (with embodiment 1) 125g, other condition is identical with embodiment 2.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 29.4MPa, and cantilever beam impact strength is 14.5kJ/m
2
Comparative example 2
Do not add high-cis cis-1,4-polybutadiene rubber 1, only add the nanometer butadiene-styrene-vinyl rubber particle 200g that embodiment 1 obtains, other condition is identical with embodiment 2.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 32.2MPa, and cantilever beam impact strength is 4.6kJ/m
2
Comparative example 3
With the cis-1,4-polybutadiene rubber 1 in high-cis cis-1,4-polybutadiene rubber 2 (BUNA HX529TC) the replacement comparative example 1 of the another kind of trade mark, other condition is identical with embodiment 2.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 35.1MPa, and cantilever beam impact strength is 11.1kJ/m
2
Embodiment 2
The nanometer butadiene-styrene-vinyl rubber particle that adds embodiment 1: 12.5g, cis-1,4-polybutadiene rubber 1:87g, high-cis cis-1,4-polybutadiene rubber 2:529T 38g, vinylbenzene 1600g and ethylbenzene 420g, other condition is identical with embodiment 1.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 28.6MPa, and cantilever beam impact strength is 19.6kJ/m
2
Comparative example 4
Do not add the nanometer butadiene-styrene-vinyl rubber particle, other condition is identical with embodiment 2.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 31.0MPa, and cantilever beam impact strength is 14.4kJ/m
2
Embodiment 3
Add high-cis cis-1,4-polybutadiene rubber 1 (with embodiment 1) 94g, add embodiment 1 gained nanometer butadiene-styrene-vinyl rubber particle 6.5g again, other condition is identical with embodiment 1.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 33.9MPa, and cantilever beam impact strength is 10.9kJ/m
2
Embodiment 4
Add high-cis cis-1,4-polybutadiene rubber 1 (with embodiment 1) 88g, add embodiment 1 gained nanometer butadiene-styrene-vinyl rubber particle 12.5g again, other condition is identical with embodiment 1.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 32.3MPa, and cantilever beam impact strength is 18.0kJ/m
2
Embodiment 5
Add high-cis cis-1,4-polybutadiene rubber 1 (with embodiment 1) 75g, add embodiment 1 gained nanometer butadiene-styrene-vinyl rubber particle 25.5g again, other condition is identical with embodiment 1.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 31.3MPa, and cantilever beam impact strength is 12.8kJ/m
2
Embodiment 6
Add high-cis cis-1,4-polybutadiene rubber 1 (with embodiment 1) 63g, add embodiment 1 gained nanometer butadiene-styrene-vinyl rubber particle 37.5g again, other condition is identical with embodiment 1.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 33.2MPa, and cantilever beam impact strength is 7.8kJ/m
2
Comparative example 5
Do not add nanometer styrene-butadiene rubber(SBR) particulate, only add high-cis cis-1,4-polybutadiene rubber 1 (with embodiment 1) 100.5g, other condition is identical with embodiment 1.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 36.0MPa, and cantilever beam impact strength is 10.2kJ/m
2
Embodiment 7
Add high-cis cis-1,4-polybutadiene rubber 1 (with embodiment 1) 63g, add embodiment 1 gained nanometer butadiene-styrene-vinyl rubber particle 12.5g again, other condition is identical with embodiment 1.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 33.2MPa, and cantilever beam impact strength is 12.8kJ/m
2
Comparative example 6
Do not add nanometer styrene-butadiene rubber(SBR) particulate, only add high-cis cis-1,4-polybutadiene rubber 1 (with embodiment 1) 75.5g, other condition is identical with embodiment 1.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 34.0MPa, and cantilever beam impact strength is 8.6kJ/m
2
Table 1
| Embodiment | The rubber particle component | Rubber content wt% | Tensile yield strength MPa | Cantilever beam impact strength kJ/m 2 |
| Embodiment 1 | (cis-1,4-polybutadiene rubber 1: nano-rubber=9: 1) | 10％ | 30.7 | 16.4 |
| Comparative example 1 | (cis-1,4-polybutadiene rubber 1) | 10％ | 29.4 | 14.5 |
| Comparative example 2 | (nano-rubber) | 15％ | 32.2 | 4.6 |
| Comparative example 3 | (cis-1,4-polybutadiene rubber 2) | 10％ | 35.1 | 11.1 |
| Embodiment 2 | (cis-1,4-polybutadiene rubber 1: cis-1,4-polybutadiene rubber 2: nano-rubber=6.3: 2.7: 1) | 10％ | 28.6 | 19.6 |
| Comparative example 4 | (cis-1,4-polybutadiene rubber 1: cis-1,4-polybutadiene rubber 2=7: 3) | 10％ | 31.0 | 14.4 |
| Embodiment | The rubber particle component | Rubber content wt% | Tensile yield strength MPa | Cantilever beam impact strength kJ/m 2 |
| Embodiment 3 | (cis-1,4-polybutadiene rubber 1: nano-rubber=7.5: 0.5) | 8％ | 33.9 | 10.9 |
| Embodiment 4 | (cis-1,4-polybutadiene rubber 1: nano-rubber=7: 1) | 8％ | 32.3 | 18.0 |
| Embodiment 5 | (cis-1,4-polybutadiene rubber 1: nano-rubber=6: 2) | 8％ | 31.3 | 12.8 |
| Embodiment 6 | (cis-1,4-polybutadiene rubber 1: nano-rubber=5: 3) | 8％ | 33.2 | 7.8 |
| Comparative example 5 | (cis-1,4-polybutadiene rubber 1) | 8％ | 31.1 | 9.7 |
| Embodiment 7 | (cis-1,4-polybutadiene rubber 1: nano-rubber=5: 1) | 6％ | 33.2 | 12.8 |
| Comparative example 6 | (cis-1,4-polybutadiene rubber 1) | 6％ | 34.0 | 8.6 |
As can be seen from the table, the introducing of nano-rubber particulate makes the resistance to impact shock of material obtain in various degree raising, keeps even improved the tensile strength of material.The weight ratio of cis-1,4-polybutadiene rubber particulate 1 and nano-rubber particulate is 7: 1 o'clock, and the resistance to impact shock of material reaches maximum value, continues to improve the content of nano-rubber particulate, and resistance to impact shock descends on the contrary.The lifting to a certain degree of getting back of the cis-1,4-polybutadiene rubber particulate 2 that adds the another kind of trade mark, the resistance to impact shock of material.
From the TEM photo of embodiment illustrated in figures 1 and 2 and comparative example as can be seen, the inside of embodiment and comparative example resulting polymers has all formed a kind of particle diameter at the cellular microgranular texture of 1～3 μ m, and the part polystyrene contains in this rubber particle inside.This structure can improve the impact property of material, and add in the embodiment of the invention among polymkeric substance Fig. 1 of gained behind the nano-rubber particulate, the nano-rubber particulate is scattered in around the cis-1,4-polybutadiene rubber particle uniformly, can know and see that a rule crazing causes, grows from the cis-1,4-polybutadiene rubber particle, finally ended by the nano-rubber particulate, the existence of this structure can make the toughness of polyphenylacetylene combination improve, and other mechanical properties such as its intensity, rigidity still can keep.
Claims (12)
1. polyphenylacetylene combination, it is characterized in that described composition comprises rubber particle 1～40wt%, described rubber particle comprises that at least a cis-1,4-polybutadiene rubber particulate and at least a median size are the nano-rubber particulate of 20～300nm, described nano-rubber particulate is at least a of following material: nanometer butadiene-styrene-vinyl rubber particle, nanotube-natural rubber particulate or nanometer divinyl rubber particulate, the gel content of described nano-rubber particulate is not less than 60wt%, and the weight ratio of described cis-1,4-polybutadiene rubber particulate and described nano-rubber particulate is 1: 0.01～1: 1;
Described polyphenylacetylene combination carries out mass polymerization by the method that adopts free radical to cause described nano-rubber particulate, cis-1,4-polybutadiene rubber, vinylbenzene and obtains, wherein said nano-rubber particulate is not more than 15 according to the swelling index of GB/T7763-1987 standard test.
2. according to the described composition of claim 1, the content that it is characterized in that described rubber particle is 3～30wt%.
3. according to the described composition of claim 2, the content that it is characterized in that described rubber particle is 5～25wt%.
4. according to the described composition of claim 1, the weight ratio that it is characterized in that described cis-1,4-polybutadiene rubber particulate and described nano-rubber particulate is 1: 0.05～1: 0.5.
5. according to the described composition of claim 1, it is characterized in that described cis-1,4-polybutadiene rubber particulate is high-cis divinyl rubber particulate or low cis divinyl rubber particulate.
6. according to the described composition of claim 1, it is characterized in that described nano-rubber diameter of particle 50～300nm.
7. according to the described composition of claim 1, it is characterized in that described nano-rubber micro gel content is not less than 70wt%.
8. according to the described composition of claim 1, it is characterized in that described nano-rubber micro gel content is not less than 90wt%.
9. according to the described composition of claim 1, it is characterized in that described nano-rubber particulate is not more than 13 according to the swelling index of GB/T7763-1987 standard test.
10. the method for preparation of compositions described in one of claim 1～9, comprise: the method that described nano-rubber particulate, cis-1,4-polybutadiene rubber, vinylbenzene adopt free radical to cause is carried out mass polymerization, its polyreaction comprises that described nano-rubber particulate swells in cinnamic original position dispersion polymerization and described cis-1,4-polybutadiene rubber particle dissolution in cinnamic graft polymerization, after described polymerization process finishes, remove unnecessary monomer and solvent, obtain polyphenylacetylene combination.
11. according to the described preparation method of claim 10; it is characterized in that; described free radical causes the employing thermal initiation or initiator causes; wherein initiator is selected from least a in Potassium Persulphate, dicumyl peroxide, hydrogen phosphide cumene, benzoyl peroxide or the peroxide di-t-butyl, and the consumption of initiator is the 0.1wt%～2wt% of styrene monomer total amount.
13., it is characterized in that described being aggregated in the organic solvent carried out according to the described preparation method of claim 11, wherein organic solvent adopts aromatic hydrocarbons, the consumption of organic solvent is 0～30wt% of styrene monomer total amount.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5685528A (en) * | 1994-11-05 | 1997-11-11 | Koenig & Bauer-Albert Aktiengesellschaft | Paper web feed for a folding apparatus |
| CN1254722A (en) * | 1998-11-20 | 2000-05-31 | 大赛璐化学工业株式会社 | Styrene resin containing rubber and preparing process thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5685528A (en) * | 1994-11-05 | 1997-11-11 | Koenig & Bauer-Albert Aktiengesellschaft | Paper web feed for a folding apparatus |
| CN1254722A (en) * | 1998-11-20 | 2000-05-31 | 大赛璐化学工业株式会社 | Styrene resin containing rubber and preparing process thereof |
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