CN100491460C - Impact-resistant polystyrene composition and its preparation method - Google Patents
Impact-resistant polystyrene composition and its preparation method Download PDFInfo
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Abstract
The invention provides a novle impact polystyrene compound, which is prepared through polymerization by using phenylethene containing small grain- size powder. Said small grain- size powder is cross-linking powder rubber with its grain size being 20- 500 nm, the gel content is no less than 60wt%, and swelling index is no more than 15. 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 impact-resistant polystyrene composition and preparation method thereof, more particularly, the present invention relates to a kind of ultra fine powder rubber enhancing touthness of polyphenylethylene by adding resin and preparation method thereof.
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, has application widely in industry and civilian every field, 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.
In order to improve the toughness of polystyrene, the method for normal at present employing polymerization or blend is mixed toughness reinforcing component in polystyrene.Polymerization is to add rubber components in the styrene polymerization process, carries out polymerization in the styrene monomer as cis-1,4-polybutadiene rubber is dissolved in.Blending method is the method that adopts rubber components and polystyrene melt blending, obtains blend composition as styrene-butadiene rubber(SBR) and polystyrene blend.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 small particle size, particularly nano level rubber particles comes the enhancing touthness of polyphenylethylene by adding resin can reach effect preferably, mostly based on nanoparticle and polystyrene blend, as patent publication No. is that CN1556139 adopts polystyrene and the blend of nano level polymeric amide-6 particle, can suitably improve the shock strength and the breaking tenacity of material, but because blend method is difficult to the dispersion state of toughness reinforcing particle in polystyrene substrate effectively controlled, consistency between rubber particles and polystyrene substrate is relatively poor, therefore, the mechanical property of resultant blend is also unsatisfactory.
Many being dissolved in based on rubber of traditional bulk polymerization carried out graft polymerization in the vinylbenzene, a kind of styrene resin that contains rubber and preparation method thereof is disclosed as patent CN1254722A, it need guarantee that the percentage of grafting of styrene monomer and divinyl rubber is not less than 1 and the control size of divinyl rubber in polystyrene, polymerizing condition harshness, technology are comparatively complicated.
Summary of the invention
The invention provides a kind of composition of new impact-resistant polystyrene, it obtains by the styrene polymerization that contains the small particle size powdered rubber.In the polyphenylacetylene combination of gained, improved the consistency between rubber particles and polystyrene substrate, the dispersion state of rubber particles in polystyrene substrate is improved.Even thereby in the presence of less rubber particles, the toughness of gained polyphenylacetylene combination all is significantly improved, and still can keep other mechanical properties such as its intensity, rigidity.
A kind of impact-resistant polystyrene composition, it obtains by the composition polyreaction that contains following component:
Rubber particle: parts by weight are 3～40
Vinylbenzene: parts by weight are 60～97
Wherein said rubber particle is that particle diameter is the cross-linked powdered rubber of 20～500nm, and its gel content is not less than 60wt%, preferably is not less than 70wt%, more preferably is not less than 90wt%.
Characteristics of described rubber particle are less, the even-grained powdered rubbers of particle diameter, and its particle diameter is generally 20～500nm, is preferably 30～400nm, more preferably 50～300nm.Its another characteristics are that crosslinking degree 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 powdered rubber generally is not less than 60wt%, preferably is not less than 70wt%, more preferably is not less than 90wt%.Preferably, the swelling index of described powdered rubber is not more than 15, preferably is not more than 13.Each particulate in preferred this powdered rubber 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 above-mentioned cross-linked powdered rubber does not have any restriction, and it can comprise at least a in powder styrene butadiene rubber, powder natural rubber and the powder divinyl rubber.
Can adopt industry known method to prepare described cross-linked powdered rubber.Preferred disclosed cross-linked powdered rubber of Chinese patent CN1145662C that adopts the applicant and preparation method thereof, its associated viscera is introduced the present invention as a reference.
Particularly, a specific embodiment for preparing rubber particle of the present invention is:
Synthetic rubber latex with cross-linking type is a raw material, and drying can obtain cross-linked powdery.Raw emulsion can adopt cross-linking type butylbenzene rubber latex, crosslinking butadiene elastoprene emulsion etc., and the gel content of emulsion should be not less than 60wt%, and swelling index should be not more than 15.Drying process can adopt spray-drying process or precipitation desiccating method.The preferably spray drying method, the inlet temperature of spray-dryer can be controlled in 100-200 ℃, and temperature out is controlled at 20-80 ℃.In the preparation process of described cross-linked powdery, for fear of the reunion of rubber particle, and the rigidity of raising final composition, can also introduce some additives such as lime carbonate etc., its median size is advisable with 50-100nm.
The synthetic rubber latex of described cross-linking type can adopt the commercially available prod, as commercially available styrene-butadiene latex, commercially available polybutadiene latex etc.In order to improve the gel content of rubber particle, the high energy gamma source ray that also can adopt before spraying drying carries out cross-linking radiation with emulsion.For example irradiation is carried out in the cobalt source, and dosage can be 2.5Mrad, and dose rate can be 50Gy/min.
The cinnamic polyreaction that contains rubber particle of the present invention 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 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 weight ratio of styrene monomer and organic solvent is generally 1:0.1-1:0.5.Styrene monomer and rubber particle are dissolved in the organic solvent, and direct heat causes or is adding initiated polymerization under an amount of initiator then.Particularly, the preparation method of impact-resistant polystyrene composition of the present invention, comprise rubber particle, vinylbenzene and optional adjuvants, be dissolved in the organic solvent, carry out Raolical polymerizable, reaction removes unnecessary monomer and solvent after finishing, obtain impact-resistant polystyrene composition, described organic solvent is the aromatic hydrocarbons of carbon number 6-20.
In above-mentioned radical polymerization process, also can add the known some other auxiliary agent of the industry in addition, as anti-aging agent, antioxidant 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 (2,4-di-t-butyl) phenyl phosphites (168); Distearyl pentaerythritol diphosphite (618); N-cyclohexyl-N '-phenyl paraphenylenediamine (4010); 2,2 '-methylene-bis (4-methyl-6-tertiary butyl) phenol (2246) etc.
In above-mentioned polyreaction, the thermal-initiated polymerization of free radical 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 ℃ reactions are 2 little, 140 ℃～170 ℃ reactions 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.
Also can adopt initiator to cause radical polymerization, initiator 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.
Usually need conventional devolatilization, drying and other steps by the poly styrene polymer that obtains after the polyreaction.
In the above-mentioned impact-resistant polystyrene composition of the present invention, owing to adopted homogeneous, nano level rubber particle, improved the consistency between rubber particles and polystyrene substrate, 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.
Simultaneously, the present invention has not only saved the process of cutting glue, colloidal sol in the traditional technology owing to adopt directly polymerization process on the throne of small particle size powder styrene butadiene rubber, and rubber grain produces grafting with vinylbenzene hardly, processing condition are comparatively simple, save unnecessary man power and material.
The polyphenylacetylene combination of gained of the present invention not only have pure polystyrene insulation, be easy to advantages such as forming process, water absorbability are little, and polymerization technique simple, have certain shock strength.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 under embodiment 1 gained polyphenylacetylene combination stretching section amplifies 40000 times
Method of testing
1, Izod notched Izod impact strength (J/m): measure Izord Impact intensity (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.
4, the mensuration of swelling index: with reference to Chinese patent CN1145662C Instructions Page 3 disclosed method.
[embodiment 1]
1, the preparation method of styrene-butadiene rubber(SBR) powder:
Commercially available carboxylic styrene butadiene latex (Yanshan Petrochemical production, the trade mark: XSBRL-54B1) place a container, under agitation dropwise addition of acrylic acid isocaprylic acid 75g with solid content 50wt%, after being added dropwise to complete, continue to stir one 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, the inlet temperature of spray-dryer is 140 ℃～160 ℃, temperature out is 40 ℃～60 ℃, collects dried carboxylic styrene-butadiene rubber powder in cyclonic separator, obtains free flowable full sulfuration carboxylic styrene-butadiene rubber powder.The particle diameter that records powdered rubber is about 150～250nm, and gel content is 92.6%, and swelling index is 7.6.
2, the preparation of polyphenylacetylene combination:
The above-mentioned styrene-butadiene rubber(SBR) powder 160g that obtains, vinylbenzene (Yanshan Petrochemical production) 2030g and ethylbenzene 228g are added in the still, stir, swelling 4 hours adds anti-aging agent RD 0.16g again, antioxidant 1681.6g.
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 excessive, suitably reduce stir speed (S.S.) to 100rpm in the polymerization process, finish polymerization process, the thickness body of polymerization gained is discharged fall into 185 ℃ devolatilizer, flash distillation rapidly removes unreacted monomer and solvent ethylbenzene under vacuum state.After the devolatilization polymkeric substance 1680g, the styrene conversion rate is 75%, the weight ratio of rubber and polystyrene is 10:90, promptly gets sample through cooling, air-dry, granulation, sample preparation, and rerum natura is measured.
Mechanical test results is that tensile yield strength is 42.7MPa, and cantilever beam impact strength is 31.1J/m.Fig. 1 is the SEM figure (U.S. FEI Co., XL-30 type field launch environment scanning electron microscope) of this sample section under 40000 times.As seen the rubber particles of small particle size is scattered in the polystyrene substrate more uniformly.
[comparative example 1]
Ethylbenzene 335g, vinylbenzene 2325g does not add toughness reinforcing component, 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 1.59 times of comparative example.
[embodiment 2]
With embodiment 1, just in polymerization process, solvent ethylbenzene consumption is brought up to 600g, reduce system viscosity.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 42.5MPa, and cantilever beam impact strength is 30.6J/m.
[embodiment 3]
Adopt butylbenzene powdered rubber 165g, vinylbenzene 2050g and the solvent ethylbenzene 200g of embodiment 1-1 preparation to add in the still, stir, swelling 4 hours adds anti-aging agent RD 1.65g and dispersion agent mineral oil 25g again.All the other conditions are identical with embodiment 1-2, and discharging 1660g, rubber content weight percent are 10%.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 38.4MPa, and cantilever beam impact strength is 34.7J/m.
[embodiment 4]
1, the preparation method of styrene-butadiene rubber(SBR) powder:
Solid content is commercially available styrene-butadiene latex (Lanhua Latex Research and Development Centre's production of 45 weight %, the trade mark: butylbenzene-50), by the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140 ℃～160 ℃, and temperature out is 40 ℃～60 ℃, collects dried butylbenzene powdered rubber in cyclonic separator, obtain cross-linking type butylbenzene powdered rubber, its particle diameter is about 100nm～200nm, and gel content is 88.9%, and swelling index is 12.7.
2, the preparation of polyphenylacetylene combination:
With above-mentioned butylbenzene powdered rubber 165g, the vinylbenzene 2050g that obtains, and solvent ethylbenzene 200g add in the still, stir, swelling 8 hours adds anti-aging agent RD 168g and dispersion agent white oil (mineral oil) 25g again.All the other conditions are identical with embodiment 1, and discharging 1780g, rubber content weight percent are 9.3%, and the Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 45.1MPa, and cantilever beam impact strength is 27.4J/m.
[embodiment 5]
Pressure polymerization: initial pressure is 0.4MPa in the still, and all the other conditions are identical with embodiment 4, and material viscosity is very big in the polymerization process.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 39MPa, and cantilever beam impact strength is 27.0J/m.
[embodiment 6]
1, contain the preparation of the powdered rubber of nano-calcium carbonate:
(nano Tyke, Beijing development of new techniques company limited produces with a certain proportion of nano-calcium carbonate slurries, median size is about 50nm) with styrene butadiene rubber latex (DB-50 with highly cross-linked structure, the Lanzhou petrochemical iy produced) mixes (dried glue and nano-calcium carbonate weight ratio are 8:2), the styrene-butadiene rubber(SBR)/nano-CaCO that obtains having the structure contained after spray-dried
3The composite elastic particle, median size is about 100～200nm.
2, the preparation of polyphenylacetylene combination:
This rubber 150g, vinylbenzene 1600g and solvent ethylbenzene 420g are added in the still, stir, swelling 4 hours adds antioxidant 1681g and dispersion agent mineral oil 18g again.All the other conditions are identical with embodiment 1-1, and discharging 1250g, rubber content weight percent are 12%.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 37.2MPa, and cantilever beam impact strength is 37.4J/m.
[embodiment 7]
All the other conditions are identical with embodiment 6, but adopt initiator to cause radical polymerization in the polymerization process.Need to add initiator isopropyl benzene hydroperoxide 0.1% (weight percent), discharging 1370g, rubber content weight percent are 11%.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 40.8MPa, and cantilever beam impact strength is 24.1J/m.
[embodiment 8]
The add-on of the powdered rubber that embodiment 1-1 is obtained increases to 260g, and all the other conditions are identical with embodiment 8, and discharging 1130g, rubber content are 23% (weight percent).The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 27.8MPa, and cantilever beam impact strength is 52.0J/m.
[embodiment 9]
The powdered rubber that embodiment 4 is obtained replaces the powdered rubber of embodiment 8, and all the other conditions are identical with embodiment 8, and discharging 1295g, rubber content weight percent are 15%.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 33.8MPa, and cantilever beam impact strength is 33.1J/m.
[embodiment 10]
Embodiment 1 gained powdered rubber 180g, thermoplastic elastomer SBS (Ba Ling petrochemical iy produced, model YH-791, butadiene content 70%) 20g, vinylbenzene 1600g and solvent ethylbenzene 420g add in the still, stir swelling 8 hours.All the other conditions are identical with embodiment 8, discharging 1300g, and each weight percentages of components is: polystyrene: rubber: SBS=85:13.5:1.5.The Mechanical test results of the final polymkeric substance of gained is that tensile yield strength is 34.7MPa, and cantilever beam impact strength is 38.7J/m.
The Mechanics Performance Testing result of table 1 S compositions
| Embodiment | Powdered rubber content wt% | Tensile yield strength MPa | Cantilever beam impact strength J/m |
| Embodiment 1 | 10 | 42.7 | 31.1 |
| Comparative example 1 | 0 | 38.0 | 19.6 |
| Embodiment 2 | 10 | 42.5 | 30.6 |
| Embodiment 3 | 10 | 38.4 | 34.7 |
| Embodiment 4 | 9.3 | 45.1 | 27.4 |
| Embodiment 5 | 10 | 39.0 | 27.0 |
| Embodiment 6 | 12 | 37.2 | 37.4 |
| Embodiment 7 | 11 | 40.8 | 24.1 |
| Embodiment 8 | 23 | 27.8 | 52.0 |
| Embodiment 9 | 15 | 33.8 | 33.15 |
| Embodiment 10 | 15 | 34.7 | 38.7 |
By above-mentioned data as can be seen, polyphenylacetylene combination of the present invention all has high impulse strength, and when the gel content of powdered rubber was higher, toughening effect was better, and cantilever beam impact strength improves with the increase of rubber content, and tensile yield strength reduces with the increase of rubber content.From Fig. 1 photo as can be seen, the rubber particle component is scattered in the polystyrene substrate more equably, median size does not increase 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.
Claims (8)
1. impact-resistant polystyrene composition, it obtains by the composition polyreaction that contains following component:
Rubber particle: parts by weight are 3～40
Vinylbenzene: parts by weight are 60～97
Wherein said rubber particle is the crosslinking-type rubber powder of 20-500nm, and its gel content is not less than 60wt%, and swelling index is not more than 15;
Described polyreaction is to adopt the method for free radical mass polymerization.
2. impact-resistant polystyrene composition according to claim 1, wherein said rubber particle are homogeneous phase.
3. impact-resistant polystyrene composition according to claim 1 and 2, the gel content of wherein said rubber particle is not less than 90wt%.
4. impact-resistant polystyrene composition according to claim 1, wherein said crosslinking-type rubber powder are selected from least a in the following material: powder styrene butadiene rubber, powder natural rubber and powder divinyl rubber.
5. impact-resistant polystyrene composition according to claim 1, wherein rubber particle is a powder styrene butadiene rubber, and its gel content is not less than 90wt%, and swelling index is not more than 13.
6. the preparation method of the described impact-resistant polystyrene composition of claim 1, comprise rubber particle, vinylbenzene and optional adjuvants, be dissolved in the organic solvent, carry out Raolical polymerizable, after reaction finishes, remove unnecessary monomer and solvent, obtain impact-resistant polystyrene composition, described organic solvent is the aromatic hydrocarbons of carbon number 6-20.
7. preparation method according to claim 6 is characterized in that, described organic solvent is selected from least a in toluene, dimethylbenzene and the ethylbenzene, and the weight ratio of styrene monomer and organic solvent is 1:0.1-1:0.5.
8. preparation method according to claim 6 is characterized in that, the temperature of polyreaction with the corresponding time is: 100 ℃～130 ℃ were reacted 1 hour down, and 130 ℃～140 ℃ were reacted 2 hours, and 140 ℃～170 ℃ were reacted 3 hours.
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| CN106867126B (en) * | 2015-12-11 | 2019-04-09 | 中国石油天然气股份有限公司 | Preparation method of special HIPS resin for refrigerator liner |
| CN114426647B (en) * | 2020-10-29 | 2024-05-24 | 中国石油化工股份有限公司 | Production process of high-glossiness impact-resistant polystyrene material |
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| 苯乙烯类聚合物的增韧增强. 王文，林美娟，章文贡.高分子材料科学与工程，第21卷第2期. 2005 |
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