CN101724130B - Toughened polystyrene composite and preparation method thereof - Google Patents
Toughened polystyrene composite and preparation method thereof Download PDFInfo
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- CN101724130B CN101724130B CN2008102248650A CN200810224865A CN101724130B CN 101724130 B CN101724130 B CN 101724130B CN 2008102248650 A CN2008102248650 A CN 2008102248650A CN 200810224865 A CN200810224865 A CN 200810224865A CN 101724130 B CN101724130 B CN 101724130B
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Abstract
The invention relates to a toughened polystyrene composite and a preparation method thereof, in particular to a toughened polystyrene composite of rubber modified polymer, wherein the sizes of particle diameters of the rubber modified polymer has the characteristic of multi-stage distribution. The rubber particles with the particle diameters of 0.1-0.3mu m account for 0.5-2% of the total rubber content, rubber particles with the particle diameters of 0.3-1mu m account for 2-20% of the total rubber content, and the rubber particles with the particle diameters of more than 1mu m account for 78-97.5% of the total rubber content; and the rubber particles form a distribution form with multiple particle diameters in polystyrene matrix, and the rubber particles with the various particle diameters are evenly distributed inside the polystyrene matrix. By adopting the rubber toughened polystyrene composite with the multiple particle diameters, the toughening effect is improved by 70%, and the tensile yield strength is also obviously improved. Furthermore, the melt index of the polymer can be improved by the ways such as adding mineral oil and the like, and the flow property of the polymer is enhanced.
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 rubber modified polymers toughened polystyrene composite, wherein the size of rubber modified polymers particle diameter has the characteristic of multistage distribution.
Background technology
PS (PS) is to use big comparatively widely kind synthetic resins at present; Have good performances such as the tint permanence transparency, electrical insulating property and processing fluidity; Have application widely in industry and civilian every field, become one of current four big general-purpose plastics.But polystyrene resin has determined the shortcoming on its mechanical property because of the immanent structure of its molecular chain; Like insufficient strength height, poor toughness etc.; Especially the brittle behaviour that shows makes its range of application receive very big restriction thus, has particularly limited its application aspect the high-impact goods.In order to improve the toughness of PS, 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.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 introducing of 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 that exists between the two and synergy contribute for the toughness that improves material.
More the method for traditional rubber toughened polystyrene adopts cis-1,4-polybutadiene rubber to be dissolved in and carries out graft polymerization in the styrene monomer, is the styron that contains rubber of CN1254722A and the method for preparation like patent publication No..This method for toughening is owing to the restriction of polymerizing condition, and the rubber grain footpath size in the gained matrix of materials is all more than 1 μ m.The resistance to impact shock of material depends on the add-on of rubber, and more rubber content then can reduce the rigidity of material.
The small particle size of employing rubber toughened polystyrene compsn is also arranged in the present research; Like patent publication No. is the rubber modified polystyrene resin of US5491195; Its rubber size between 0.1～1 μ m, the entanglement described in can forming as indicated or the structure of concentric shells, but this method for toughening is not because there is the existence of big particle diameter rubber particle; Be unfavorable for that material produces crazing in impact process, so toughening effect is limited.
The inventor, is promptly not only contained the big particle diameter rubber particle more than the 1 μ m but also the small particle size rubber particle between 0.1～1 μ m is arranged in polystyrene substrate if the rubber particle of enhancing touthness of polyphenylethylene by adding resin forms the multistage distribution of big small particle size through discovering.The multistage distributional pattern of this big or small its size of rubber particle produces a kind of effect of coordination plasticizing.This method for toughening makes material in receiving ballistic process, not only effectively cause the generation of crazing, and helps the formation of shear zone, controls the expansion of crazing, effectively improves the toughening effect of rubber.
Summary of the invention
The purpose of this invention is to provide a kind of polyphenylacetylene combination; Said compsn is a dispersion rubber particulate in polystyrene substrate, and the content of rubber particle is 1～40wt% in said compsn, is preferably 3～30wt%; More preferably 5～25wt%, most preferably 5～10wt%.Rubber particle forms the multistage distribution of big small particle size; The particle diameter of rubber particle accounts for 0.5～2% of total rubber content 0.1～0.3 μ m's; The particle diameter of rubber particle accounts for 2～20% of total rubber content 0.3～1 μ m's; The particle diameter of rubber particle accounts for 78～97.5% of total rubber content more than 1 μ m, rubber particle forms the multistage distributional pattern of a kind of particle diameter in polystyrene substrate, and the rubber particle of various particle diameters is evenly distributed in the polystyrene substrate.
Generally be the multipolymer of a kind of homopolymer, diolefine or the multipolymer of ethene, propylene and any one non-conjugated diene hydrocarbon by the used rubber of the polymkeric substance of modified rubber among the present invention.The rubber phase of preferentially selecting for use is 1; 3-conjugated diolefin homopolymerization thing; Like divinyl rubber, synthetic polyisoprene, m-pentadiene rubber, neoprene and similar conjugated diene and one or more monomeric multipolymers, these monomers comprise single inferior ethene aromatic hydrocarbon (vinylbenzene), unsaturated nitrile (vinyl cyanide) and alkene (ethene, propylene) or the like.Preferentially selecting polybutadiene rubber for use is that rubber is used in modification.
The particle size distribution of rubber phase is among the present invention:
The particle diameter of rubber particle is that 0.1～0.3 μ m accounts for total rubber
0.5～2% of glue content, form are solid bulk; The particle diameter of rubber particle is that 0.3～1 μ m accounts for 2～20% of total rubber content, and form is single or a plurality of structure of containing; The particle diameter of rubber particle be 1 μ m above account for 78～97.5% of total rubber content, form is a plurality of set of containing structure.Therefore rubber particle forms a kind of distributional pattern of multiple particle diameter in polystyrene substrate, and the rubber particle of various particle diameters is evenly distributed in the matrix.
Another object of the present invention provides a kind of preparation of compositions method of impact-resistant polystyrene; Adopt the method for radical initiation to carry out mass polymerization rubber modified polymers and vinylbenzene; The swelling and rubber and the cinnamic grafting process that comprise rubber in the described polymerization process, polymerization process removes unnecessary monomer and solvent after finishing; Obtain the polystyrene resin of high impact strength, concrete steps are following:
(1) styrene monomer and rubber particle are dissolved in the organic solvent; The consumption of organic solvent is 0～60wt% of styrene monomer total amount; Be preferably 10～30wt%, carry out thermal initiation again or add an amount of initiator initiated polymerization, described organic solvent adopts aromatic hydrocarbon solvent; During the initiator initiated polymerization, initiator can be selected from least a in Potassium Persulphate, Di Cumyl Peroxide 99, hydrogen phosphide cumene, Lucidol or the peroxide di-t-butyl.The consumption of initiator is 0～1000ppm, in above-mentioned radical polymerization process, adds anti-aging agent or inhibitor;
(2) polyreaction is 100 ℃～130 ℃ following polymerizations 4 hours, 130 ℃～140 ℃ following polymerizations 2 hours, 140 ℃～170 ℃ following polymerizations 1 hour; Poly styrene polymer obtains product after devolatilization, drying.
The compsn of impact-resistant polystyrene preferably obtains through divinyl rubber and styrene polymerization.In the polyphenylacetylene combination of gained; Formed the effect of the rubber particle coordination plasticizing polystyrene of multiple particle diameter; 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, given full play to the toughening effect of rubber p-poly-phenyl ethene matrix.
Polymerization process of the present invention: the method that divinyl rubber, vinylbenzene adopt radical to cause is carried out mass polymerization, comprise swelling and the rubber and the cinnamic grafting process of rubber in the described polymerization process.Said polymerization process removes unnecessary monomer and solvent after finishing, and obtains 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, Di Cumyl Peroxide 99, hydrogen phosphide cumene, Lucidol or the peroxide di-t-butyl.The consumption of initiator is 0～1000ppm, and 0～500ppm is advisable, and 0～200ppm is best.
Above-mentioned radical polymerization randomly adds organic solvent dilutes, and described organic solvent preferably adopts aromatic hydrocarbons, like toluene, YLENE 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 is like anti-aging agent, inhibitor; Concrete as: 2; 2,4-trimethylammonium-1,2-EEDQ 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 '-diphenyl-para-phenylene diamine (4010), 2,2 '-methylene-bis (4-methyl-6-tertiary butyl) phenol (2246), 3,5-di-t-butyl-4 hydroxy phenyl propionic acid octadecanol ester (1076) etc.; Softening agent, concrete as: Zinic stearas, lead stearate, cadmium stearate etc.
The whipped form that the present invention adopts can adopt anchor stirrer, grid agitator, single helix agitator, double ribbon agitator, the stirring of set square middle and upper part, bottom helical-ribbon type, wherein ribbon can be single ribbon or two ribbon.The present invention is big, mobile poor because of material stirs viscosity, and needs rubber is fully disperseed, and reaches multistage size distribution, preferentially selects set square middle and upper part, bottom ribbon combined type whisking appliance for use, and stir speed (S.S.) is 100～180r/min, is preferably 120～140r/min.
The molecular weight of PS 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 site 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 PS weight-average molecular weight between 10～400,000.Being aggregated under 100～170 ℃ of temperature that the present invention 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 polymerization temperature of the present invention and corresponding time: 100 ℃～130 ℃ following polymerizations 4 hours, 130 ℃～140 ℃ polymerizations 2 hours, 140 ℃～170 ℃ polymerizations 1 hour.Poly styrene polymer through obtaining after the polyreaction needs conventional devolatilization, drying and other steps usually.
Above-mentioned polyphenylacetylene combination not only have pure PS 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.
Description of drawings
The TEM figure of Fig. 1 embodiment 1
The TEM figure of Fig. 2 comparative example 1
Embodiment
The invention is further illustrated by the following examples, to deepen understanding of the present invention.Below given embodiment be for better the explanation rather than the restriction the present invention.
The physical property measurement method
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/T18474-2001.
4, the mensuration of swelling index: test according to GB/T7763-1987.
Embodiment 1
High-cis cis-1,4-polybutadiene rubber 1 (BR-9004; Yanshan Petrochemical production) 114.7g, vinylbenzene (Yanshan Petrochemical production) 1700g and anti-aging agent 10761.8g add in the still, adopt double ribbon agitator, stir under the 170rpm stir speed (S.S.); 35 ℃ of swellings 8 hours add ethylbenzene 300g in the still again.With nitrogen with air displacement in the still.Adopt the method polymerization of radical mass polymerization, initiating method adopts thermal initiation.Polymeric kettle heats up under the 138rpm stir speed (S.S.), 120 ℃ of following polymerizations 4 hours, 130 ℃ of following polymerizations 2 hours, 157 ℃ of following polymerizations 1.5 hours.Accomplish polymerization process, the thickness body of polymerization gained is escaped and enter in 232 ℃ the devolatilizer, rapid flash distillation under vacuum state removes unreacted monomer and solvent ethylbenzene.Obtain polymkeric substance after the devolatilization and promptly get sample, rerum natura is measured through cooling, granulation, sample preparation.Mechanical test results is that tensile yield strength is 36.8MPa, and cantilever beam impact strength is 17.6kJ/m
2, melting index is 2.91g/10min, the result sees table 1.
Embodiment 2
Reduce mixing speed to 105rpm, other conditions are with embodiment 1.Mechanical test results is that tensile yield strength is 34.6MPa, and cantilever beam impact strength is 17.3kJ/m
2, melting index is 4.74g/10min, the result sees table 1.
Embodiment 3
Reduce cis-1,4-polybutadiene rubber content to 103g, other conditions are identical with embodiment 1.Mechanical test results is that tensile yield strength is 38MPa, and cantilever beam impact strength is 16.6kJ/m
2, melting index is 3.71g/10min, the result sees table 1.
Embodiment 4
The consumption that improves the solvent ethylbenzene is to 400g, and other conditions are identical with embodiment 1.Mechanical test results is that tensile yield strength is 33.8MPa, and cantilever beam impact strength is 16.2kJ/m
2, melting index is 5.54g/10min, the result sees table 1.
Embodiment 5
Add 65g MO, the flowing property of telomerized polymer on the basis of embodiment 1.Other conditions are identical with embodiment 1.Mechanical test results is that tensile yield strength is 25.8MPa, and cantilever beam impact strength is 14.8kJ/m
2, melting index is 6.07g/10min, the result sees table 1.
Comparative example 1
Adopt traditional method to prepare the rubber toughened polystyrene polymkeric substance, it is identical with instance 5 to fill a prescription, and the average rubber particle diameter is more than 1 μ m.Mechanical test results is that tensile yield strength is 24.6MPa, and cantilever beam impact strength is 10.4kJ/m
2, melting index is 5.12g/10min, the result sees table 1.
Embodiment 6
The content that improves MO is to 83g, and other conditions are with embodiment 1.Mechanical test results is that tensile yield strength is 27.9MPa, and cantilever beam impact strength is 13.0kJ/m
2, melting index is 9.17g/10min, the result sees table 1.
Embodiment 7
Continue to improve MO content to 120g, other conditions are with embodiment 1.Mechanical test results is that tensile yield strength is 27.8MPa, and cantilever beam impact strength is 11.4kJ/m
2, melting index is 13.41g/10min, the result sees table 1.
Table 1
| Embodiment | Rubber content wt% | Tensile yield strength MPa | Cantilever beam impact strength kJ/m 2 | Melting index g/10min | Remarks |
| Embodiment 1 | 8％ | 36.8 | 17.6 | 2.91 | |
| Embodiment 2 | 8％ | 34.6 | 17.3 | 4.74 | Rotating speed falls to 105r/min |
| Embodiment 3 | 7％ | 38 | 16.6 | 3.71 | Reduce rubber content |
| Embodiment 4 | 8％ | 33.8 | 16.2 | 5.54 | Improve the ethylbenzene consumption |
| Embodiment 5 | 8％ | 25.8 | 14.8 | 6.07 | Add MO 65g |
| Comparative example 1 | 8％ | 24.6 | 10.4 | 5.12 | |
| Embodiment 6 | 8％ | 9.17 | Add MO 83g | ||
| Embodiment 7 | 8％ | 27.8 | 11.4 | 13.41 | Add MO 120g |
Can find out that from table 1 adopt multiple particle diameter rubber toughened polystyrene polymkeric substance, its toughening effect has improved 70%, and tensile yield strength also has the raising of obvious degree.And can improve the flowing property of polymkeric substance through adding the melting index of mineral wet goods means raising polymkeric substance.
Claims (5)
1. polyphenylacetylene combination; Said compsn is in polystyrene substrate, to disperse the divinyl rubber particulate; The content of divinyl rubber particulate is 1～40wt% in said compsn; Rubber particle forms the multistage distribution of big small particle size, and the particle diameter of rubber particle accounts for 0.5～2% of total rubber content 0.1～0.3 μ m's, and form is solid bulk; The particle diameter of rubber particle accounts for 2～20% of total rubber content 0.3～1 μ m's, and form is single or a plurality of structure of containing; The particle diameter of rubber particle accounts for 78～97.5% of total rubber content more than 1 μ m, form is a plurality of set of containing structure; Rubber particle forms a kind of distributional pattern of multiple particle diameter in polystyrene substrate, and the rubber particle of various particle diameters is evenly distributed in the polystyrene substrate.
2. polyphenylacetylene combination according to claim 1, the content of rubber particle is 5～25wt% in said compsn.
3. polyphenylacetylene combination according to claim 1, the content of rubber particle is 5～10wt% in the said compsn.
4. the preparation method of each said polyphenylacetylene combination of claim 1～3; It is characterized in that, adopt the method for radical initiation to carry out mass polymerization divinyl rubber and vinylbenzene, comprise swelling and the rubber and the cinnamic grafting process of rubber in the described polymerization process; After polymerization process finishes; Remove unnecessary monomer and solvent, obtain the polystyrene resin of high impact strength, concrete steps are following:
(1) styrene monomer and rubber particle are dissolved in the organic solvent; The consumption of organic solvent is 0～60wt% of styrene monomer total amount; Carry out thermal initiation again or add an amount of initiator initiated polymerization; Described organic solvent adopts aromatic hydrocarbon solvent, and during the initiator initiated polymerization, initiator is selected from least a in Potassium Persulphate, Di Cumyl Peroxide 99, hydrogen phosphide cumene, Lucidol or the peroxide di-t-butyl; The consumption of initiator is 1～1000ppm, in above-mentioned radical polymerization process, adds anti-aging agent;
(2) polyreaction is 100 ℃～130 ℃ following polymerizations 4 hours, 130 ℃～140 ℃ following polymerizations 2 hours, 140 ℃～170 ℃ following polymerizations 1 hour; Poly styrene polymer obtains product after devolatilization, drying.
5. according to the preparation method of the said polyphenylacetylene combination of claim 4; It is characterized in that; The consumption of described organic solvent is 10～30wt% of styrene monomer total amount, and organic solvent adopts toluene, YLENE or ethylbenzene, and the consumption of initiator is 1～200ppm.
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