CN1045006C - Thermoplastic polystyrene composition - Google Patents
Thermoplastic polystyrene composition Download PDFInfo
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- CN1045006C CN1045006C CN94119665A CN94119665A CN1045006C CN 1045006 C CN1045006 C CN 1045006C CN 94119665 A CN94119665 A CN 94119665A CN 94119665 A CN94119665 A CN 94119665A CN 1045006 C CN1045006 C CN 1045006C
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Abstract
The present invention relates to a heat plastic polystyrene composition comprising polystyrene, the high shock block copolymer of polystyrene, phenylethylene and conjugation diene, an inorganic filler and an additive agent and a preparation method thereof. The heat plastic polystyrene composition has good combined property, and the heat plastic polystyrene composition is superior to HIPS and is similar to ABS. Because the preparation method of the heat plastic polystyrene composition has the advantages of simple and convenient manufacture and low cost, the heat plastic polystyrene composition can replace ABS, and the heat plastic polystyrene composition can be widely used for the plate materials and the sheet materials of the injection moulding products of domestic electric appliances, automobiles and construction.
Description
The present invention relates to a kind of thermoplastic polystyrene composition, particularly relate to by vinylbenzene conjugated diene block copolymer, polystyrene, high impact polystyrene, filler and additive through thermoplastic polystyrene composition of blending and modifying and preparation method thereof.
Cinnamic homopolymer and multipolymer have been widely used in the various fields, and it is a kind of universal thermoplastics.Polystyrene is that a kind of transparency and rigidity are held concurrently resin excellent, good moldability, but its shock resistance is very poor and crisp easy fracture, so limited its application.As everyone knows, add the shock resistance that thermoplastic elastic body improves polystyrene usually, High Impact Polystyrene (HIPS) HIPS occurs, though its shock resistance improvement, but still lower, low-temperature performance is also poor; Or obtain the fair ABS resin of over-all properties by copolymerization, but use material toxicity bigger, the manufacturing process technology complexity, cost is higher, has limited use range.
English Patent (GB) 138991 discloses the blend of being made up of polystyrene PS, high impact polystyrene HIPS and butadiene styrene block copolymerization thing, though its notched Izod impact strength is better than high impact polystyrene, but still it is low, and the consumption of butadiene styrene block copolymerization thing is also very big, and rigidity is lower.
Japanese kokai publication sho 47-34808 discloses the formed sheet of being made up of polystyrene, high impact polystyrene and butadiene styrene block copolymerization thing, and wherein polybutadiene rubber content is 15% in the high-impact polystyrene.
The open blend of forming by polystyrene, high impact polystyrene and styrene butadiene of Japanese kokai publication sho 57-30747, wherein polybutadiene rubber content 0.5～1.0%, and impact property is low, does not satisfy market demands.
The contriver adopts suitable starting material and proportioning through deeply and carefully discovering, by blending modification method, obtains over-all properties and is better than high impact polystyrene HIPS, can compare U.S. with ABS (acrylonitrile butadient styrene), is better than ABS in some performance.
The object of the invention provides that a kind of to contain with polystyrene and high impact polystyrene be base-material, the thermoplastic elastomer of conjugated diolefine vinylbenzene or substituted phenylethylene is a properties-correcting agent, is equipped with the novel thermoplastic polyphenylacetylene combination of good processibility of having of filler and suitable additive and mechanical property again.
Another purpose of the present invention is to compare the method and the various goods of beautiful thermoplastic compounds with ABS by the blending and modifying preparation.
Polyphenylacetylene combination of the present invention is to be base resin with polystyrene PS and high impact polystyrene HIPS, benzene second combustion conjugated diene block copolymer is a properties-correcting agent, be equipped with suitable filler and additive again, get by blend method, described polyphenylacetylene combination contains 5-40% (weight) polystyrene, the high impact polystyrene of 50-87% (weight), 2-15% (weight) vinylbenzene conjugation Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, 5-30% (weight) mineral filler, 0.2-0.8% (weight) oxidation inhibitor four (4-hydroxyl-3.5-tert-butyl-phenyl propionic acid) pentaerythritol ester (antioxidant 1010), lubricant 0.5-3.0% (weight).
Polystyrene described in the present composition is commercially available General Purpose Polystyrenre, and its consumption in composition is 5-40%.
High impact polystyrene described in the present composition can adopt the whole bag of tricks such as mass polymerization or breast to gather-the mass polymerization gained, and polybutadiene content is 6-8.0% (weight) in the structure, is preferably 6-7% (weight).
The segmented copolymer of described vinylbenzene conjugated diolefine is meant three block line style or star copolymers of vinylbenzene and divinyl or isoprene, and its general formula is that SBS or SIS reach (SB)
4Or (SI)
4S represents polystyrene block in the formula, B represents polybutadiene block, I represents polyisoprene blocks, wherein cinnamic content is 30-40% (weight fraction), the content of divinyl or isoprene is 60-70% (weight), and the total number-average molecular weight of segmented copolymer is a 100000-150000 gram/mole, and the segmented copolymer of described vinylbenzene conjugated diolefine is good with the segmented copolymer of styrene butadiene.Consumption is generally 2-15% (weight) in composition, is preferably 5-10% (weight).
Used mineral filler is selected from light calcium carbonate, talcum powder, wollastonite in the present composition, is advisable with light calcium carbonate especially.Wherein light calcium carbonate and talcum powder both can use separately also and can be used, and were advisable with 1: 1 proportioning when cooperation is shared.The consumption of filler in composition is generally 5-30% (weight), is preferably 5-20% (weight).
Described additive is that oxidation inhibitor four (4-hydroxyl-3.5-tert-butyl-phenyl propionic acid) pentaerythritol ester is called for short antioxidant 1010 in this application, and its consumption is 0.2-0.8% (weight), is preferably 0.3-0.7%; Lubricant is that tristearin is joined calcium or low molecular polyethylene.Its amount is 0.5-3.0% (weight).
A kind of embodiment of the present invention can adopt single stage method or two-step approach to make polyphenylacetylene combination of the present invention; described two-step approach is meant the vinylbenzene conjugated diene block copolymer; the part polystyrene; high impact polystyrene and additive are made master batch earlier in Banbury mixer; then with master batch; remaining polystyrene and mineral filler are by above-mentioned given formula rate; metering is after in the high-speed mixing adding double-screw extruding pelletizing machine; through mixing; extruder grain; can obtain polyphenylacetylene combination of the present invention; described single stage method is meant vinylbenzene conjugated diene block copolymer polystyrene and high impact polystyrene; mineral filler and additive are by above-mentioned given formula rate; after the metering; through high-speed mixing; as go in the twin screw Squeezinggranulator; through mixing; extruding; cooling and dicing; can make polyphenylacetylene combination of the present invention, preferred version is a single stage method, and single stage method prepares the block diagram of polyphenylacetylene combination of the present invention and sees Fig. 1.
Because selecting for use, polyphenylacetylene combination of the present invention closes the vinylbenzene conjugated diene block copolymer known and the high impact polystyrene of certain polybutadiene rubber content, select light calcium carbonate simultaneously for use, both improved hardness, tensile modulus and the resistance to deflection of composition finished commodities, can remedy again because the reduction of elastomer copolymer performance that adding causes.Prepared polyphenylacetylene combination of the present invention is that the excellent impact resistance energy is arranged, higher modulus in flexure, high temperature performance is good, surpass commercially available high impact polystyrene, can compare U.S. with ABS, moulding easily, manufacturing is simple, easy to process, cost is low, can replace ABS to be widely used in injection-molded item in household electrical appliance, household electrical appliance, automobile and the building trade, sheet material and sheet material, and various products.
The present invention further proves composition of the present invention with the following example, but does not limit the claim of the present composition.
Embodiment 1
With polystyrene 20 parts of (weight), high impact polystyrene 70 parts of (weight), styrene butadiene block copolymer 10 parts of (weight), 15 parts of talcum powder (weight), 0.5 part of calcium stearate (weight), antioxidant 1010 0.3 part (weight) and low molecular polyethylene 1 part (weight) measure back blending in super mixer respectively, with twin screw extruder granulation unit, at 170-210 ℃ of following fusion extruding pelletization, make thermoplastic polystyrene composition, its tensile strength, elongation at break, notched Izod impact strength and Brinell hardness are respectively 26.5MPa, 31%; 117J/m and 85.
Embodiment 2
With 40 parts of polystyrene (weight); 50 parts of high impact polystyrenes (weight); 10 parts of styrene butadiene block copolymers (weight); 7.5 parts of talcum powder (weight); 7.5 parts of light calcium carbonates (weight); 0.5 part of calcium stearate (weight); antioxidant 1010 is blending in super mixer after 0.3 part (weight) difference juice amount; with twin screw extruder grain unit at 170-210 ℃ of following fusion extruder grain; make thermoplastic polystyrene composition, its tensile strength; notched Izod impact strength; elongation at break and cloth soft are respectively 28.3MPa; 108J/m; 27% and 90.
Embodiment 3
With 5 parts of polystyrene (weight); 87 parts of high impact polystyrene (weight); 8 parts of styrene butadiene block copolymers (weight); 10 parts of talcum powder (weight); 0.4 part of calcium stearate (weight); antioxidant 1010 0.4 part of (weight) and 1 part of low molecular polyethylene (weight); metering back blending in super mixer respectively; 170-230 ℃ of following fusion, extruder grain makes thermoplastic polystyrene composition with twin screw extruder grain unit, its tensile strength; elongation at break; notched Izod impact strength and Brinell hardness are respectively 32.1MPa, and 34%, 125J/m and 87.
The used analytical procedure of mass analysis adopts national standard (GB) and the standard (HG of the Ministry of Chemical Industry in an embodiment
2) be that tensile strength and elongation at break are undertaken by the regulation of GB1040; Notched Izod impact strength is undertaken by the regulation of GB1843; Brinell hardness is undertaken by the regulation of HG2-168.Several groups of comparing embodiments are listed in table 1.
The typical comparing embodiment of table 1
| Comparing embodiment | Essentially consist | Salient features |
| PS HIPS properties-correcting agent | Tensile strength MPa, elongation at break %, notched Izod impact strength J/m | |
| Comparative example 1 | 90 ′ 10 | 29.4 51 14 |
| Comparative example 2 | ′ 100 ′ | 24.5 44 42 |
| Comparative example 3 | 50 25 20 | ′ ′ 78 |
| Embodiment 1 | 20 70 10 | 26.5 31 117 |
| Embodiment 2 | 40 50 10 | 28.3 27 108 |
| Embodiment 3 | 5 87 8 | 32.1 34 125 |
The present invention's as can be seen from Table 1 " novel thermoplastic polyphenylacetylene combination " excellent shock resistance, tensile strength is also higher.
Claims (6)
1. thermoplastic polystyrene composition, contain 5-40% (weight) polystyrene, 50-87% (weight) high impact polystyrene, 2-15% (weight) vinylbenzene conjugated diene block copolymer, 5-30% (weight) mineral filler, 0.2-0.8% (weight) four (4-hydroxyls-3,5-tert-butyl-phenyl propionic acid) pentaerythritol ester, lubricant 0.5-3.0% (weight), wherein said vinylbenzene conjugated diene block copolymer is three block line style or star copolymers of vinylbenzene and divinyl or isoprene, and its general formula is that SBS or SIS reach (SB)
4Or (SI)
4, S represents polystyrene block in the formula, and B represents polybutadiene block, and I represents the polyprene block, wherein the content 60-70% (weight) of divinyl or isoprene.
2. according to the thermoplastic polystyrene composition of claim 1, polybutadiene rubber content is 6-8% (weight) in the wherein said high impact polystyrene.
3. according to the thermoplastic polystyrene composition of claim 1, it is characterized in that described filler is meant is selected from light calcium carbonate, talcum powder, wollastonite, wherein light calcium carbonate and talcum powder both can also use separately and can be used, and its ratio is 1: 1 when being used.
4. according to the thermoplastic polystyrene composition of claim 1, wherein lubricant is a low molecular polyethylene.
5. method for preparing thermoplastic polystyrene composition; with polystyrene, high impact polystyrene, vinylbenzene conjugated diene block copolymer; mineral filler and additive in the metering of the given ratio of claim 1 through high-speed mixing, add twin screw extruder grain unit in 170-230 ℃ of following blending, extrude, cooling and dicing gets described composition.
6. be used for various profits according to the thermoplastic polystyrene composition of claim 1 and mould goods, sheet material and sheet material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94119665A CN1045006C (en) | 1994-12-16 | 1994-12-16 | Thermoplastic polystyrene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94119665A CN1045006C (en) | 1994-12-16 | 1994-12-16 | Thermoplastic polystyrene composition |
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| Publication Number | Publication Date |
|---|---|
| CN1107486A CN1107486A (en) | 1995-08-30 |
| CN1045006C true CN1045006C (en) | 1999-09-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN94119665A Expired - Fee Related CN1045006C (en) | 1994-12-16 | 1994-12-16 | Thermoplastic polystyrene composition |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5054978B2 (en) * | 2004-11-19 | 2012-10-24 | パナソニック株式会社 | Flame retardant resin composition, production method thereof and molding method thereof |
| CN101928441B (en) * | 2009-06-24 | 2012-10-03 | 漯河市罗孚文具制造有限公司 | Styrenic block copolymer wear-resistant material and preparation method thereof |
| CN102844376A (en) | 2011-02-24 | 2012-12-26 | 松下电器产业株式会社 | Outer covering and method for producing same |
| WO2012114397A1 (en) | 2011-02-24 | 2012-08-30 | パナソニック株式会社 | Outer covering and method for producing same |
| CN105733118B (en) * | 2016-02-29 | 2018-08-14 | 金发科技股份有限公司 | A kind of K resin combinations and the preparation method and application thereof |
| CN107254112A (en) * | 2017-07-31 | 2017-10-17 | 昆山恒光塑胶股份有限公司 | A kind of high intensity PS sheet materials of blister packaging |
| CN114213778B (en) * | 2021-11-30 | 2024-03-19 | 上海金发科技发展有限公司 | High-impact high-gloss HIPS material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907930A (en) * | 1973-11-09 | 1975-09-23 | Monsanto Co | Toughened polymeric polyblend having high flow and ductility |
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1994
- 1994-12-16 CN CN94119665A patent/CN1045006C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907930A (en) * | 1973-11-09 | 1975-09-23 | Monsanto Co | Toughened polymeric polyblend having high flow and ductility |
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| CN1107486A (en) | 1995-08-30 |
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