CN1311023C - Flame-proof and highly impact-resistant polystyrene composition and its preparation method - Google Patents
Flame-proof and highly impact-resistant polystyrene composition and its preparation method Download PDFInfo
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Abstract
The present invention provides a flame-proof and high impact-resistant polystyrene composition and a preparation method thereof, which belongs to the field of modified high impact-resistant polystyrene. The flame-proof and high impact-resistant polystyrene composition is obtained by melting and blending high impact-resistant polystyrene resin, bromine flame-proof agents, antimony oxide type auxiliary flame-proof agents and powdered rubber with the average particle diameter of 50 to 200 nm and the gel content of 60% or even more by weight, wherein the high impact-resistant polystyrene resin counted by 100 parts by weight comprises 6 to 30 parts of bromine flame-proof agent, 2 to 12 parts of auxiliary flame-proof agent, and 0.5 to 10 parts of powdered rubber. The flame-proof and high impact-resistant polystyrene composition of the present invention has the advantages of high flame-proof performance and good impact performance, is particularly suitable for manufacturing electronic components, constructional elements and shell materials of electronic devices requiring flame-proof performance, and can have great market application prospects.
Description
Technical field
The present invention relates to a kind of modified polystyrene composition, say further, relate to a kind of flame-proof and highly impact-resistant polystyrene composition and preparation method thereof.
Background technology
High-impact polystyrene (HIPS) normally improves by add rubber phase in the styrene polymerization process that the shock resistance of polystyrene obtains.It has good processability, excellent combination property and lower-price characteristic.As an important branch of general-purpose plastics polystyrene, high-impact polystyrene is used for making the case material of electronic devices and components, member and electronics more, as television cabin, recording casing etc.Under most of situations, these use occasions need it to have high flame retardant resistance, except that some small members, require it can reach the V-0 level flame-retardant standard of UL94-96 (U.S.'s instrument and the parts incendivity testing standard of plastic material) usually.
Because the high-impact polystyrene self property determines that it is the inflammableness plastics.The manufacture method of flame-proof highly anti-flush polyphenylacetylene comprises in the polystyrene system introduces fire retardant, and modal fire retardant systems has the halogen based compound, as bromide fire retardant and chlorine-based flame retardant.The halogen based compound often by with the shared flame retardant effect that improves of auxiliary flame retardant.Auxiliary flame retardant is those significant more mineral-type auxiliary flame retardants of flame retardant effect that can make fire retardant, mainly is sb oxide, and the most frequently used sb oxide is an antimonous oxide.As Chinese patent application CN 1163630A " mouldings of flame-proofed polystyrene based resin composition and polystyrene resin ", Chinese patent application CN 1298898A " mixture of light aging resisting high tenacity flame retardant thermoplastic styrene base polymer ", flame-retardant system described in scientific and technical literature " fire-retardant HI high impact degree polystyrene (HIPS) " (" plastics science and technology " 1994 the 5th phase 1～3 page) and " development of high-impact polystyrene resin flame-retardant color master batch grain " (" petrochemical technology and application " 1999 the 3rd phase 134～138 pages) all is to be made of bromine system or chlorine-based flame retardant and auxiliary flame retardant system.
The HIPS flame retardant area is in common knowledge, add bromine compounds and auxiliary flame retardant, the flame retardant properties of product can be significantly improved (see " fire retardant material and utilisation technology " that Chemical Industry Press published in 2003 the 39th page described in antimony halogen synergistic effect).When the addition of bromine compounds and auxiliary flame retardant reached a certain value, it is fire-retardant that product will reach the V-O level.But after in HIPS, adding bromine compounds and auxiliary flame retardant, because the consistency of fire retardant and matrix HIPS resin is relatively poor, not fusion in its processing temperature is so must cause its degradation, impact strength decreased particularly, this is the deficiency of this technology maximum at present.Need in the flame-proof highly anti-flush polyphenylacetylene system, add the impact property that toughner improves flame-proof highly anti-flush polyphenylacetylene for this reason.Toughening material commonly used in the prior art is styrenic elastomericss such as SBS, though the adding of toughner makes toughness obtain to a certain degree recovery, but flame retardant properties is reduced.In order to ensure that flame retardant properties needs to strengthen the consumption of fire retardant again, so flame retardant resistance and impact can not well be coordinated.
Summary of the invention
The present invention is directed to the problem that exists in the existing flame-proof highly anti-flush polyphenylacetylene modification technology, be intended to make high-impact polystyrene flame retardant properties under the situation of low consumption fire retardant of modification can reach the V-0 level, make flame-proof highly anti-flush polyphenylacetylene have good toughness simultaneously.
Therefore, the purpose of this invention is to provide a kind of flame-proof and highly impact-resistant polystyrene composition with high flame resistance and excellent impact resistance energy.
Another object of the present invention provides the preparation method of described flame-proof and highly impact-resistant polystyrene composition.
The contriver finds in the process of research flame-proof and highly impact-resistant polystyrene composition, in the process of this kind of preparation composition, be added in that finely disseminated elasticity powdered rubber can produce synergistic effect with fire retardant in the polystyrene, under the situation that ensures flame retardant properties V-0, reduce the consumption of fire retardant, thereby effectively reduce the density of composition, and in certain amplitude, reduce the cost of composition, make flame-proof highly anti-flush polyphenylacetylene have good toughness simultaneously.
A kind of flame-proof and highly impact-resistant polystyrene composition provided by the present invention includes the following component of blend: high-impact polystyrene, brominated flame retardant, auxiliary flame retardant and powdered rubber.Be 100 parts by weight in high-impact polystyrene resin wherein, brominated flame retardant content is 6～30 parts, preferred 9～20 parts; Described assisting flame-resistant agent content is 2～12 parts, preferred 3～8 parts; Described powdered rubber content is 0.5～10 part, preferred 3～7 parts.
In the above highly anti-flush polyphenylacetylene composition of the present invention, high-impact polystyrene resin comprises the disclosed various types of high-impact polystyrene resins of prior art, selects the general injection grade product that is used for industries such as household electrical appliances usually for use.
In the above highly anti-flush polyphenylacetylene composition of the present invention, brominated flame retardant is selected from one or more in aliphatics and the aromatic brominated flame retardant.Preferred one or more in decabromodiphenyl oxide, octa-BDE, hexabromocyclododecane, pentabromotoluene, tetrabromo-bisphenol, tribromophenol, brominated Polystyrene.
In the above highly anti-flush polyphenylacetylene composition of the present invention, auxiliary flame retardant is the mineral-type auxiliary flame retardant, mainly is sb oxide, and the most frequently used sb oxide is antimonous oxide (Sb2O3).
In the above highly anti-flush polyphenylacetylene composition of the present invention, powdered rubber is median size 50～200nm, is preferably 80～150nm; Gel content is 60% weight or higher, is preferably 80% weight or higher powdered rubber.This kind powdered rubber is preferably the rubber particles of equal phase structure.This kind powdered rubber is selected from a kind of or its mixing in butylbenzene powdered rubber, polyhutadiene powdered rubber and the carboxyl butylbenzene powdered rubber.
The above powdered rubber can adopt according to the inventor in the prepared fully vulcanized powder rubber of the Chinese patent ZL00816450.9 of on September 18th, 2000 application (is right of priority with Chinese patent application 99125530.5, priority date on December 3rd, 1999).Be preferably a kind of or its mixing in form of finely divided powder, mehtod styrene-butadiene rubber(SBR), form of finely divided powder, mehtod polybutadiene rubber and the form of finely divided powder, mehtod carboxylic styrene-butadiene rubber.This kind fully vulcanized powder rubber gel content reaches 60% weight or higher, need not after the drying to get final product unrestricted flow with separant.Each particulate in this fully vulcanized powder 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.This fully vulcanized powder rubber gets by to the rubber latex cross-linking radiation rubber particles particle diameter being fixed.So the particle diameter of latex particle is consistent substantially in its median size and the rubber latex, the size scope of the latex particle that described rubber latex obtains when synthetic is the particle size range of gained fully vulcanized powder rubber particle, be generally 20～2000nm, preferred 30～1500nm, more preferably 50～500nm.
The above powdered rubber can also adopt the prepared cross-linked powdered rubber of Chinese patent ZL00130386.4 in application on November 3rd, 2000 according to the applicant.Be preferably a kind of or its mixing in cross-linking type butylbenzene powdered rubber, cross-linked powdery polybutadiene rubber and the cross-linked powdery carboxylic styrene-butadiene rubber.This kind cross-linked powdered rubber is a kind ofly (to have some rubber latexs between the rubber molecule certain cross can take place in the synthetic process with cross-linking type synthetic rubber latex, thereby make resulting rubber latex have certain crosslinking degree, be referred to as crosslinking-type rubber latex) be raw material, the powdered rubber that drying obtains.The particle diameter of latex particle is consistent substantially in its median size and the crosslinking-type rubber latex, and the size scope of the latex particle that crosslinking-type rubber latex obtains when synthetic is the particle size range of gained cross-linked powdered rubber particle, is generally 50～300nm.This cross-linked powdered rubber need not add separant and get final product unrestricted flow.Its gel content is consistent with gel content as the cross-linking type synthetic rubber latex of raw material, is 80% weight or higher, is preferably 85% weight or higher.Each particulate in this cross-linked 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.
Powdered rubber in the highly anti-flush polyphenylacetylene composition of the present invention also can be the mixing of the above fully vulcanized powder rubber and cross-linked powdered rubber.
Can also include some auxiliary agents commonly used in the high-impact polystyrene course of processing such as toughener, weighting agent, lubricant, look mother etc. in the composition of flame-proof and highly impact-resistant polystyrene composition of the present invention, its consumption is conventional amount used, or adjusts according to practical requirements.
The preparation method of flame-proof and highly impact-resistant polystyrene composition of the present invention, comprise that the component that will include described high-impact polystyrene resin, brominated flame retardant, auxiliary flame retardant, powdered rubber carries out melt blending, thereby make described highly anti-flush polyphenylacetylene composition.Normally each component is mixed, carry out melt blending then.
Among the above preparation method of the present invention, high-impact polystyrene resin comprises the disclosed various types of high-impact polystyrene resins of prior art, selects the general injection grade product that is used for industries such as household electrical appliances usually for use.
Among the above preparation method of the present invention, brominated flame retardant is selected from one or more in aliphatics and the aromatic brominated flame retardant.Preferred one or more in decabromodiphenyl oxide, octa-BDE, hexabromocyclododecane, pentabromotoluene, tetrabromo-bisphenol, tribromophenol, brominated Polystyrene.
Among the above preparation method of the present invention, auxiliary flame retardant is the mineral-type auxiliary flame retardant, mainly is sb oxide, and the most frequently used sb oxide is antimonous oxide (Sb2O3).
Among the above preparation method of the present invention, powdered rubber is median size 50～200nm, is preferably 80～150nm; Gel content is 60% weight or higher, is preferably 80% weight or higher powdered rubber.This kind powdered rubber is preferably the rubber particles of equal phase structure.This kind powdered rubber is selected from a kind of or its mixing in butylbenzene powdered rubber, polyhutadiene powdered rubber and the carboxyl butylbenzene powdered rubber.(with Chinese patent application 99125530.5 is right of priority to powdered rubber described in the inventive method Chinese patent ZL00816450.9 preferred above-mentioned, that the inventor applied on September 18th, 2000, priority date on December 3rd, 1999) cross-linked powdered rubber that the fully vulcanized powder rubber that is provided, and/or the inventor is provided in the Chinese patent ZL00130386.4 of application on November 3rd, 2000.
Be 100 parts by weight in high-impact polystyrene resin among the above preparation method of the present invention, described brominated flame retardant content is 6～30 parts, preferred 9～20 parts; Described assisting flame-resistant agent content is 2～12 parts, preferred 3～8 parts; Described powdered rubber content is 0.5～10 part, preferred 3～7 parts.
In the preparation process of the long flame-proof and highly impact-resistant polystyrene composition of the present invention, material melt blending temperature is used blending temperature in the common HIPS processing, can decide according to the HIPS melt temperature, should select not only guaranteeing the complete fusion of HIPS matrix plastic but also can not make in the scope of its decomposition, be generally 160 ℃～200 ℃.In addition, according to the processing needs, can in the blend material, add some auxiliary agents commonly used in the high-impact polystyrene course of processing such as toughener, weighting agent, lubricant, look mother etc. in right amount.Its consumption is conventional amount used, or adjusts according to practical requirements.
The blending equipment of mixing of materials can adopt various mixing equipments used in the prior art in the preparation method of the invention described above, as stirrer, kneading machine etc.
Employed melt blending equipment is the general blending equipment in the rubber and plastic processing industry in the method for the invention described above, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.
Be added in finely disseminated elasticity powdered rubber in the polystyrene in the flame-proof and highly impact-resistant polystyrene composition of the present invention, can produce synergistic effect with fire retardant, under the situation that ensures high flame resistance, reduce the consumption of fire retardant, thereby effectively reduce the density of composition, and in certain amplitude, reduce the cost of composition, make flame-proof highly anti-flush polyphenylacetylene have good toughness simultaneously.Flame-proof and highly impact-resistant polystyrene composition of the present invention has shock resistance and well reaches advantages such as flame retardant properties excellence, be specially adapted to make the products such as case material that need fire-retardant electronic devices and components, member and electronics, huge market application foreground will be arranged.Preparation method's technology of the present composition is simple, easy handling, is suitable for industrial applications.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Embodiment 1～5
With form of finely divided powder, mehtod styrene-butadiene rubber(SBR) (VP-101, the Beijing Chemical Research Institute produces, particle diameter 80～110nm, gel content 90.4%wt) and the high-impact polystyrene pellet (Dow chemical company produces, trade mark A-Tech1300), (U.S. Albemarle company produces decabromodiphenyl oxide, Saytex 102E), antimonous oxide (Hunan, Hunan Lengshuijiang Hsikwangshan Twinkling Star company produces, the flash star board) and antioxidant 1010 (Switzerland vapour Ba Jiaji production) uniform mixing in homogenizer.With the ZSK-25 twin screw extruder melt blending extruding pelletization of mixture by German WP company, each section of forcing machine temperature is respectively then: 170 ℃, 180 ℃, 180 ℃, 180 ℃, 180 ℃ and 180 ℃ (head temperature).Pellet is made the standard batten through injection moulding, carries out every Mechanics Performance Testing.Testing standard sees Table 1.Concrete prescription sees Table 2.Wherein the content of oxidation inhibitor is the per-cent of composition gross weight.Test result is as shown in table 3.
Comparative Examples 1～2:
Except not adding form of finely divided powder, mehtod styrene-butadiene rubber(SBR), all the other compositions and preparation condition are with embodiment 1.Concrete prescription sees Table 2.Test result is as shown in table 3.
Comparative Examples 3～4:
In addition, all the other compositions and preparation condition are with embodiment 1 except form of finely divided powder, mehtod styrene-butadiene rubber(SBR) being replaced with SBS (Yanshan Petrochemical synthetic rubber plant in Beijing produces, and SBS 1401).Concrete prescription sees Table 2.Test result is as shown in table 3.
Table 1
| Performance | Unit | Testing method |
| Tensile strength | MPa | ASTM D638-02 |
| Elongation at break | ％ | ASTM D638-02 |
| Flexural strength | MPa | ASTM D790-03 |
| The Izod notched Izod impact strength | J/m | ASTM 256-02 |
| Flame retardant properties | - | UL 94-96 |
Table 2
| HIPS | Decabromodiphenyl oxide | Antimonous oxide | VP101 | SBS | Oxidation inhibitor | |
| Unit | Parts by weight | ％wt | ||||
| Embodiment 1 | 100 | 19 | 8 | 7 | 0 | 0.2 |
| Embodiment 2 | 100 | 12 | 5 | 6 | 0 | 0.2 |
| Embodiment 3 | 100 | 10 | 4 | 6 | 0 | 0.2 |
| Embodiment 4 | 100 | 9 | 4 | 4 | 0 | 0.2 |
| Embodiment 5 | 100 | 12 | 5 | 4 | 0 | 0.2 |
| Comparative Examples 1 | 100 | 14 | 6 | 0 | 0 | 0.2 |
| Comparative Examples 2 | 100 | 12 | 5 | 0 | 0 | 0.2 |
| Comparative Examples 3 | 100 | 15 | 6 | 0 | 6 | 0.2 |
| Comparative Examples 4 | 100 | 12 | 5 | 0 | 6 | 0.2 |
Table 3
| Tensile strength | Elongation at break | Flexural strength | The Izod notched Izod impact strength | UL94 is fire-retardant | |
| Embodiment 1 | 30.2 | 16 | 47.1 | 108 | V-0 |
| Embodiment 2 | 29.8 | 23 | 47.5 | 127 | V-0 |
| Embodiment 3 | 30.1 | 25 | 45.6 | 131 | V-0 |
| Embodiment 4 | 30.9 | 22 | 48.3 | 127 | V-0 |
| Embodiment 5 | 29.7 | 13 | 45.7 | 120 | V-2 |
| Comparative Examples 1 | 32.2 | 13 | 47.6 | 119 | V-1 |
| Comparative Examples 2 | 29.2 | 22 | 47.0 | 129 | Can not classification |
| Comparative Examples 3 | 29.0 | 38 | 45.7 | 176 | V-2 |
| Comparative Examples 4 | 29.2 | 39 | 46.5 | 168 | Can not classification |
Claims (10)
1. flame-proof and highly impact-resistant polystyrene composition includes the following component of blend:
A. high-impact polystyrene resin 100 parts by weight
B. brominated flame retardant 6～30 parts by weight
C. auxiliary flame retardant 2～12 parts by weight
D. powdered rubber 0.5～10 parts by weight
Wherein said amount of component b auxiliary flame retardant is a sb oxide; Wherein said component d is median size 50～200nm, and gel content is 60% weight or higher powdered rubber, comprises a kind of or its mixing in butylbenzene powdered rubber, polyhutadiene powdered rubber and the carboxyl butylbenzene powdered rubber.
2. highly anti-flush polyphenylacetylene composition according to claim 1 includes the following component of blend:
A. high-impact polystyrene 100 parts by weight
B. brominated flame retardant 9～20 parts by weight
C. auxiliary flame retardant 3～8 parts by weight
D. powdered rubber 3～7 parts by weight.
3. highly anti-flush polyphenylacetylene composition according to claim 1, wherein said components b brominated flame retardant are selected from least a in aliphatics and the aromatic brominated flame retardant.
4. highly anti-flush polyphenylacetylene composition according to claim 3, wherein said components b brominated flame retardant are selected from least a in decabromodiphenyl oxide, octa-BDE, hexabromocyclododecane, pentabromotoluene, tetrabromo-bisphenol, tribromophenol, the brominated Polystyrene.
5. highly anti-flush polyphenylacetylene composition according to claim 1, wherein said amount of component b auxiliary flame retardant is an antimonous oxide.
6. highly anti-flush polyphenylacetylene composition according to claim 1, the powdered rubber of wherein said component d are the rubber particles of equal phase structure.
7. highly anti-flush polyphenylacetylene composition according to claim 1, the median size of the powdered rubber of wherein said component d are 80～150nm.
8. highly anti-flush polyphenylacetylene composition according to claim 1, the powdered rubber gel content of wherein said component d is 80% weight or higher.
9. highly anti-flush polyphenylacetylene composition according to claim 1, the powdered rubber of wherein said component d are one or more in fully vulcanized powder rubber and the cross-linked powdered rubber.
10. according to the preparation method of the described flame-proof and highly impact-resistant polystyrene composition of one of claim 1～9, comprise the component that includes described high-impact polystyrene, brominated flame retardant, auxiliary flame retardant and powdered rubber is carried out melt blending by described component concentration.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100372886C (en) * | 2006-11-24 | 2008-03-05 | 北京理工大学 | Flame-proof polystyrene composition and its preparation method |
| CN101486824B (en) * | 2008-01-17 | 2012-06-27 | 深圳市亚塑科技有限公司 | Preparation of low temperature resistant environment friendly flame-retardant high impact resistance polystyrene composition |
| CN101864137B (en) * | 2010-06-30 | 2013-05-08 | 银禧工程塑料（东莞）有限公司 | High impact-resistance anti-smoldering polystyrene resin composite and preparation method thereof |
| CN104497428A (en) * | 2014-11-24 | 2015-04-08 | 苏州新区佳合塑胶有限公司 | Preparation method of polystyrene plastic fire retardant |
| CN113402836B (en) * | 2021-07-14 | 2022-10-21 | 上海葛蓝化工科技有限公司 | Macromolecular phosphorus-halogen flame retardant modified high impact polystyrene resin composition and preparation method thereof |
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