CN1212353C - Polyvinyl chloride and phenylethylene-maleic anhydride multipolymer composition - Google Patents
Polyvinyl chloride and phenylethylene-maleic anhydride multipolymer composition Download PDFInfo
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- CN1212353C CN1212353C CN 02137449 CN02137449A CN1212353C CN 1212353 C CN1212353 C CN 1212353C CN 02137449 CN02137449 CN 02137449 CN 02137449 A CN02137449 A CN 02137449A CN 1212353 C CN1212353 C CN 1212353C
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- maleic anhydride
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Abstract
The present invention relates to compositions of copolymers of polyvinyl chloride and styrene-maleic anhydride, which mainly solve problems which exist compositions prepared by former technologies, such as poor heat resistance performance and low shock resistance performance. The compositions better solve the problems by adopting the technical scheme that copolymers of acrylonitrile, butadiene and styrene, or segmented copolymers of butadiene and styrene, and copolymers of toluene methyl acrylate, butadiene and styrene are added in copolymers of the polyvinyl chloride and the styrene-maleic anhydride, and the compositions can be used in an industrial production of high molecular plastic alloys.
Description
Technical field
The present invention relates to polyvinyl chloride and phenylethylene-maleic anhydride multipolymer composition, particularly about (being commonly called as: maleic anhydride) multipolymer (SMA), vinylformic acid (ester)-butadiene-styrene copolymer (MBS), styrene-butadiene-styrene multipolymer (SBS), the prepared composition of acrylonitrile-butadiene-styrene copolymer (ABS) (abbreviation alloy) with polyvinyl chloride, phenylethylene-maleic anhydride.
Background technology
Polyvinyl chloride (PVC) is that a kind of output is only second to polyolefinic general-purpose plastics, and 1995～1998 years PVC of China consume average growth rate per annum 22.3%, account for 20%, 1999 year degree of self-sufficiency 59.5% of five big general-purpose plastics aggregate consumptions.Though PVC has light weight, corrosion-resistant, insulation, characteristic such as transparent, fire-retardant, poor processability, notched Izod impact strength is low, thermostability is low and the resistance toheat difference is to limit the obstacle that its application surface enlarges.According to annual 50～60 trades mark of PVC blend PP Pipe Compound of releasing of the reported in literature U.S..Therefore, develop special-purpose powder of a series of high performance PVC alloys and pellet, as impact-resistant PVC bottle material, heat-resisting electronic apparatus PP Pipe Compound, medical PVC alloy, building materials PP Pipe Compound etc., satisfying the PVC PP Pipe Compound market requirement is the effective way that improves the PVC degree of self-sufficiency.
Bourland etc. (Bourland L G, Braunstein D M.[J] .J.Appl.Polym.Sci.1986,32 (8): 6131-49.) the PVC/SMA co-mixing system had once been carried out comparatively systematic research.Its result shows that PVC/SMA belongs to the compatible co-mixing system of part, and MA content among the consistency of this system and the SMA (8～17 weight %) is irrelevant.Be rich in SMA mutually in the saturated compatible amount of PVC about 6%; Be rich in PVC mutually in the saturated compatible amount of SMA about 12%; Be rich in PVC phase T
gBe lower than and be rich in SMA phase T
gBourland etc. (Bourland L G.[J] .J.Vinyl Technol.1988,10 (4): 191-9.) also think when SMA content reaches 40% high T
gBe rich in the original position enhancement that SMA has produced the alloy resistance toheat mutually.
Introduced the prescription that uses various SMA, CPE system PVC/SMA (weight ratio 50/50) alloy in the patent that the Jones of U.S. Ethyl Corporation company (US:4513108,1985) Ceng Zaiqi delivers.Alloy heat-drawn wire and shock strength are respectively 67～79 ℃ and 43～123 joules per meter.Jones etc. (US:4510280,1985) also select for use and make Dylark134,290,332,350 (containing rubber), 218 (the containing rubber) of Arco company PVC/SMA (weight ratio 50/50) alloy.The heat-drawn wire of these alloys is near 70 ℃, and is higher than significantly than with not containing the alloy that rubber SMA makes with containing alloy shock resistance that rubber SMA (Dylark218,350) makes, but very limited, about 60 joules per meter.
The Bryner of Monsanto company (Bryner J G.[J] .J.Vinyl Technol.1990,12 (2): 105-10.) once introduced and specialize in the ELIX300 series SMA properties-correcting agent (having heat-resisting and impact-resistant modified effect concurrently) that PVC processing is used, wherein optimum quantum of utilization is 40～50% when ELIX330 and PVC blend; Optimum quantum of utilization is 30～40% when ELIX332 and PVC blend.
Though low because of having good thermotolerance, melt fluidity, flame retardant resistance, dimensional stability and cost, the PVC/SMA alloy successively has been subjected to company (US:4329272,1982 such as DOW, Monsanto, ARCO and Ethyl Corporation; US:4311806,1982; US:4371666,1983; US:4798868,1989) concern, and ARCO and Monsanto company also once released the PVC/SMA alloy respectively, but the technical indicator of relevant product is not seen full report.
Summary of the invention
Technical problem to be solved by this invention be overcome that the polyvinyl chloride that makes in the conventional art and styrene maleic anhydride copolymer form composition exist resistance toheat poor, the problem that shock resistance is low provides a kind of new polyvinyl chloride and phenylethylene-maleic anhydride multipolymer composition.It is good that said composition has resistance toheat, simultaneously the high characteristics of erosion-resisting characteristics.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of polyvinyl chloride and phenylethylene-maleic anhydride multipolymer composition comprise following component by weight percentage:
A) 1.5～25% vinyl cyanide and divinyl and cinnamic multipolymer or divinyl and cinnamic segmented copolymer, wherein butadiene content is 20～80% by weight percentage;
B) 1.5～25% methyl methacrylates, divinyl and cinnamic multipolymer, wherein butadiene content is 20～70% by weight percentage;
C) 13.5～45% vinylbenzene and maleic anhydride copolymer, wherein MALEIC ANHYDRIDE content is 14～25% by weight percentage;
D) 50～70% polyvinyl chloride.
In the technique scheme, the consumption preferable range of vinyl cyanide and divinyl and cinnamic multipolymer or divinyl and cinnamic segmented copolymer is 1.5～22.5% by weight percentage, and wherein butadiene content is 50～70% by weight percentage; The consumption preferable range of methyl methacrylate, divinyl and cinnamic multipolymer is 1.5～22.5% by weight percentage, and wherein butadiene content is 40～65% by weight percentage; The consumption preferable range of vinylbenzene and maleic anhydride copolymer is 15～40% by weight percentage, and wherein MALEIC ANHYDRIDE content is 16～20% by weight percentage.
Used ABS is the product that blending method or grafting method are produced among the present invention, and preferred version is a grafting method product.The technology of producing this kind product can be:
1, chemical graft process comprises letex polymerization grafting method, emulsion-mass polymerization grafting method, body-suspension polymerization grafting method and continuous bulk polymerization grafting method;
2, chemical graft blending method comprises that the poly-grafted ABS latex of breast+poly-SAN (styrene-acrylonitrile copolymer) latex of breast condenses altogether, breast gathers grafted ABS powder+suspension polymerization SAN pellet blend, the poly-grafted ABS powder of breast+mass polymerization SAN pellet blend.
SBS used among the present invention forms with the anionic polymerisation process copolymerization with styrenic and butadiene type monomer.
MBS used among the present invention produces with the emulsion graft copolymerization method.Concrete production technique can be with reference to CN1198442, USP3985704, EP0144081, EP77038, EP0517539, EP62901.
SMA used among the present invention forms with solution method or substance law copolymerization with styrenic and maleic anhydride monomer.Concrete production technique can be with reference to Chinese patent ZL91107516.X and ZL93114923.1.
Used PVC is the product that suspension method and emulsion method are produced among the present invention.
Preparation method of composition of the present invention is earlier granular or pulverous polymeric components to be mixed, again under the plasticization temperature and time of plasticization temperature of being scheduled to premix (180 ℃, 15 minutes) to the material of premix plastify, knead, extrude, compressing tablet.Generally speaking, component order by merging is not critical especially.
Except above-mentioned polymeric components, adding some auxiliary agents also is necessary sometimes.Auxiliary agent has stablizer, fluidizer, oxidation inhibitor etc.Add the method for auxiliary agent and prepare PVC blend method usually identical.It should be noted that because of alkaline lead compound can with the reaction of maleic anhydride among the SMA, impel its open loop and make the fracture of SMA macromolecular chain, and make alkaline lead compound not play heat stabilization effectively and PVC is degraded under processing temperature, so should select the not thermo-stabilizer of lead-containing compounds for use.
Among the present invention, because having added ABS or SBS and MBS in PVC and SMA simultaneously forms, make the composition of acquisition have high resistance to impact shock, notched Izod impact strength is up to 152 joules per meter, had simultaneously good heat-resistant again, vicat softening temperature is up to 101.9 ℃, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1～3]
Count by weight, 25 parts of granular SMA (wherein the MALEIC ANHYDRIDE weight content is 18%), 10 parts of granular SBS (wherein the polyhutadiene weight content is 60%), 15 parts of powdery MBS (wherein the polyhutadiene weight content is 65%) and 50 parts of PVC are put into a container, stir up and down repeatedly, mix.Again this Preblend is sent on the open mill 180 ℃ of plasticizings 15 minutes down, mixing after, compressing tablet on vulcanizing press, and cut into batten is used for the heat-resisting and impact resistance of test material, test result sees Table 1.
In order to further specify the present invention,, change SBS and make different miscellanys with MBS content with same method.Every test result sees Table 1.
[embodiment 4～6]
With the operating method among the embodiment 1,32 parts of granular SMA (wherein the MALEIC ANHYDRIDE weight content is 18%), 3.2 parts of granular SBS (wherein the polyhutadiene weight content is 60%), 4.8 parts of powdery MBS (wherein the polyhutadiene weight content is 65%) and 60 parts of PVC are put into a container, stir up and down repeatedly, mix, process and test performance.
In order to further specify the present invention,, change SBS and make different miscellanys with MBS content with same method.Every test result sees Table 1.
[embodiment 7]
With the operating method among the embodiment 1,24 parts of granular SMA (wherein the MALEIC ANHYDRIDE weight content is 18%), 3 parts of granular SBS (wherein the polyhutadiene weight content is 60%), 3 parts of powdery MBS (wherein the polyhutadiene weight content is 40%) and 70 parts of PVC are put into a container, stir up and down repeatedly, mix, process and test performance.Every test result sees Table 1.
[embodiment 8]
With the operating method among the embodiment 1,35 parts of granular SMA (wherein the MALEIC ANHYDRIDE weight content is 20%), 9 parts of granular SBS (wherein the polyhutadiene weight content is 50%), 6 parts of powdery MBS (wherein the polyhutadiene weight content is 40%) and 50 parts of PVC are put into a container, stir up and down repeatedly, mix, process and test performance.Every test result sees Table 1.
[embodiment 9]
With the operating method among the embodiment 1,35 parts of granular SMA (wherein the MALEIC ANHYDRIDE weight content is 16%), 9 parts of granular SBS (wherein the polyhutadiene weight content is 50%), 6 parts of powdery MBS (wherein the polyhutadiene weight content is 40%) and 50 parts of PVC are put into a container, stir up and down repeatedly, mix, process and test performance.Every test result sees Table 1.
[comparative example 1～2]
With the operating method among the embodiment 1,50 parts of granular SMA, 0 part of granular SBS (wherein the polybutadiene rubber weight content is 60%) and 50 parts of PVC are mixed, process and test performance.Every test result sees Table 1.
The present invention for convenience of explanation with same method, changes SBS and makes different miscellanys with SMA content.Every test result sees Table 1.
The above only is the preferred embodiments of the present invention, and modification or change by the present invention's spirit category is made all ought to be included in this case claim.
Table 1
| Numbering | Blend component (parts by weight) | The notched Izod impact strength joules per meter | Vicat softening temperature ℃ | |||
| SMA | SBS | MBS | PVC | |||
| Embodiment 1 | 25 | 10 | 15 | 50 | 152 | 88 |
| Embodiment 2 | 25 | 5 | 20 | 50 | 150.2 | 85 |
| Embodiment 3 | 25 | 20 | 5 | 50 | 79.0 | 88.5 |
| Embodiment 4 | 32 | 3.2 | 4.8 | 60 | 36.3 | 101.7 |
| Embodiment 5 | 32 | 2 | 6 | 60 | 32 | 100 |
| Embodiment 6 | 32 | 6 | 2 | 60 | 31.5 | 101.7 |
| Embodiment 7 | 24 | 3 | 3 | 70 | 30 | 101.9 |
| Embodiment 8 | 35 | 9 | 6 | 50 | 41.0 | 97.2 |
| Embodiment 9 | 35 | 9 | 6 | 50 | 38.9 | 90.8 |
| Comparative example 1 | 50 | 0 | 0 | 50 | 13.6 | 109 |
| Comparative example 2 | 25 | 25 | 0 | 50 | 38 | 78 |
Claims (4)
1, a kind of polyvinyl chloride and phenylethylene-maleic anhydride multipolymer composition comprise following component by weight percentage:
A) 1.5～25% vinyl cyanide and divinyl and cinnamic multipolymer or divinyl and cinnamic segmented copolymer, wherein butadiene content is 20～80% by weight percentage;
B) 1.5～25% methyl methacrylates, divinyl and cinnamic multipolymer, wherein butadiene content is 20～70% by weight percentage;
C) 13.5～45% vinylbenzene and maleic anhydride copolymer, wherein MALEIC ANHYDRIDE content is 14～25% by weight percentage;
D) 50～70% polyvinyl chloride.
2, according to described polyvinyl chloride of claim 1 and phenylethylene-maleic anhydride multipolymer composition, it is characterized in that the consumption of vinyl cyanide and divinyl and cinnamic multipolymer or divinyl and cinnamic segmented copolymer is 1.5～22.5% by weight percentage, wherein butadiene content is 50～70% by weight percentage.
3, according to described polyvinyl chloride of claim 1 and phenylethylene-maleic anhydride multipolymer composition, it is characterized in that the consumption of methyl methacrylate, divinyl and cinnamic multipolymer is 1.5～22.5% by weight percentage, wherein butadiene content is 40～65% by weight percentage.
4, according to described polyvinyl chloride of claim 1 and phenylethylene-maleic anhydride multipolymer composition, it is characterized in that the consumption of vinylbenzene and maleic anhydride copolymer is 15～40% by weight percentage, wherein MALEIC ANHYDRIDE content is 16～20% by weight percentage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02137449 CN1212353C (en) | 2002-10-16 | 2002-10-16 | Polyvinyl chloride and phenylethylene-maleic anhydride multipolymer composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02137449 CN1212353C (en) | 2002-10-16 | 2002-10-16 | Polyvinyl chloride and phenylethylene-maleic anhydride multipolymer composition |
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| Publication Number | Publication Date |
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| CN1490353A CN1490353A (en) | 2004-04-21 |
| CN1212353C true CN1212353C (en) | 2005-07-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101229489B (en) * | 2007-10-26 | 2010-11-03 | 泉州索爱膜科技开发有限公司 | Film making liquid for polyvinyl chloride hydrophilicity alloy separating film and preparing method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105086240A (en) * | 2015-08-24 | 2015-11-25 | 华南理工大学 | Styrene-maleic anhydride-acrylonitrile copolymer modified polyvinyl chloride and preparation method thereof |
| CN114149647A (en) * | 2021-12-30 | 2022-03-08 | 深圳恒方大高分子材料科技有限公司 | High-transparency high-heat-resistance medical hard PVC alloy material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101229489B (en) * | 2007-10-26 | 2010-11-03 | 泉州索爱膜科技开发有限公司 | Film making liquid for polyvinyl chloride hydrophilicity alloy separating film and preparing method thereof |
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| CN1490353A (en) | 2004-04-21 |
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