CN103497441A - Polyphenyl ether resin alloy material, and preparation method and application thereof - Google Patents
Polyphenyl ether resin alloy material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of high-polymer alloy materials, and particularly relates to a polyphenyl ether resin alloy material used for processing automobile spare tire covers and a preparation method of the polyphenyl ether resin alloy material. The polyphenyl ether resin alloy material is prepared by, by weight, 20-40 parts of polyphenyl ether resin, 50-80 parts of polystyrene resin, 1-3 parts of polyolefin, 1-8 parts of elastomer, 1-15 parts of flame retardant, 0.05-0.30 part of lubricant, 1-3 parts of inorganic filler, 3-8 parts of grafting bodies, and 0.10-0.50 part of antioxidant. By adjusting formula composition and selecting proper process and extruding conditions, the problem about mobility of the polyphenyl ether resin alloy material is solved. The polyphenyl ether resin alloy material has high mobility and no stress cracking after spraying, is capable of sufficiently meeting operating requirements of the application field of automobile parts and quite applicable to raw materials for automobile spare tire covers.
Description
Technical field
The invention belongs to the high molecule alloy material field, be specifically related to a kind of polyphenylene oxide resin alloy material, its preparation method and application.
Background technology
Polyphenylene oxide resin has the performance of a lot of excellences, and such as mechanical property, hydrolysis, acid-alkali-corrosive-resisting, resistance toheat, dimensional stability etc., its product is applied to the fields such as electronic apparatus, automobile component, water treating equipment, chemical industry widely.Although the resistance toheat of polyphenylene oxide alloy material and physical strength are excellent especially, also have some fatal defects, such as poor fluidity, oil-proofness is poor, stress cracking is serious etc.For larger accessory, need high workability for automobile, do not occur stress cracking after spraying, this always since, be a major challenge that polyphenylene oxide resin is used field.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of polyphenylene oxide resin alloy material is provided.
The present invention also provides a kind of preparation method of polyphenylene oxide resin alloy material simultaneously.
For solving above technical problem, the present invention adopts following technical scheme:
A kind of polyphenylene oxide resin alloy material, in weight part, described polyphenylene oxide resin alloy material comprises following recipe ingredient:
Wherein:
Described elastomerics is one or more the mixture in styrene-butadiene rubber(SBR), HSBR, ethylene propylene rubber, terpolymer EP rubber, polyacrylic rubber, Toughening Effect of Ethylene Copolymer Elastomer, polyisoprene elastomerics, 1,2 polybutadiene elastomer;
Described grafting body is that to take the mixture of the one or both in described styrene-butadiene rubber(SBR), HSBR be base material, and the grafts of described grafting body is one or more the mixture in diacetyl oxide, propionic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, benzoyl oxide, Tetra hydro Phthalic anhydride.
Described polyphenylene oxide resin is the polymkeric substance, 2 of 2,6-xylenol, the mixture of the one or both in the multipolymer of 6-xylenol and 2,3,6-TMP, and its limiting viscosity is 0.2-0.6dl/g.
Described polystyrene resin is the mixture of the one or both in polystyrene, high-impact polystyrene.
Described polyolefine is one or more the mixture in polyethylene, polypropylene, ethylene propylene copolymer, polybutene, ethylene-butylene copolymer, ethene-unsaturated ester multipolymer.
Described fire retardant is that phosphorus flame retardant and nitrogen based flame retardant are the compound system that 2～4:1 forms by weight, and wherein, described phosphorus flame retardant is one or more the mixture in phosphoric acid ester fire retardant, ammonium polyphosphate based flame retardant, inorganic phosphorus based flame retardant; Described nitrogen based flame retardant is a kind of in trimeric cyanamide, Dyhard RU 100 based flame retardant.
Described lubricant is one or more the mixture in calcium stearate, Zinic stearas, stearic acid, butyl stearate, oleylamide, ethylene bis stearamide, silicone oil.
Described mineral filler is one or more the mixture in titanium white, zinc white, mica, nano-calcium carbonate, nano imvite, superfine talcum powder.
Described oxidation inhibitor is that primary antioxidant and auxiliary antioxidant are the mixture that 1～3:1 forms by weight, wherein, described primary antioxidant is 3,5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester, β-(3, the 5-di-tert-butyl-hydroxy phenyl) mixture of one or more in propionic acid stearyl alcohol ester, 2,2 methylene-biss (4-methyl-6-tert-butylphenol); Described auxiliary antioxidant is one or more the mixture in three (Isosorbide-5-Nitrae-di-tert-butyl-phenyl) phosphorous acid, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate, two (octadecyl) pentaerythritol diphosphate.
In the present invention, whole described raw materials all can prepare by being purchased and/or taking known means, while not specified, all meet the requirement of stdn chemical product.
Polyphenylene oxide resin alloy material of the present invention can be used for the automobile spare tire cover.
The another technical scheme that the present invention takes is: a kind of preparation method of above-mentioned polyphenylene oxide resin alloy material, described preparation method is: by the formula of described polyphenylene oxide resin alloy material, first described polyolefine, elastomerics, fire retardant, lubricant, mineral filler, grafting body, oxidation inhibitor are mixed to the formation mixture, then by described polyphenylene oxide resin, described polystyrene resin and described mixture from the different charging openings of twin screw extruder add, melt extruded.
Due to the enforcement of technique scheme, the present invention compared with prior art has following advantage:
Polyphenylene oxide resin alloy material of the present invention, by being used in conjunction with polyphenylene oxide resin, polystyrene resin, polyolefine, elastomerics, fire retardant, lubricant, mineral filler, grafting body, oxidation inhibitor, the usage ratio of reasonably optimizing above-mentioned raw materials simultaneously, make the polyphenylene oxide resin alloy material have the advantages such as high workability, good oil-proofness, anti-stress cracking performance.This polyphenylene oxide resin alloy material is applied to the automobile spare tire cover, occurs the problem of stress cracking fully meeting the service requirements of auto parts machinery Application Areas after can effectively solving poor fluidity, spraying.The preparation method of polyphenylene oxide resin alloy material of the present invention is simple to operate, with low cost, productivity effect is high, and prepared polyphenylene oxide resin alloy material has good oil-proofness, anti-stress cracking performance, is suitable for suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Each raw material weight umber is in Table 1.The manufacturer of each raw material is:
Embodiment 1
The raw material that the present embodiment adopts and consumption are referring to table 1, wherein:
Polyphenylene oxide resin: be selected from the polymkeric substance of 2,6-xylenol, its limiting viscosity is 0.4dl/g;
Polystyrene resin: formed for 1:3 by weight by polystyrene, high-impact polystyrene;
Polyolefine: formed for 3:1:1 by weight by polypropylene, ethylene propylene copolymer, polybutene;
Elastomerics: be that 4:4:1:1 forms by weight by styrene-butadiene rubber(SBR), HSBR, polyacrylic rubber, 1,2 polybutadiene elastomer;
Fire retardant: by phosphorus flame retardant and nitrogen based flame retardant, by weight for 3:1 forms, wherein, phosphorus flame retardant is the phosphoric acid ester fire retardant, and the nitrogen based flame retardant is trimeric cyanamide;
Lubricant: formed for 1:1:1 by weight by calcium stearate, Zinic stearas, stearic acid;
Mineral filler: formed for 1:2:1 by weight by titanium white, zinc white, mica;
The grafting body: take styrene-butadiene rubber(SBR), HSBR is base material by weight the mixture for the 1:1 composition, and grafts is propionic anhydride;
Oxidation inhibitor: by primary antioxidant and auxiliary antioxidant, by weight for 2:1 forms, wherein, primary antioxidant is β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester, and auxiliary antioxidant is pair (octadecyl) pentaerythritol diphosphate;
The preparation method of polyphenylene oxide resin alloy material is:
By formula, first polyolefine, elastomerics, fire retardant, lubricant, mineral filler, grafting body, oxidation inhibitor are mixed to the formation mixture, then by polyphenylene oxide resin from the first weightless charging opening add, polystyrene resin from the second weightless feeder mouth add, mixture adds from the 3rd weightless feeder mouth, through twin screw extruder plasticizing, melting, extrude, tie rod, cooling, pelletizing.Pellet is at 120 ℃ of dry 2-4h of gas blower drying oven, and then injection moulding prepares test bars and goods.
Embodiment 2
The raw material that the present embodiment adopts and consumption are referring to table 1, and the raw material outside polyphenylene oxide resin, polystyrene resin, grafting body is all identical with embodiment 1.
In this example, polyphenylene oxide resin: by the polymkeric substance, 2 of 2,6-xylenol, the multipolymer of 6-xylenol and 2,3,6-TMP is by weight the mixture formed for 2:1, and its limiting viscosity is 0.5dl/g;
In this example, polystyrene resin: be selected from polystyrene;
In this example, the grafting body: take styrene-butadiene rubber(SBR) as base material, grafts is that diacetyl oxide, Succinic anhydried, benzoyl oxide are by weight the mixture formed for 3:1:1
In this example, the preparation method of polyphenylene oxide resin alloy material, with embodiment 1, no longer repeats at this.
Embodiment 3
The raw material that the present embodiment adopts and consumption are referring to table 1, and the raw material outside polyolefine, elastomerics, oxidation inhibitor is all identical with embodiment 1.
In this example, polyolefine: be selected from polyethylene;
In this example, elastomerics: the mixture formed for 1:1 by weight by HSBR, ethylene propylene rubber;
In this example, oxidation inhibitor: formed for 3:1 by weight by primary antioxidant and auxiliary antioxidant, wherein, primary antioxidant is 3,5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester, 2,2 methylene-biss (4-methyl-6-tert-butylphenol) are by weight the mixture formed for 1:1, and auxiliary antioxidant is that two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate, two (octadecyl) pentaerythritol diphosphate are by weight forming for 1:1;
In this example, the preparation method of polyphenylene oxide resin alloy material, with embodiment 1, no longer repeats.
Embodiment 4
The raw material that the present embodiment adopts and consumption are referring to table 1, and the raw material outside fire retardant, lubricant, mineral filler, grafting body is all identical with embodiment 1.
In this example, fire retardant: by phosphorus flame retardant and nitrogen based flame retardant by weight for 4:1 forms, wherein, phosphorus flame retardant be ammonium polyphosphate based flame retardant, inorganic phosphorus based flame retardant by weight being the 1:1 composition, the nitrogen based flame retardant is the Dyhard RU 100 based flame retardant;
In this example, lubricant: formed for 1:1:1 by weight by oleylamide, ethylene bis stearamide, silicone oil;
In this example, mineral filler: formed for 1:1:2:1 by weight by titanium white, nano-calcium carbonate, nano imvite, superfine talcum powder;
In this example, the grafting body: take styrene-butadiene rubber(SBR), HSBR is base material by weight the mixture for the 1:1 composition, and grafts is MALEIC ANHYDRIDE;
In this example, the preparation method of polyphenylene oxide resin alloy material, with embodiment 1, no longer repeats.
Comparative Examples 1
The raw material that this Comparative Examples adopts and consumption are referring to table 1, and this Comparative Examples does not add the grafting body when preparing the polyphenylene oxide resin alloy material, and all the other raw materials are identical with embodiment 1.
The preparation method of the polyphenylene oxide resin alloy material of this Comparative Examples is: by formula, first polyolefine, elastomerics, fire retardant, lubricant, mineral filler, oxidation inhibitor are mixed to the formation mixture, then by polyphenylene oxide resin from the first weightless charging opening add, polystyrene resin from the second weightless feeder mouth add, mixture adds from the 3rd weightless feeder mouth, through twin screw extruder plasticizing, melting, extrude, tie rod, cooling, pelletizing.Pellet is at 120 ℃ of dry 2-4h of gas blower drying oven, and then injection moulding prepares test bars and goods.
The raw material weight umber proportioning of table 1 embodiment 1～4, Comparative Examples 1
| Component | Comparative Examples 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Polyphenylene oxide resin | 27 | 20 | 22 | 26 | 28 |
| Polystyrene resin | 57 | 56 | 56.5 | 57.5 | 58 |
| Polyolefine | 2 | 2 | 2 | 2 | 2 |
| Elastomerics | 1 | 1 | 1 | 1 | 1 |
| Fire retardant | 11 | 15 | 13 | 9 | 7 |
| Lubricant | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Mineral filler | 1.5 | 2.5 | 2 | 1 | 0.5 |
| The grafting body | 0 | 3 | 3 | 3 | 3 |
| Oxidation inhibitor | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
Composition properties test result in table 2 embodiment and Comparative Examples
From the performance test table of table 2, can find out, the polyphenylene oxide resin alloy material of embodiment 1～4 has good oil-proofness and anti-stress cracking performance.
The performance of composition in test and Evaluation operation example and Comparative Examples by the following method.
(1) tensile strength
Described tensile strength is pressed ASTM D-638 test.
(2) flexural strength
Described flexural strength is pressed ASTM D-790 test.
(3) modulus in flexure
Described modulus in flexure is pressed ASTM D-790 test
(4) notched Izod impact strength
Described notched Izod impact strength is pressed ASTM D-256 test.
(5) heat-drawn wire
Described heat-drawn wire is pressed ASTM D-648 standard testing.
(6) melting index
Described melting index is pressed ASTM D-1238 standard testing.
(7) flame retardant properties
Described flame retardant properties is pressed the UL94 standard testing.
(8) oil resistant cracking test
The product outside surface of injection moulding is coated with the last layer mineral oil, under room temperature standing 24 hours, sees whether product exists cracking phenomena.
Above the present invention is described in detail; its purpose is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; and the invention is not restricted to the embodiments described; the equivalence that all spirit according to the present invention are done changes or modifies, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. a polyphenylene oxide resin alloy material, is characterized in that, in weight part, described polyphenylene oxide resin alloy material comprises following recipe ingredient:
Polyphenylene oxide resin 20-40 part;
Polystyrene resin 50-80 part;
Polyolefine 1-3 part;
Elastomerics 1-8 part;
Fire retardant 1-15 part;
Lubricant 0.05-0.30 part;
Mineral filler 1-3 part;
Grafting body 3-8 part;
Oxidation inhibitor 0.10-0.50 part;
Wherein:
Described elastomerics is one or more the mixture in styrene-butadiene rubber(SBR), HSBR, ethylene propylene rubber, terpolymer EP rubber, polyacrylic rubber, Toughening Effect of Ethylene Copolymer Elastomer, polyisoprene elastomerics, 1,2 polybutadiene elastomer;
Described grafting body is that to take the mixture of the one or both in described styrene-butadiene rubber(SBR), HSBR be base material, and the grafts of described grafting body is one or more the mixture in diacetyl oxide, propionic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, benzoyl oxide, Tetra hydro Phthalic anhydride.
2. polyphenylene oxide resin alloy material according to claim 1, is characterized in that, described polyphenylene oxide resin is 2, the polymkeric substance of 6-xylenol, 2,6-xylenol and 2,3, the mixture of the one or both in the multipolymer of 6-pseudocuminol, its limiting viscosity is 0.2-0.6dl/g.
3. polyphenylene oxide resin alloy material according to claim 1, is characterized in that, described polystyrene resin is the mixture of the one or both in polystyrene, high-impact polystyrene.
4. polyphenylene oxide resin alloy material according to claim 1, it is characterized in that, described polyolefine is one or more the mixture in polyethylene, polypropylene, ethylene propylene copolymer, polybutene, ethylene-butylene copolymer, ethene-unsaturated ester multipolymer.
5. polyphenylene oxide resin alloy material according to claim 1, it is characterized in that, described fire retardant is that phosphorus flame retardant and nitrogen based flame retardant are the compound system that 2 ~ 4:1 forms by weight, wherein, described phosphorus flame retardant is one or more the mixture in phosphoric acid ester fire retardant, ammonium polyphosphate based flame retardant, inorganic phosphorus based flame retardant; Described nitrogen based flame retardant is a kind of in trimeric cyanamide, Dyhard RU 100 based flame retardant.
6. polyphenylene oxide resin alloy material according to claim 1, is characterized in that, described lubricant is one or more the mixture in calcium stearate, Zinic stearas, stearic acid, butyl stearate, oleylamide, ethylene bis stearamide, silicone oil.
7. polyphenylene oxide resin alloy material according to claim 1, is characterized in that, described mineral filler is one or more the mixture in titanium white, zinc white, mica, nano-calcium carbonate, nano imvite, superfine talcum powder.
8. polyphenylene oxide resin alloy material according to claim 1, it is characterized in that, described oxidation inhibitor is that primary antioxidant and auxiliary antioxidant are the mixture that 1 ~ 3:1 forms by weight, wherein, described primary antioxidant is 3, the mixture of one or more in 5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester, 2,2 methylene-biss (4-methyl-6-tert-butylphenol); Described auxiliary antioxidant is one or more the mixture in three (Isosorbide-5-Nitrae-di-tert-butyl-phenyl) phosphorous acid, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate, two (octadecyl) pentaerythritol diphosphate.
9. the preparation method as the described polyphenylene oxide resin alloy material of any one claim in claim 1 to 8, it is characterized in that, described preparation method is: by the formula of described polyphenylene oxide resin alloy material, first described polyolefine, elastomerics, fire retardant, lubricant, mineral filler, grafting body, oxidation inhibitor are mixed to the formation mixture, then by described polyphenylene oxide resin, described polystyrene resin and described mixture from the different charging openings of twin screw extruder add, melt extruded.
10. the application of polyphenylene oxide resin alloy material as described as claim 1 to 8 any one in the automobile spare tire cover.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105504767A (en) * | 2016-01-04 | 2016-04-20 | 江苏沃特新材料科技有限公司 | Polyphenyl ether resin alloy material, preparation method thereof and refrigeration compressor |
| CN105968775A (en) * | 2016-05-31 | 2016-09-28 | 苏州市奎克力电子科技有限公司 | Polyphenyl ether-polyarylene ether ether nitriles alloy material and preparation method thereof |
| CN106589896A (en) * | 2016-11-18 | 2017-04-26 | 江苏沃特新材料科技有限公司 | High-impact-resistant polyphenyl-ether engineering plastic and preparing method and application thereof |
| CN106800713A (en) * | 2016-12-22 | 2017-06-06 | 芜湖天鸿汽车零部件有限公司 | A kind of automobile trunk plastic base plate and preparation method thereof |
| CN107880421A (en) * | 2017-11-21 | 2018-04-06 | 丁妙严 | Heat resistant type PS, PPO blending formula |
| CN108219433A (en) * | 2017-12-19 | 2018-06-29 | 宁波甬尚聚新材料有限公司 | A kind of polyphenylene oxide resin alloy and preparation method thereof |
| CN108676345A (en) * | 2018-04-24 | 2018-10-19 | 嘉兴希卡姆复合材料有限公司 | A kind of Noryl and acrylic resin alloy material and preparation method thereof |
| CN109852032A (en) * | 2019-02-13 | 2019-06-07 | 湖南恒屹新材料有限公司 | A kind of polyphenylene oxide resin based composites and its preparation method and application |
| CN112322020A (en) * | 2020-11-25 | 2021-02-05 | 湖南恒屹新材料有限公司 | Polyphenyl ether resin composition and preparation method thereof, and wire slot and preparation method thereof |
| CN112745653A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Modified polyphenyl ether, halogen-free flame-retardant TPV, preparation methods and applications of modified polyphenyl ether and halogen-free flame-retardant TPV, and composition for preparing halogen-free flame-retardant TPV |
| CN116769298A (en) * | 2023-05-26 | 2023-09-19 | 湖南恒屹新材料有限公司 | High-strength modified polyphenyl ether engineering material for vehicles and preparation method thereof |
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| CN105504767A (en) * | 2016-01-04 | 2016-04-20 | 江苏沃特新材料科技有限公司 | Polyphenyl ether resin alloy material, preparation method thereof and refrigeration compressor |
| CN105968775B (en) * | 2016-05-31 | 2018-10-12 | 马鞍山市恒达工模具材料有限公司 | A kind of polyphenylene ether-poly aryl oxide ether nitrile alloy material and preparation method thereof |
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| CN106589896A (en) * | 2016-11-18 | 2017-04-26 | 江苏沃特新材料科技有限公司 | High-impact-resistant polyphenyl-ether engineering plastic and preparing method and application thereof |
| CN106800713A (en) * | 2016-12-22 | 2017-06-06 | 芜湖天鸿汽车零部件有限公司 | A kind of automobile trunk plastic base plate and preparation method thereof |
| CN107880421A (en) * | 2017-11-21 | 2018-04-06 | 丁妙严 | Heat resistant type PS, PPO blending formula |
| CN108219433A (en) * | 2017-12-19 | 2018-06-29 | 宁波甬尚聚新材料有限公司 | A kind of polyphenylene oxide resin alloy and preparation method thereof |
| CN108676345A (en) * | 2018-04-24 | 2018-10-19 | 嘉兴希卡姆复合材料有限公司 | A kind of Noryl and acrylic resin alloy material and preparation method thereof |
| CN109852032A (en) * | 2019-02-13 | 2019-06-07 | 湖南恒屹新材料有限公司 | A kind of polyphenylene oxide resin based composites and its preparation method and application |
| CN112745653A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Modified polyphenyl ether, halogen-free flame-retardant TPV, preparation methods and applications of modified polyphenyl ether and halogen-free flame-retardant TPV, and composition for preparing halogen-free flame-retardant TPV |
| CN112322020A (en) * | 2020-11-25 | 2021-02-05 | 湖南恒屹新材料有限公司 | Polyphenyl ether resin composition and preparation method thereof, and wire slot and preparation method thereof |
| CN116769298A (en) * | 2023-05-26 | 2023-09-19 | 湖南恒屹新材料有限公司 | High-strength modified polyphenyl ether engineering material for vehicles and preparation method thereof |
| CN116769298B (en) * | 2023-05-26 | 2024-04-26 | 湖南恒屹新材料有限公司 | High-strength modified polyphenyl ether engineering material for vehicles and preparation method thereof |
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