CN101724252A - Semi-aromatic nylon and polyphenyl ether alloy - Google Patents
Semi-aromatic nylon and polyphenyl ether alloy Download PDFInfo
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- CN101724252A CN101724252A CN200910201442A CN200910201442A CN101724252A CN 101724252 A CN101724252 A CN 101724252A CN 200910201442 A CN200910201442 A CN 200910201442A CN 200910201442 A CN200910201442 A CN 200910201442A CN 101724252 A CN101724252 A CN 101724252A
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Abstract
The invention discloses a semi-aromatic nylon and polyphenyl ether alloy, which comprises the following components in percentage by weight: 10 to 80 percent of semi-aromatic nylon, 10 to 80 percent of polyphenyl ether, 0.1 to 3 percent of compatibilizer, 1 to 10 percent of flexibilizer and 0 to 60 percent of modifier, wherein the total weight of the components is 100 percent; the semi-aromatic nylon may be PA6T, PA9T, PA10T or PA12T. The product of the invention has excellent heat resistance, dimension stability and solvent resistance, is particularly suitable for the replacement of steel by plastic and is suitable for manufacturing heat resistant parts in automobile, machine and electronic/electrical industries. The product of the invention has a simple preparation process and low cost, meets industrial production requirements and has a wide market application prospect.
Description
Technical field
The present invention relates to the alloy of a kind of semi-aromatic nylon and polyphenylene oxide, specifically, relate to a kind of have good heat resistance energy, dimensional stability and solvent resistance, Dai Gang be can mould, the semi-aromatic nylon of heat-resistant part in making automobile, machinery, the electronics/electrical industry and the alloy that polyphenylene oxide is formed are applicable to.
Background technology
Semi-aromatic nylon is by the diacid or the diamines of aliphatie diamine or diacid and band aromatic nucleus, makes through polycondensation, and be a kind of of aromatic nylon.Because the nylon molecular backbone chain has been introduced aromatic ring structure, thereby the resistance toheat of nylon product and mechanical property are improved, water-intake rate also has reduction in various degree simultaneously, and cost performance is preferably arranged, be the high heat resistance resin between general engineering plastic nylon and thermostability engineering plastic PEEK, be mainly used in automobile and electric and electronic industry.According to the product performance requirement, each manufacturer develops the semi-aromatic nylon product of the multiple trade mark.For example: among the English Patent GB1070416, the Davis Anthony Charles of ICI company etc. has disclosed the synthetic method of a series of semi-aromatic nylons such as PA7T, PA9T, PA10T, PA12T.In addition, in U.S. Pat 5502155, DUPONT company has also mentioned with terephthalic acid and the synthetic PA10T polymkeric substance of decamethylene diamine; Patent US4022756, GB1526329, US4113708 etc. have all disclosed the preparation method of PA6T.Because semi-aromatic nylon is compared with nylon 66, its maximum characteristics are fine heat-resisting performance; Simultaneously, compare with all aromatic nylon, it has the characteristic of easy processing.Therefore, along with the needs with environmental protection cause of developing rapidly of new and high technology, its market requirement is in rising trend, and its application and development also has new progress.
Polyphenylene oxide is a kind of heat-resisting amorphous material, has very low water-intake rate and good dimensional stability.As far back as the eighties in last century, companies such as GE Plastic, Mitsubishi and Asahi just succeed in developing polyphenylene oxide and nylon 6 in succession, or the alloy of nylon 66 (seeing US4315086, US4600741, US4732938 etc. for details), be widely used in automobile, industry such as electric, but have good heat resistance energy, dimensional stability and solvent resistance, can mould Dai Gang, be applicable to that the semi-aromatic nylon of heat-resistant part in making automobile, machinery, the electronics/electrical industry is not seen relevant report as yet with the alloy technology of polyphenylene oxide.
Summary of the invention
The objective of the invention is to aim to provide a kind of have good heat resistance energy, dimensional stability and solvent resistance, can mould Dai Gang, be applicable to the semi-aromatic nylon of heat-resistant part in making automobile, machinery, the electronics/electrical industry and the alloy that polyphenylene oxide is formed, to fill up the blank of prior art.
For achieving the above object, the technical solution used in the present invention is as follows:
The alloy of semi-aromatic nylon of the present invention and polyphenylene oxide, the weight percent that it is formed and each is formed is as follows:
Semi-aromatic nylon 10%～80%
Polyphenylene oxide 10%～80%
Expanding material 0.1%～3%
Toughner 1%～10%
Properties-correcting agent 0%～60%
Above-mentioned each weight percent sum of forming is 100%; Described semi-aromatic nylon is any one among PA6T, PA9T, PA10T and the PA12T.
The preferred PA10T of described semi-aromatic nylon.
Described polyphenylene oxide comprises polyphenylene oxide homopolymer and the multipolymer that all are conventional, but preferably contain 2, the homopolymer of 6-dimethyl benzene ether unit or contain 2,6-dimethyl benzene ether unit and 2,3,6-trimethylammonium-1, the multipolymer of 4 phenylene ether units or contain derived from 2 6-dimethyl benzene phenol unit and 2,3, the multipolymer of 6-trimethylammonium-1,4 phenol units or the grafts of above-mentioned homopolymer and multipolymer.
Described expanding material be meant those can with polyphenylene oxide and polyamide resin or with both can both interactional polyfunctional compound.These interactions can be chemical (as grafting) or physical property (if can influence the biphase interfacial characteristics), the preferably expanding material of those chemical.Can multifunctional chemistry expanding material used in this invention can be both to have contained carbon-to-carbon double bond or carbon-to-carbon triple bond, the compound that contains at least one carboxylic acid, acid anhydrides, acid amides, fat, imide, amino again, as toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, glycidyl acrylate etc., the present invention preferentially selects maleic anhydride and fumaric acid; Can be aliphatic polycarboxylic acid, ester and acid amides also, as citric acid, oxysuccinic acid and their salt; It can also be the epoxide group that has more than two or two.
Described toughner can be all toughner that are applicable to polyphenylene oxide and polymeric amide, is preferably any one or a few the compound in styrene-butadiene-styrene triblock copolymer (SBS), vinylbenzene/hydrogenated isoprene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (SEP) and the hydrogenated styrene-butadiene-styrene triblock copolymer (SEBS).
Described properties-correcting agent can comprise strengthening fills the class filler, as glass fibre, mica, talcum powder, wollastonite, clay, lime carbonate etc.; Also can comprise auxiliary agent with anti-flaming function, as bromination epoxies, bromination PC, ten bromine ethylbenzenes of bromine system, the MPP of nitrogen phosphorus system, pyrophosphate salt, hypophosphite etc., the MCA and the inorganic hydroxide (as aluminium hydroxide and magnesium hydroxide) of nitrogen system; Also can comprise in lubricant, oxidation inhibitor, photostabilizer, pigment, dyestuff, anti-dripping agent, static inhibitor and the softening agent etc. one or more.
The preparation of semi-aromatic nylon of the present invention and polyphenylene oxide alloy is at first by list/twin screw extruder all components to be homogenized, and obtains the stable blend of phase, carries out melt pelletization then and gets final product.Can put in the forcing machine all components is disposable, also several orders successively wherein can be dropped into, that is: at first with polyphenylene oxide and expanding material, toughner and properties-correcting agent behind premix under the suitable temperature, add semi-aromatic nylon then and carry out blend.
Compared with prior art, product of the present invention has good heat resistance energy, dimensional stability and solvent resistance, is particularly suitable for to mould Dai Gang, is applicable to make heat-resistant part in automobile, machinery, the electronics/electrical industry; And the preparation technology of product of the present invention is simple, with low cost, meets the suitability for industrialized production requirement, has wide market application prospect.
Embodiment
Is doing further in detail of how realizing, explanation clearly and completely below in conjunction with specific embodiment to the present invention, and listed embodiment only gives further instruction to the present invention, and is not thereby limiting the invention.
Select for use among the embodiment:
Semi-aromatic nylon-PA10T is produced by JinFa Science Co., Ltd to provide;
Polyphenylene oxide PPE is produced by China LanXing chemical industry group to provide, and the trade mark is LXR045;
The expanding material maleic anhydride is to be produced by the living flower bud chemical industry in Shanghai company limited to provide; The expanding material glycidyl acrylate is to be produced by company of Du Pont (Dupont) to provide, and the trade mark is Elvaloy PTW;
Toughner SEBS is produced by (Kraton) company of rising of section to provide, and the trade mark is KRATONSEBS1651;
Properties-correcting agent silicone oil is to mark U.S. fluosilicic fine chemistry industry institute by Guangdong to produce and provide, and the trade mark is KH560.
Embodiment 1
At first 80 weight part polyphenylene oxide, 2 weight part maleic anhydrides, 5 weight part SEBS toughner and 3 weight part silicone oil are added in the twin screw extruder, carry out premix at 280～300 ℃; Add 10 weight part semi-aromatic nylon-PA10T then, continue insulation and carry out blend at 280～320 ℃; Carrying out melt pelletization at last under 290～320 ℃ gets final product.
Embodiment 2
At first 10 weight part polyphenylene oxide, 2 parts by weight of acrylic acid glycidyl esters, 5 weight part SEBS toughner and 3 weight part silicone oil are added in the twin screw extruder, carry out premix at 280～300 ℃; Add 10 weight part semi-aromatic nylon-PA10T then, continue insulation and carry out blend at 280～320 ℃; Carrying out melt pelletization at last under 290～320 ℃ gets final product
Embodiment 3
At first 45 weight part polyphenylene oxide, 2 parts by weight of acrylic acid glycidyl esters, 5 weight part SEBS toughner and 3 weight part silicone oil are added in the twin screw extruder, carry out premix at 280～300 ℃; Add 10 weight part semi-aromatic nylon-PA10T then, continue insulation and carry out blend at 280～320 ℃; Carrying out melt pelletization at last under 290～320 ℃ gets final product.
The made sample of the various embodiments described above is carried out following performance test:
Tensile property: press the ISO527-2 test, tension testing machine model: newly think carefully electronic universal tester, test speed: 50mm/min;
Bending property: press the ISO178 test, tension testing machine model: newly think carefully electronic universal tester, test speed: 2mm/min;
Notch shock: press the ISO180/1A test, shock-testing machine model: TINIUS OLSEN ModelImpact 104;
Heat-drawn wire: press the ISO75-2 test, testing tool: COESFELD 40-197-006;
Molding shrinkage: press the ISO2577 test;
Rate of moisture absorption: press ISO 62 tests.
Embodiment 1～3 prepared sample performance test result is shown in Table 1:
Table 1 embodiment 1～3 prepared sample performance test result
By table 1 as seen: the alloy of semi-aromatic nylon-PA10T of the present invention and polyphenylene oxide has excellent comprehensive mechanical properties and good heat-resistant, applicable to the heat-resistant part of making in automobile, machinery, the electronics/electrical industry.
In addition, experiment also proves: the semi-aromatic nylon-PA10T in the foregoing description can be replaced by PA6T, PA9T or PA12T; Expanding material maleic anhydride or glycidyl acrylate can be replaced by toxilic acid, fumaric acid, methylene-succinic acid, citric acid, oxysuccinic acid, Citrate trianion or malate; Toughner SEBS can be replaced by SBS or SEP; Properties-correcting agent silicone oil can be enhanced fills in class filler, fire retardant, lubricant, oxidation inhibitor, photostabilizer, pigment, dyestuff, anti-dripping agent, static inhibitor and the softening agent any one or a few and replaces.
Claims (6)
1. the alloy of semi-aromatic nylon and polyphenylene oxide is characterized in that, weight percent that it is formed and each is formed is as follows:
Semi-aromatic nylon 10%～80%
Polyphenylene oxide 10%～80%
Expanding material 0.1%～3%
Toughner 1%～10%
Properties-correcting agent 0%～60%
Above-mentioned each weight percent sum of forming is 100%; Described semi-aromatic nylon is any one among PA6T, PA9T, PA10T and the PA12T.
2. the alloy of semi-aromatic nylon according to claim 1 and polyphenylene oxide is characterized in that, described semi-aromatic nylon is PA10T.
3. the alloy of semi-aromatic nylon according to claim 1 and polyphenylene oxide, it is characterized in that described polyphenylene oxide is for containing 2, the homopolymer of 6-dimethyl benzene ether unit or contain 2,6-dimethyl benzene ether unit and 2,3, the multipolymer of 6-trimethylammonium-1,4 phenylene ether units or contain derived from 2,6-dimethyl benzene phenol unit and 2,3, the multipolymer of 6-trimethylammonium-1,4 phenol units or the grafts of above-mentioned homopolymer and multipolymer.
4. the alloy of semi-aromatic nylon according to claim 1 and polyphenylene oxide, it is characterized in that described expanding material is any one or a few the compound in toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, glycidyl acrylate, citric acid, oxysuccinic acid, Citrate trianion and the malate.
5. the alloy of semi-aromatic nylon according to claim 1 and polyphenylene oxide, it is characterized in that described toughner is any one or a few the compound in styrene-butadiene-styrene triblock copolymer (SBS), vinylbenzene/hydrogenated isoprene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (SEP) and the hydrogenated styrene-butadiene-styrene triblock copolymer (SEBS).
6. the alloy of semi-aromatic nylon according to claim 1 and polyphenylene oxide, it is characterized in that described properties-correcting agent comprises any one or a few in enhancing filling class filler, fire retardant, lubricant, oxidation inhibitor, photostabilizer, pigment, dyestuff, anti-dripping agent, static inhibitor and the softening agent.
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| CN200910201442A CN101724252A (en) | 2009-12-18 | 2009-12-18 | Semi-aromatic nylon and polyphenyl ether alloy |
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| CN200910201442A CN101724252A (en) | 2009-12-18 | 2009-12-18 | Semi-aromatic nylon and polyphenyl ether alloy |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103382305A (en) * | 2012-05-04 | 2013-11-06 | 金发科技股份有限公司 | Alloy of polysulfone resin and semi-aromatic nylon and preparation method thereof |
| CN103804906A (en) * | 2014-02-27 | 2014-05-21 | 苏州市涵信塑业有限公司 | Improved PPA plastic |
| CN103804901A (en) * | 2012-11-14 | 2014-05-21 | 上海杰事杰新材料(集团)股份有限公司 | Liquid crystal polymer/ semi-aromatic nylon alloy material and preparation method thereof |
| CN103910989A (en) * | 2012-12-31 | 2014-07-09 | 第一毛织株式会社 | Thermoplastic Resin Composition And Molded Product Including Same |
| CN104098890A (en) * | 2013-04-10 | 2014-10-15 | 上海杰事杰新材料(集团)股份有限公司 | HPN (high temperature resistant nylon)/(thermotropic liquid crystal polymer) / HNTs (halloysite nanotubes) composite material and preparation method thereof |
| CN105733253A (en) * | 2016-04-08 | 2016-07-06 | 中山大学 | Halogen-free flame-retardant high-temperature-resistant nylon composite |
| CN106566168A (en) * | 2015-10-13 | 2017-04-19 | 上海杰事杰新材料(集团)股份有限公司 | Heat-resistant semi-aromatic nylon/polyphenyl ether alloy material and preparation method thereof |
| CN106609034A (en) * | 2015-10-22 | 2017-05-03 | 上海杰事杰新材料(集团)股份有限公司 | Flame-retardant reinforced semi-aromatic nylon/polyphenylether composite and preparation method thereof |
| CN106928702A (en) * | 2015-12-31 | 2017-07-07 | 上海杰事杰新材料(集团)股份有限公司 | A kind of high temperature resistant nylon/polyphenylene oxide composite material and preparation method thereof |
-
2009
- 2009-12-18 CN CN200910201442A patent/CN101724252A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103382305A (en) * | 2012-05-04 | 2013-11-06 | 金发科技股份有限公司 | Alloy of polysulfone resin and semi-aromatic nylon and preparation method thereof |
| CN103804901A (en) * | 2012-11-14 | 2014-05-21 | 上海杰事杰新材料(集团)股份有限公司 | Liquid crystal polymer/ semi-aromatic nylon alloy material and preparation method thereof |
| CN103910989A (en) * | 2012-12-31 | 2014-07-09 | 第一毛织株式会社 | Thermoplastic Resin Composition And Molded Product Including Same |
| CN103910989B (en) * | 2012-12-31 | 2016-06-22 | 第一毛织株式会社 | Thermoplastic resin composition and the mechanograph including said composition |
| CN104098890A (en) * | 2013-04-10 | 2014-10-15 | 上海杰事杰新材料(集团)股份有限公司 | HPN (high temperature resistant nylon)/(thermotropic liquid crystal polymer) / HNTs (halloysite nanotubes) composite material and preparation method thereof |
| CN103804906A (en) * | 2014-02-27 | 2014-05-21 | 苏州市涵信塑业有限公司 | Improved PPA plastic |
| CN106566168A (en) * | 2015-10-13 | 2017-04-19 | 上海杰事杰新材料(集团)股份有限公司 | Heat-resistant semi-aromatic nylon/polyphenyl ether alloy material and preparation method thereof |
| CN106609034A (en) * | 2015-10-22 | 2017-05-03 | 上海杰事杰新材料(集团)股份有限公司 | Flame-retardant reinforced semi-aromatic nylon/polyphenylether composite and preparation method thereof |
| CN106928702A (en) * | 2015-12-31 | 2017-07-07 | 上海杰事杰新材料(集团)股份有限公司 | A kind of high temperature resistant nylon/polyphenylene oxide composite material and preparation method thereof |
| CN105733253A (en) * | 2016-04-08 | 2016-07-06 | 中山大学 | Halogen-free flame-retardant high-temperature-resistant nylon composite |
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Open date: 20100609 |