CN101747616A - Modified polyphenyl ether material and preparation method thereof - Google Patents
Modified polyphenyl ether material and preparation method thereof Download PDFInfo
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- CN101747616A CN101747616A CN200910191871A CN200910191871A CN101747616A CN 101747616 A CN101747616 A CN 101747616A CN 200910191871 A CN200910191871 A CN 200910191871A CN 200910191871 A CN200910191871 A CN 200910191871A CN 101747616 A CN101747616 A CN 101747616A
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- polyphenyl ether
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Abstract
The invention provides a modified polyphenyl ether material, which has lower cost, good flame retardant property and good mechanical property at the same time. The modified polyphenyl ether material consists of the following raw materials in part by weight: 60 to 90 parts of polyphenyl ether, 5.6 to 8.4 parts of high impact polystyrene, 9 to 13.6 parts of flame retardant, 4.8 to 7.2 parts of toughening agent, 0.4 to 0.6 part of antioxidant, 0.16 to 0.24 part of light stabilizer and 0.48 to 0.72 part of toner. The flame retardant is phosphate flame retardant or the flame retardant compounded by phosphate flame retardant and nitrogen flame retardant; the flame retardant is bisphenol A bi(diphenyl phosphate); the toughening agent is SEBS or SBS; the light stabilizer is zinc oxide and/or sulfur oxide; and the toner is colorant such as carbon black powder.
Description
Technical field
The present invention relates to the polymer materials field, be specifically related to a kind of modified polyphenyl ether composition that is applicable to the solar junction box raw material.
Background technology
Polyphenylene oxide resin (PPO) belongs to the thermoplasticity general engineering plastic, have excellent physical and mechanical properties, thermotolerance and electric insulating quality, its water absorbability is low, intensity is high, dimensional stability is good, creep resistant is optimum in all thermoplastic engineering plastics under the high temperature, but because the PPO flowability is relatively poor, common and other plastic blend modification.Modified polyphenylene ether resin (PPO) has excellent comprehensive performances and moulding processability, thereby has purposes widely in fields such as conveying machinery, building materials, aviation and military affairs such as electric and household electrical appliance, office automation machinery, automobiles.
Noryl in the prior art, especially solar junction box are higher with the Noryl production cost, and base resin all adopts imported product with main auxiliary agent, and production cost is higher.At present, be mainly used in performance perameter such as the following table of the MODIFIED PP O of solar junction box material both at home and abroad:
| Performance perameter and testing standard | ??PX9406 | ??V0150B |
| Tensile strength (ASTM D638) | ??55.8MPa | ??60.0MPa |
| Elongation at break (ASTM D638) | ??18％ | ??7％ |
| Outstanding notch shock (ASTM D256) | ??160J/m | ??14KJ/m 2 |
| Modulus in flexure (ASTM D790) | ??2650MPa | ??2550MPa |
| Flexural strength (ASTM D790) | ??112MPa | ??105MPa |
| Thermal distortion (ASTM D648) | ??122℃ | ??135℃ |
| Molten refer to (ASTM D1238) | ??3.5g/10min | |
| Flame retardant resistance (UL-94) | ??V-0 | ??V-0 |
As can be seen from the above table, though the adding of existing fire retardant can make the flame retardant properties of material reach V-0, can influence every mechanical properties such as shock resistance of material.
Summary of the invention
In view of this, in order to address the above problem, the present invention proposes a kind of modified polyphenyl ether material, cost is lower, when having the good flame-retardance energy, also has the good mechanical performance.
The object of the present invention is achieved like this: modified polyphenyl ether material, form by following weight part raw material:
Polyphenylene oxide 60-90 part;
Fire retardant 9-13.6 part;
High-impact polystyrene 5.6-8.4 part;
Toughner 4.8-7.2 part;
Oxidation inhibitor 0.4-0.6 part;
Photostabilizer 0.16-0.24 part;
Toner 0.48-0.72 part.
Further, described fire retardant is the phosphoric acid ester fire retardant, or phosphoric acid ester fire retardant and the composite fire retardant of nitrogen based flame retardant;
Further, described fire retardant is dihydroxyphenyl propane two (diphenyl phosphoester);
Further, described toughner is polystyrene-poly ethene-polybutene-polystyrene (SEBS) or polystyrene-poly butylene (SBS);
Further, described photostabilizer is zinc oxide and/or zinc sulphide;
Further, described toner is a tinting material, as carbon powder;
Further, described oxidation inhibitor is tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester;
Further, form by following weight part raw material:
75 parts of polyphenylene oxide;
Two (diphenyl phosphoesters) 11.3 parts of dihydroxyphenyl propane;
7 parts of high-impact polystyrenes;
6 parts of polystyrene-poly ethene-polybutene-polystyrene;
0.5 part of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester;
0.1 part in zinc oxide;
0.1 part in zinc sulphide;
0.6 part of carbon powder.
The present invention also provides the method for the above-mentioned modified polyphenyl ether material of preparation, comprises the steps:
1) processing of getting the raw materials ready: polyphenylene oxide is done drying treatment; Fire retardant, high-impact polystyrene and photostabilizer are prepared burden, and mix stirring 3-6 minute, add toughner, oxidation inhibitor and toner then with dried polyphenylene oxide;
2) compound with the step 1) gained mixes, and adopts forcing machine to extrude after temperature reaches set(ting)value 15-20 minute;
3) with step 2) extruded stock of gained crosses water cooling;
4) with cooled extruded stock pelletizing;
5) big or small underproof particle in the step 4) is removed in screening;
6) cooling of modified polyphenyl ether material particle, dehumidifying, the homogenizing after will screening obtains the modified polyphenyl ether material finished product.
Further, the drying described in the step 1) is with polyphenylene oxide under 104-110 ℃ temperature condition dry 3-4 hour.
Further, step 2) adopt twin screw to extrude smelting process in and extrude, the engine speed of institute's employing forcing machine is 335-400r/min, vacuum tightness＞0.06MPa, and input speed is 20-50Kg/h.The complete processing temperature is as follows: twin screw extruder one district temperature 275-285 ℃, two district temperature 280-290 ℃, three district temperature 280-290 ℃, four district temperature 285-295 ℃, five district temperature 285-295 ℃, six district temperature 285-295 ℃, seven district temperature 270-280 ℃, eight district temperature 280-290 ℃, nine district temperature 285-295 ℃, head temperature 285-295 ℃.
Phosphorus flame retardant all can be brought into play fire retardation simultaneously in gas phase and condensed phase, comprise that the surface barrier, the acid catalysis that suppress flame, molten stream heat dissipation, phosphoric acid formation become the heat insulation and oxygen barrier of carbon, carbon-coating etc., these influencing factors to fire-retardant Relative Contribution with relevant with the fire condition by the classification of fire-retardant superpolymer, but the multiple binding mode that all relates under many circumstances, phosphorus fire retardant.At condensed phase, phosphorus generates phosphoric acid in when burning, generates metaphosphoric acid under higher temperature, and phosphoric acid and metaphosphoric acid all are dewatering agents, makes the polymkeric substance carbonization of directly dewatering, and avoids inflammable gas to generate; Form coke layer on the combustionmaterial surface simultaneously, it can intercept contacting of combustion gases and flame front on the one hand, again air and heat are separated from the combustionmaterial surface on the other hand, thereby stop burning away of object, therefore the fire retardant as modified polyphenyl ether material has good effect, easy to manufacture, the low price, easy to use of fire retardant of the additive-based phosphoric acid ester system that the present invention simultaneously adopts.And the nitrogen flame retardant is the most effective fire retardant at present.Under the state that initially is heated, nitrogen flame retardant generation thermolysis, the absorption portion heat has reached the purpose that cools; Discharge non-flammable gas N simultaneously
2, form barrier, the combustionvelocity of polymer materials is slowed down or burning is extinguished, play the flame retardant effect of gas phase shielding.Two kinds of composite uses of fire retardant have the advantage of two kinds of fire retardants simultaneously, play better flame retardant effect, but because the nitrogen flame retardant can produce the gas of contaminate environment, so a kind of in the fire retardant as composite use.Adding the composite fire retardant of phosphoric acid ester fire retardant or phosphoric acid ester fire retardant and nitrogen based flame retardant makes Flame Retardancy of the present invention reach V-0; Add toughner simultaneously at the adding fire retardant, make material not only have excellent flame-retardant performance, and have the good mechanical performance.
Other advantages of the present invention, target, to set forth in the following description to a certain extent with feature, and to a certain extent,, perhaps can obtain instruction from the practice of the present invention based on being conspicuous to those skilled in the art to investigating hereinafter.Target of the present invention and other advantages can be passed through following specification sheets, claims, and the specifically noted structure realizes and obtains in the accompanying drawing.
Embodiment
Below will be described in detail the preferred embodiments of the present invention.
Embodiment 1
The modified polyphenyl ether material of present embodiment is made up of following weight part raw material:
60 parts of polyphenylene oxide;
Dihydroxyphenyl propane two (diphenyl phosphoesters) and nitrogen based flame retardant by weight 2: 1 composite 9 parts; Described nitrogen based flame retardant is mixed with arbitrary proportion by trimeric cyanamide and melamine salt;
8.4 parts of high-impact polystyrenes;
4.8 parts of polystyrene-poly ethene-polybutene-polystyrene (SEBS);
0.4 part of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester;
0.10 part in zinc oxide;
0.06 part in zinc sulphide;
0.48 part of carbon powder.
Embodiment 2
The modified polyphenyl ether material of present embodiment is made up of following weight part raw material:
75 parts of polyphenylene oxide;
Two (diphenyl phosphoesters) 11.3 parts of dihydroxyphenyl propane;
7 parts of high-impact polystyrenes;
6 parts of polystyrene-poly ethene-polybutene-polystyrene (SEBS);
0.5 part of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester;
0.1 part in zinc oxide;
0.1 part in zinc sulphide;
0.6 part of carbon powder.
Embodiment 3
The modified polyphenyl ether material of present embodiment is made up of following weight part raw material:
90 parts of polyphenylene oxide;
Two (diphenyl phosphoesters) 13.6 parts of dihydroxyphenyl propane;
5.6 parts of high-impact polystyrenes;
7.2 parts of polystyrene-poly butylene (SBS);
0.6 part of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester;
0.15 part in zinc oxide;
0.09 part in zinc sulphide;
0.72 part of carbon powder.
The method for preparing modified polyphenyl ether material of present embodiment comprises the steps:
1) processing of getting the raw materials ready: with base resin at 104-110 ℃ of dry 3-4 hour; With fire retardant, high-impact polystyrene and photostabilizer batching batching, and with dried major ingredient mixing 3-6 minute, add toughner, oxidation inhibitor and toner again, mixing can be adopted SHR-25A type high mixer; Fire retardant, photostabilizer, oxidation inhibitor and toughner can adopt raw material commonly used at present in this area, but use the raw material of selecting for use among the present invention can obtain better effect;
2) compound with the step 1) gained mixes, and adopts twin screw to extrude smelting process and extrudes, and can adopt CTE35 type twin screw extruder, best: the twin screw extruder processing temperature reaches 275 ℃ of district's temperature, 280 ℃ of two district's temperature, 280 ℃ of three district's temperature, 285 ℃ of four district's temperature, 285 ℃ of five district's temperature, 285 ℃ of six district's temperature, 270 ℃ of seven district's temperature, 280 ℃ of eight district's temperature, 285 ℃ of nine district's temperature, 285 ℃ of head temperatures were extruded after 15-20 minute; Preferably, engine speed is 335-400r/min, vacuum tightness＞0.06MPa, and input speed is 20-50Kg/h; More excellent, engine speed is 360r/min, input speed is 35Kg/h;
3) with step 2) extruded stock of gained crosses water cooling, and the water coolant plane control is below tank volumetrical 2/3-3/4 plane, and water temperature is controlled at below 60 ℃;
4) with cooled extruded stock pelletizing, granular size φ 3 * 3mm;
5) big or small underproof particle in the step 4) is removed in screening;
6) cooling of modified polyphenyl ether material particle, dehumidifying, the homogenizing after will screening obtains the modified polyphenyl ether material finished product.
Modified polyphenyl ether material performance perameter with said ratio and method preparation is as follows:
| Performance perameter and testing standard | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Tensile strength (ASTM D638) | ??64.9MPa | ??64.84MPa | ??65.3MPa |
| Elongation at break (ASTM D638) | ??7.6％ | ??13.88％ | ??9.9％ |
| Performance perameter and testing standard | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Outstanding notch shock (ASTM D256) | ??21.68KJ/m 2 | ??22.82KJ/m 2 | ??23.54KJ/m 2 |
| Modulus in flexure (ASTM D790) | ??1864.7MPa | ??1867.52MPa | ??1905.1MPa |
| Flexural strength (ASTM D790) | ??90.6MPa | ??89.04MPa | ??88.4MPa |
| Thermal distortion (ASTM D648) | ??131℃ | ??140℃ | ??136℃ |
| Molten refer to (ASTM D1238) | ??22.0g/10min | ??22.2g/10min | ??22.3g/10min |
| Flame retardant resistance (UL-94) | ??V-0 | ??V-0 | ??V-0 |
As can be seen from the above table, modified polyphenyl ether material of the present invention is except that the mechanics of bending performance, and all the other mechanical properties are all above existing imported product, and cost reduces by 25% than existing imported product.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and obviously, those skilled in the art can carry out various changes and modification and not break away from the spirit and scope of the present invention the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1. modified polyphenyl ether material is characterized in that: be made up of following weight part raw material:
Polyphenylene oxide 60-90 part;
Fire retardant 9-13.6 part;
High-impact polystyrene 5.6-8.4 part;
Toughner 4.8-7.2 part;
Oxidation inhibitor 0.4-0.6 part;
Photostabilizer 0.16-0.24 part;
Toner 0.48-0.72 part.
2. modified polyphenyl ether material as claimed in claim 1 is characterized in that: described fire retardant is the phosphoric acid ester fire retardant, or phosphoric acid ester fire retardant and the composite fire retardant of nitrogen based flame retardant.
3. modified polyphenyl ether material as claimed in claim 2 is characterized in that: described fire retardant is dihydroxyphenyl propane two (diphenyl phosphoester).
4. modified polyphenyl ether material as claimed in claim 1 is characterized in that: described toughner is polystyrene-poly ethene-polybutene-1-polystyrene or polystyrene-poly butylene.
5. modified polyphenyl ether material as claimed in claim 1 is characterized in that: described photostabilizer is zinc oxide and/or zinc sulphide.
6. modified polyphenyl ether material as claimed in claim 1 is characterized in that: described toner is a tinting material.
7. as each described modified polyphenyl ether material in the claim 1 to 6, it is characterized in that: form by following weight part raw material:
75 parts of polyphenylene oxide;
Two (diphenyl phosphoesters) 11.3 parts of dihydroxyphenyl propane;
7 parts of high-impact polystyrenes;
6 parts of polystyrene-poly ethene-polybutene-polystyrene;
0.5 part of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester;
0.1 part in zinc oxide;
0.1 part in zinc sulphide;
0.6 part of carbon powder.
8. prepare the method for modified polyphenyl ether material, it is characterized in that: comprise the steps:
1) processing of getting the raw materials ready: polyphenylene oxide is done drying treatment; Fire retardant, high-impact polystyrene and photostabilizer are prepared burden, and mix stirring 3-6 minute, add toughner, oxidation inhibitor and toner then with dried polyphenylene oxide;
2) compound with the step 1) gained mixes, and adopts forcing machine to extrude after temperature reaches set(ting)value 15-20 minute;
3) with step 2) extruded stock of gained crosses water cooling;
4) with cooled extruded stock pelletizing;
5) big or small underproof particle in the step 4) is removed in screening;
6) cooling of modified polyphenyl ether material particle, dehumidifying, the homogenizing after will screening obtains the modified polyphenyl ether material finished product.
9. the method for preparing modified polyphenyl ether material as claimed in claim 8 is characterized in that: the drying described in the step 1) is with polyphenylene oxide under 104-110 ℃ temperature condition dry 3-4 hour.
10. the method for preparing modified polyphenyl ether material as claimed in claim 9, it is characterized in that: step 2) in adopt twin screw to extrude smelting process to extrude, the engine speed of institute's employing forcing machine is 335-400r/min, vacuum tightness＞0.06MPa, and input speed is 20-50Kg/h; Temperature control is as follows in the complete processing: twin screw extruder one district temperature 275-285 ℃, two district temperature 280-290 ℃, three district temperature 280-290 ℃, four district temperature 285-295 ℃, five district temperature 285-295 ℃, six district temperature 285-295 ℃, seven district temperature 270-280 ℃, eight district temperature 280-290 ℃, nine district temperature 285-295 ℃, head temperature 285-295 ℃.
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| CN102311634A (en) * | 2011-04-29 | 2012-01-11 | 深圳市科聚新材料有限公司 | PPO (poly phenylene oxide) composite material as well as preparation method and application thereof |
| CN102796362A (en) * | 2011-05-24 | 2012-11-28 | 比亚迪股份有限公司 | Polyphenylether material and preparation method thereof |
| CN103562314A (en) * | 2011-05-26 | 2014-02-05 | 沙伯基础创新塑料知识产权有限公司 | Molding composition for photovoltaic junction boxes and connectors |
| CN103554420A (en) * | 2013-10-25 | 2014-02-05 | 马鞍山市佳源环保科技有限公司 | Novel insulating polyurethane foam material |
| CN103788621A (en) * | 2014-01-27 | 2014-05-14 | 上海日之升新技术发展有限公司 | Ultrahigh-CTI (Comparative Tracking Index) halogen-free and flame-retardant polyphenyl ether alloy and preparation method thereof |
| CN103937221A (en) * | 2014-04-18 | 2014-07-23 | 安徽省中日农业环保科技有限公司 | Heat-resisting flame retardant modified polyphenyl ether material for automotive plastic parts |
| CN104231588A (en) * | 2014-09-29 | 2014-12-24 | 中节能太阳能科技（镇江）有限公司 | Photovoltaic wiring box body material and preparing method thereof |
| CN104893223A (en) * | 2015-06-18 | 2015-09-09 | 青岛海信电器股份有限公司 | Electronic equipment casing material and preparation method thereof |
| CN104900642A (en) * | 2015-03-26 | 2015-09-09 | 苏州市德莱尔建材科技有限公司 | MPPO board for integrated circuit and manufacturing method thereof |
| CN106366616A (en) * | 2016-08-26 | 2017-02-01 | 青岛海尔新材料研发有限公司 | MPPO (modified polyphenylene oxide) composite material and preparation method thereof |
| US10189990B2 (en) | 2015-04-27 | 2019-01-29 | Sabic Global Technologies B.V. | Poly(phenylene ether) composition and article |
| CN109679316A (en) * | 2018-12-28 | 2019-04-26 | 上海普利特伴泰材料科技有限公司 | A kind of PPO plastics and preparation method thereof for making coal mine water supply and sewerage pipeline |
| CN110591331A (en) * | 2019-08-16 | 2019-12-20 | 杭州博适特新材料科技有限公司 | Modified polyphenylene sulfide or modified polyphenylene oxide foamed bead and preparation method thereof |
| CN110982245A (en) * | 2019-12-17 | 2020-04-10 | 宁波华腾首研新材料有限公司 | Modified polyphenyl ether resin material and preparation method and application 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 |
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2009
- 2009-12-11 CN CN200910191871A patent/CN101747616A/en active Pending
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| CN102311634A (en) * | 2011-04-29 | 2012-01-11 | 深圳市科聚新材料有限公司 | PPO (poly phenylene oxide) composite material as well as preparation method and application thereof |
| CN102311634B (en) * | 2011-04-29 | 2014-05-28 | 深圳市科聚新材料有限公司 | PPO (poly phenylene oxide) composite material as well as preparation method and application thereof |
| CN102796362A (en) * | 2011-05-24 | 2012-11-28 | 比亚迪股份有限公司 | Polyphenylether material and preparation method thereof |
| CN102796362B (en) * | 2011-05-24 | 2015-12-02 | 比亚迪股份有限公司 | A kind of polyphenyl ether material and preparation method thereof |
| CN103562314A (en) * | 2011-05-26 | 2014-02-05 | 沙伯基础创新塑料知识产权有限公司 | Molding composition for photovoltaic junction boxes and connectors |
| CN103554420A (en) * | 2013-10-25 | 2014-02-05 | 马鞍山市佳源环保科技有限公司 | Novel insulating polyurethane foam material |
| CN103554420B (en) * | 2013-10-25 | 2015-05-13 | 马鞍山市佳源环保科技有限公司 | Novel insulating polyurethane foam material |
| CN103788621A (en) * | 2014-01-27 | 2014-05-14 | 上海日之升新技术发展有限公司 | Ultrahigh-CTI (Comparative Tracking Index) halogen-free and flame-retardant polyphenyl ether alloy and preparation method thereof |
| CN103937221A (en) * | 2014-04-18 | 2014-07-23 | 安徽省中日农业环保科技有限公司 | Heat-resisting flame retardant modified polyphenyl ether material for automotive plastic parts |
| CN104231588A (en) * | 2014-09-29 | 2014-12-24 | 中节能太阳能科技（镇江）有限公司 | Photovoltaic wiring box body material and preparing method thereof |
| CN104900642A (en) * | 2015-03-26 | 2015-09-09 | 苏州市德莱尔建材科技有限公司 | MPPO board for integrated circuit and manufacturing method thereof |
| US10189990B2 (en) | 2015-04-27 | 2019-01-29 | Sabic Global Technologies B.V. | Poly(phenylene ether) composition and article |
| CN104893223A (en) * | 2015-06-18 | 2015-09-09 | 青岛海信电器股份有限公司 | Electronic equipment casing material and preparation method thereof |
| CN104893223B (en) * | 2015-06-18 | 2018-09-14 | 青岛海信电器股份有限公司 | Sheathing material of a kind of electronic equipment and preparation method thereof |
| CN106366616A (en) * | 2016-08-26 | 2017-02-01 | 青岛海尔新材料研发有限公司 | MPPO (modified polyphenylene oxide) composite material and preparation method thereof |
| CN106366616B (en) * | 2016-08-26 | 2018-04-06 | 青岛海尔新材料研发有限公司 | A kind of MPPO composites and preparation method thereof |
| CN109679316A (en) * | 2018-12-28 | 2019-04-26 | 上海普利特伴泰材料科技有限公司 | A kind of PPO plastics and preparation method thereof for making coal mine water supply and sewerage pipeline |
| CN110591331A (en) * | 2019-08-16 | 2019-12-20 | 杭州博适特新材料科技有限公司 | Modified polyphenylene sulfide or modified polyphenylene oxide foamed bead 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 |
| CN110982245A (en) * | 2019-12-17 | 2020-04-10 | 宁波华腾首研新材料有限公司 | Modified polyphenyl ether resin material and preparation method and application thereof |
| CN116552074A (en) * | 2023-05-05 | 2023-08-08 | 江门建滔电子发展有限公司 | High-heat-dissipation low-dielectric copper-clad plate and preparation method thereof |
| CN116552074B (en) * | 2023-05-05 | 2023-12-19 | 江门建滔电子发展有限公司 | High-heat-dissipation low-dielectric copper-clad plate and preparation method thereof |
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