CN103849146A - Polyphenylene sulfide composite material with high welding mark strength and preparation method of composite material - Google Patents
Polyphenylene sulfide composite material with high welding mark strength and preparation method of composite material Download PDFInfo
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- CN103849146A CN103849146A CN201210514562.9A CN201210514562A CN103849146A CN 103849146 A CN103849146 A CN 103849146A CN 201210514562 A CN201210514562 A CN 201210514562A CN 103849146 A CN103849146 A CN 103849146A
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Abstract
The invention discloses a polyphenylene sulfide composite material with high welding mark strength and a preparation method of the composite material. The composite material mainly consists of the following components in parts by weight: relative to 100 weight parts of the polyphenylene sulfide, 0.5-10 weight parts of a melt strength reinforcing agent. According to the invention, the polyphenylene sulfide composite material is excellent in mechanical performance, high in welding mark strength, heat-resistance, excellent in solvent resistance and capable of being widely applied to cars and electric products.
Description
Technical field:
The present invention relates to polymeric material field, be specifically related to a kind of high weld mark strength polyphenyl thioether composite material and preparation method thereof.
Background technology
Polyphenylene sulfide (PPS) is a kind of thermoplastic special engineering plastic of excellent combination property, PPS material has outstanding thermotolerance, excellent chemical-resistant resistance, solvent resistance and erosion resistance, intrinsic flame retardant resistance own, good mechanical property and electrical property, outstanding dimensional stability and good moulding processability, and have relatively low cost value, available multiple method for processing forming carries out forming process, and can precise forming.Be mainly used in automobile, electronics and electrical equipment, machinery, chemical industry and medicine and other fields, make long fiber composites for the special dimension such as military project, aerospace.
Due to injection moulding process moulded products, on goods, inevitably there is weld mark, although that these weld marks are naked eyes is indiscoverable, the weakest link on its certain product strength.For avoiding weld mark to bring infringement to the use of goods, common terms of settlement one is that product material is carried out modification or the structure of mould is carried out to modification, the 2nd, weld mark is stayed to stressed less, non-key position, and these two kinds of methods also can be used together certainly.
Improve the existing many publications of method of weld mark from mould structure, as CN 03139111.7(can eliminate mould and the using method thereof of the porose products appearance weld mark of injection moulding), mono-kind of CN 200720121116.6(can eliminate the injection mold of weld mark), the improved injection moulding process of CN 200710037661.1(, the adapted to injection system that installs and comprise lid arrangement) and CN 201010161629.6(improve the method for polymkeric substance Interpretation of The Weld Mark In The Injection Molded Part mechanical property) etc.But these angles from injection-moulding device are improved the method for weld mark, increase the input of equipment cost.
Improve disclosed patent CN101735577A(high weld mark strength reinforced polybutylene terephthalate and preparation method thereof of method of weld mark from the angle of material) and a CN101735508A(high weld mark strength reinforced polypropylene material and preparation method thereof), they set about from material modified formula, explore and improve material weld mark strength additive, the optimization of filling a prescription, is improved their weld mark strength.
Summary of the invention
The object of the invention is in order to overcome the deficiencies in the prior art, from the angle of optimization of C/C composites, a kind of modified polyphenyl thioether material of high weld mark strength is provided, can, under the prerequisite of expendable material physicals not, the weld mark strength of polyphenylene sulfide is improved.
In order to realize the weld mark strength that improves polyphenyl thioether composite material, the present invention has adopted following technical scheme.A kind of high weld mark strength polyphenyl thioether composite material, comprises polyphenylene sulfide compounds and melt strength toughener; Wherein, described melt strength toughener is selected from one or several in the epoxy resin of following formula 1 or formula 2 structures,
(formula 1);
(formula 2);
Wherein, R1 represents that carbon atom number is 1～3 alkyl, and R2 represents that carbon atom number is 1～4 alkyl, and n represents 10～50 integer; R3 represent methylidene or ethyl group, R4 represents the group containing Sauerstoffatom that hexyl or carbon atom number are 1～4.
Consider that material has the wider scope of application, in high weld mark strength polyphenyl thioether composite material of the present invention, with respect to the polyphenylene sulfide of 100 weight parts, the amount of melt strength toughener is preferably 0.5～10 weight part.
Consider that material has the wider scope of application, in high weld mark strength polyphenyl thioether composite material of the present invention, described melt strength toughener is preferably Study On O-cresol Epoxy Resin, 2-(3,4-epoxy cyclohexane base) one or more of ethyl trimethoxy silane, γ-glycidoxypropyltrimethoxy silane or γ-epoxypropoxy triethoxyl silane.
The present invention provides a kind of preparation method of above-mentioned high weld mark strength modified polyphenyl thioether material in addition.
By after raw material blending dispersion, 310 DEG C～350 DEG C of extruding zone temperature, through melting, extrude, coolingly obtain high weld mark strength polyphenyl thioether composite material; Wherein: raw material packet is containing polyphenylene sulfide compounds and melt strength toughener; Wherein, described melt strength toughener is selected from one or several in the epoxy resin of following formula 1 or formula 2 structures,
(formula 2);
Wherein, R1 represents that carbon atom number is 1～3 alkyl, and R2 represents that carbon atom number is 1～4 alkyl, and n represents 10～50 integer; R3 represent methylidene or ethyl group, R4 represents the group containing Sauerstoffatom that hexyl or carbon atom number are 1～4.
Preparation method of the present invention, the amount of melt strength toughener and kind are as described above.
In the present invention, can further add appropriate mineral filler.Optional mineral filler is one or more in glass fibre, mica, talcum powder, hydrotalcite, kaolin, polynite, silicon-dioxide, Calucium Silicate powder, calcium metasilicate, calcium carbonate, magnesiumcarbonate, barium sulfate or hollow glass bead.Above-mentioned mineral filler also can be processed with surface treatment agent, and preferably the surface treatment agent of use comprises the known method of silane coupling agent, titanate coupling agent or aluminate coupling agent and carries out surface treatment.
In the present invention, can further add appropriate amount of addition agent, described auxiliary agent comprises lubricant or nucleator.Lubricant is the one in high density polyethylene(HDPE), medium-density polyethylene, Low Density Polyethylene, polyethylene wax or tetrafluoroethylene.Nucleator is the one in talcum powder or calcium carbonate.
The present invention is from the modification of filling a prescription of the angle of material polyphenylene sulfide, and by adding weld mark strength toughener, the optimization of filling a prescription, under the prerequisite of expendable material physicals not, can make the weld mark strength of polyphenyl thioether material improve 30%.Obtain high weld mark strength material by moulding, do not need to use the excess stock such as screw, caking agent, can reduce production costs, can reduce the pollution to environment simultaneously.
Polyphenyl thioether composite material of the present invention, due to its good thermotolerance, mechanical property, high strength weld mark performance and excellent flame retardant properties itself, the fields such as widespread use automobile, electronic apparatus component.
Embodiment
Adopt melt blending extrusion mechanism standby, the length-to-diameter ratio of twin screw extruder is 45, has 13 heating zone; There is the feeding device of two cuff measuring instruments; With vacuum-pumping equipment.
Raw material explanation:
PPS be toray Co., Ltd. produce fusing point be 278 DEG C, melt viscosity be 295Pa.s (330 DEG C/6min, velocity of shear 400s
-1) the trade mark be that L2120 and fusing point are 283 DEG C, melt viscosity be 104Pa.s (330 DEG C/6min, velocity of shear 400s
-1) the trade mark mixture that is L4230; Glass fibre is that the diameter of Chongqing matrix material company limited is 8～12 μ m, and the trade mark that length is 3mm is ECS309A; Inorganic mineral filler is the calcium carbonate that the trade mark of Cologne, city of south china powder company limited production is CC-918.
Performance test:
Mechanics Performance Testing:
Tensile strength and weld mark strength: measure by standard ISO 527 with the standard batten that injection moulding is good, rate of extension 5mm/min, averages for 6 every group;
Flexural strength and modulus in flexure: measure by standard ISO 178 with the standard batten that injection moulding is good, bending speed 2mm/min, averages for 6 every group;
Shock strength: measure by standard ISO 179 with the standard batten that injection moulding is good, average for 6 every group.
Below in conjunction with specific embodiment, the present invention is done to further detailed explanation, but is not limited to these embodiment:
Embodiment 1:
Raw material is as shown in table 1.After polyphenylene sulfide and melt strength toughener are mixed in high-speed mixer, add from forcing machine spout, extruder temperature within the scope of 310 DEG C～350 DEG C, through melting, extrude, cooling, pelletizing obtains high weld mark strength polyphenyl thioether composite material; The polyphenyl thioether composite material particle that pelletizing is obtained after dry 3h, is injection molded into standard batten in the baking oven of 140 DEG C, carries out performance test by above-mentioned testing method.Results of property is shown in table 2.
Embodiment 2-5:
Identical with embodiment 1 preparation method.Raw material is as shown in table 1.Results of property is shown in table 2.
Comparative example 1:
Identical with embodiment 1 preparation method, do not add melt strength toughener.Raw material is as shown in table 1.Results of property is shown in table 2.
Table 1
Table 2
Embodiment 6:
Raw material is as shown in table 3.After polyphenylene sulfide, melt strength toughener, mineral filler, nucleator and lubricant are mixed in high-speed mixer, add from extruder main spout, side spout adds glass fibre, extruder temperature within the scope of 310 DEG C～350 DEG C, through melting, extrude, cooling, pelletizing obtains high weld mark strength polyphenyl thioether composite material; The polyphenyl thioether composite material particle that pelletizing is obtained after dry 3h, is injection molded into standard batten in the baking oven of 140 DEG C, carries out performance test by above-mentioned testing method.Results of property is shown in table 4.
Embodiment 7-9:
Identical with embodiment 6 preparation methods.Raw material is as shown in table 3.Results of property is shown in table 4.
Comparative example 2:
Identical with embodiment 6 preparation methods, do not add melt strength toughener.Raw material is as shown in table 3.Results of property is shown in table 4.
Table 3
Table 4
Embodiment 10-13:
Identical with embodiment 6 preparation methods.Raw material is as shown in table 5.Results of property is shown in table 6.
Table 5
Table 6
Embodiment 14-17:
Identical with embodiment 6 preparation methods.Raw material is as shown in table 7.Results of property is shown in table 8.
Table 7
Table 8
Claims (6)
1. a high weld mark strength polyphenyl thioether composite material, is characterized in that: comprise polyphenylene sulfide compounds and melt strength toughener; Wherein, described melt strength toughener is selected from one or several in the epoxy resin of following formula 1 or formula 2 structures,
Wherein, R1 represents that carbon atom number is 1～3 alkyl, and R2 represents that carbon atom number is 1～4 alkyl, and n represents 10～50 integer; R3 represent methylidene or ethyl group, R4 represents the group containing Sauerstoffatom that hexyl or carbon atom number are 1～4.
2. high weld mark strength polyphenyl thioether composite material according to claim 1, is characterized in that: with respect to the polyphenylene sulfide of 100 weight parts, the amount of melt strength toughener is 0.5～10 weight part.
3. high weld mark strength polyphenyl thioether composite material according to claim 1, it is characterized in that: described melt strength toughener is Study On O-cresol Epoxy Resin, 2-(3 4-epoxy cyclohexane base) one or more of ethyl trimethoxy silane, γ-glycidoxypropyltrimethoxy silane or γ-epoxypropoxy triethoxyl silane.
4. prepare the method for high weld mark strength polyphenyl thioether composite material described in claim 1 for one kind, it is characterized in that: by after raw material blending dispersion, 310 DEG C～350 DEG C of extruding zone temperature, through melting, extrude, coolingly obtain high weld mark strength polyphenyl thioether composite material;
Wherein: raw material packet is containing polyphenylene sulfide compounds and melt strength toughener; Wherein, described melt strength toughener is selected from one or several in the epoxy resin of following formula 1 or formula 2 structures,
(formula 2);
Wherein, R1 represents that carbon atom number is 1～3 alkyl, and R2 represents that carbon atom number is 1～4 alkyl, and n represents 10～50 integer; R3 represent methylidene or ethyl group, R4 represents the group containing Sauerstoffatom that hexyl or carbon atom number are 1～4.
5. preparation method according to claim 4, is characterized in that: with respect to the polyphenylene sulfide of 100 weight parts, the amount of melt strength toughener is 0.5～10 weight part.
6. preparation method according to claim 4, it is characterized in that: described melt strength toughener is Study On O-cresol Epoxy Resin, 2-(3 4-epoxy cyclohexane base) one or more of ethyl trimethoxy silane, γ-glycidoxypropyltrimethoxy silane or γ-epoxypropoxy triethoxyl silane.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105985615A (en) * | 2015-02-13 | 2016-10-05 | 汉达精密电子(昆山)有限公司 | Polylactic acid composite material and its product |
| CN105985616A (en) * | 2015-02-13 | 2016-10-05 | 汉达精密电子(昆山)有限公司 | Biodegradable coffee-ground composite material and its product |
| CN107304293A (en) * | 2016-04-21 | 2017-10-31 | 东丽先端材料研究开发（中国）有限公司 | A kind of moulded products of the polyphenyl thioether resin composition containing weld bond |
| CN108424648A (en) * | 2018-04-20 | 2018-08-21 | 江苏澳盛复合材料科技有限公司 | A kind of injection molding carbon fibre composite |
| CN110819082A (en) * | 2019-09-30 | 2020-02-21 | 广东轻工职业技术学院 | High-weld-mark-strength glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
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| CN1031847A (en) * | 1987-08-03 | 1989-03-22 | 聚塑料株式会社 | The polyarylene sulfide resin molded article that contains weld seam |
| CN1253149A (en) * | 1998-10-29 | 2000-05-17 | 住友胶木株式会社 | Polyphenylene sulfoether resin compound material |
| CN1292019A (en) * | 1998-12-24 | 2001-04-18 | 出光石油化学株式会社 | Polyarylene sulfide resin composition for electronic part encapsulation |
| CN101134847A (en) * | 2007-09-30 | 2008-03-05 | 深圳市科聚新材料有限公司 | Polyphenylene sulfide/polyamide composite material and method for making same |
| CN101735577A (en) * | 2008-11-25 | 2010-06-16 | 金发科技股份有限公司 | High weld mark strength reinforced polybutylene terephthalate material and preparation method thereof |
| CN102153860A (en) * | 2011-04-22 | 2011-08-17 | 江苏金发科技新材料有限公司 | Modified nylon material with high weld line strength and preparation method thereof |
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| CN1031847A (en) * | 1987-08-03 | 1989-03-22 | 聚塑料株式会社 | The polyarylene sulfide resin molded article that contains weld seam |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105985615A (en) * | 2015-02-13 | 2016-10-05 | 汉达精密电子(昆山)有限公司 | Polylactic acid composite material and its product |
| CN105985616A (en) * | 2015-02-13 | 2016-10-05 | 汉达精密电子(昆山)有限公司 | Biodegradable coffee-ground composite material and its product |
| CN105985616B (en) * | 2015-02-13 | 2018-05-25 | 汉达精密电子(昆山)有限公司 | Bioerodible coffee grounds composite material and products thereof |
| CN107304293A (en) * | 2016-04-21 | 2017-10-31 | 东丽先端材料研究开发（中国）有限公司 | A kind of moulded products of the polyphenyl thioether resin composition containing weld bond |
| CN107304293B (en) * | 2016-04-21 | 2021-04-30 | 东丽先端材料研究开发（中国）有限公司 | Formed product of polyphenylene sulfide resin composition containing weld line |
| CN108424648A (en) * | 2018-04-20 | 2018-08-21 | 江苏澳盛复合材料科技有限公司 | A kind of injection molding carbon fibre composite |
| CN110819082A (en) * | 2019-09-30 | 2020-02-21 | 广东轻工职业技术学院 | High-weld-mark-strength glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN110819082B (en) * | 2019-09-30 | 2021-07-06 | 广东轻工职业技术学院 | High-weld-mark-strength glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
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