CN102675878A - Manufacturing method for polyphenyl thioether alloy as insulating material of high-speed railway - Google Patents
Manufacturing method for polyphenyl thioether alloy as insulating material of high-speed railway Download PDFInfo
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- CN102675878A CN102675878A CN2012101204153A CN201210120415A CN102675878A CN 102675878 A CN102675878 A CN 102675878A CN 2012101204153 A CN2012101204153 A CN 2012101204153A CN 201210120415 A CN201210120415 A CN 201210120415A CN 102675878 A CN102675878 A CN 102675878A
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Abstract
The invention discloses a manufacturing method for a polyphenyl thioether alloy as an insulating material of a high-speed railway. The weight percentage of PPS (Polyphenylene Sulfide) to glass fiber to polyamide resin to antioxidant in the polyphenyl thioether alloy is (45.8-49.2) : (30-40) : (24-10) : (0.2-0.8). The manufacturing method comprises the following steps: obtaining polyphenyl thioether resin premixed material from the PPS, the glass fiber, the polyamide resin and the antioxidant; inputting the polyphenyl thioether resin premixed material and the glass fiber treated by 0.33 percent by weight of vinyl tri-(beta-methoxyethoxy) silane A-172 surfactant into a double-screen extruder for mixing, extruding and forming; and carrying out cooling and particle dicing to obtain a finished alloy. The polyphenyl thioether alloy obtained by the manufacturing method disclosed by the invention has high insulating performance and high wear resisting performance and can be widely applied to the fields of insulating materials for electricity and electronics, machinery, chemical engineering, petroleum, military industry and space flight and aviation and has remarkable advantages as the insulating material of the high-way railway.
Description
Affiliated technical field
The invention belongs to speciality polymer material Application Areas.
Background technology
Polyphenylene sulfide (PPS) good heat stability; Have outstanding high thermal resistance, fusing point reaches 285 ℃, is higher than other special engineering plastics of present suitability for industrialized production; The PPS alloy has good injection processing characteristics, can be processed into the PPS composite product of all size, different shape.But, explore and find that the more good PPS matrix material of performance is still the target that people pursue in the more harsh field of some application conditions.
Introduced among the Chinese patent CN:1667044A and a kind ofly added aromatic phosphoric ester and polyphenylene oxides is the method for manufacture of the polyphenyl thioether composite material of resin, its objective is at injection molding SHI and improve the heat-resistant stability of matrix material and the surface smoothness of shaped material.But the dispersion effect of aromatic phosphoric ester in polyphenylene sulfide is undesirable, is prone to when under the general technology level, producing in pellet, form the parcel phenomenon, thereby directly has influence on high-temperature mechanical property.
Introduced among the Chinese patent CN:1253149A and a kind ofly added epoxy silane compounds and high component is inorganic, the method for manufacture of the polyphenylene sulfide of organic fibre (PPS) matrix material, its objective is and want to reduce the overlap of this matrix material at injection molded.Thereby a kind of polyphenyl thioether composite material with good processing properties, physical strength is provided; Though the overlap behind the packing materials such as adding epoxy silane compounds when being injected into part reduces, and has but reduced the resistance to impact shock and the tensile strength of polyphenyl thioether composite material.
Introduced the method for manufacture that employing zinc oxide palpus crystalline substance and spun glass or thomel and polyphenylene sulfide (PPS) resin carry out polyphenylene sulfide (PPS) matrix material of blending and modifying among the Chinese patent CN:1272124A; Its objective is that adopting zinc oxide is that corrosion inhibitor improves corrosion of metal property, can eliminate the detrimentally affect of mechanical-physical character; But after adding zinc oxide, the tensile strength and the elongation at break of the polyphenylene sulfide of processing (PPS) matrix material injection forming decrease, and its resistance to impact shock also decreases.
At the one Chinese patent application number: introduced a kind of thermo-stabilizer and working method that can be used for the polyphenylene sulfide alloy of high ferro insulating material 3 penta different third glue, phenyl alkylsulf, PS, clorafin thing of adding among the 200710050119.x, this patent is to adopt very common method poly-p-phenylene sulfide ether resin to carry out modification to strengthen in fact.
In view of the above shortcoming of prior art, the objective of the invention is to study a kind ofly produce shock-resistant, high stabile against thermal denaturation, tensile strength is good and the polyphenyl thioether composite material that contains spun glass low to metallic corrosion, good processability.
The inventive method gained alloy has high insulating property, high-weatherability ability.Can be widely used in the insulating material field of electronic apparatus, machinery, chemical industry, oil, military project, space flight and aviation, especially have obvious advantages as the high-speed railway insulating material.
Summary of the invention:
Its main technique comprises:
A kind of method of manufacture that can be used for the polyphenylene sulfide alloy of high ferro insulating material; Weight percent in the polyphenylene sulfide alloy between PPS and spun glass and polyamide resin and the oxidation inhibitor is=45.8～49.2: 30～40: 24～10: 0.2～0.8; Said polyphenylene sulfide cladodification degree is 0.1%mol; Percent crystallinity is 70%, and melt flow rate is 600～800g/10min, adopts following process step:
1) it is even to add behind oxidation inhibitor, the polyamide resin weighting agent in impeller thorough mixing in the polyphenylene sulfide, obtains polyphenylene sulfide Preblend with this;
2) with 1) Preblend of gained polyphenylene sulfide again with handle the twin screw extruder of spun glass input later through 0.33%wt vinyl three ('beta '-methoxy oxyethyl group) silane surface treatment agent, form the finished product alloy through the mixing extrusion molding of twin screw extruder, cooling, pelletizing.
The purpose that adds polyamide resin (PA1010) in the process of the present invention is to reduce the burr (overlap) of moulding on the one hand; Improve the melt strength of matrix material in injection moulding process on the other hand; The 3rd, reduce the percent crystallinity of matrix material and the crystallization velocity of raising matrix material; Can reduce the various losses of matrix material in injection moulding process like this, improve the yield rate of moulding.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention.
The product performance table that Fig. 2 obtains for embodiment of the invention experiment.
Embodiment
With weight-average molecular weight is 3.5 ten thousand; Melt flow index be 800g/10min and MWD coefficient be 2.5 and the cladodification degree be 0.1%mol; Percent crystallinity is 70% branched chain type polyphenylene sulfide (in polyphenylene sulfide, containing the trichlorobenzene of 0.05%mol, the tetrachlorobenzene of 0.01%mol, the pentachlorobenzene of 0.015%mol and 0.025% branched chain type structures such as Perchlorobenzene); Add in the impeller; Its add-on is that 45.8%wt polyphenylene sulfide, 0.2%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, 24%wt granularity are high-speed stirring 3h behind polymeric amide (PA1010) resin of 35um; Make it be mixed into the uniform polyphenylene sulfide mixture of quality; Single fiber diameter is the spun glass input twin screw extruder of 30um after handling through 0.33%wt vinyl three ('beta '-methoxy oxyethyl group) silane (A-172) surface treatment agents with 30%wt then, forms the finished product alloy through the mixing extrusion molding of twin screw extruder, cooling, pelletizing, packs at last, puts in storage, uses.
The various physicalies of the polyphenyl thioether composite material that obtains with aforesaid method will show in Fig. 2.
Embodiment 2
With weight-average molecular weight is 4.3 ten thousand; Melt flow index be 600g/10min and MWD coefficient be 2.5 and the cladodification degree be 0.1%mol; Percent crystallinity is 70% branched chain type polyphenylene sulfide (in polyphenylene sulfide, containing the trichlorobenzene of 0.05%mol, the tetrachlorobenzene of 0.01%mol, the pentachlorobenzene of 0.015%mol and 0.025% branched chain type structures such as Perchlorobenzene); Add in the impeller; Its add-on is that 49.2%wt polyphenylene sulfide, 0.8%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, 10%wt granularity are high-speed stirring 3h behind polymeric amide (PA1010) resin of 35um; Make it be mixed into the uniform polyphenylene sulfide mixture of quality; Single fiber diameter is the spun glass input twin screw extruder of 30um after handling through 0.33%wt vinyl three ('beta '-methoxy oxyethyl group) silane (A-172) surface treatment agents with 40%wt then, forms the finished product alloy through the mixing extrusion molding of twin screw extruder, cooling, pelletizing, packs at last, puts in storage, uses.
The various physicalies of the polyphenyl thioether composite material that obtains with aforesaid method will show in Fig. 2.
The comparative example 1
With weight-average molecular weight is 40,000; Melt flow index is that 430g/10min and MWD coefficient are 2.8 polyphenylene sulfide; Add in the impeller; Stir 3h after wherein adding 98%wt polyphenylene sulfide, 2%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, make it be mixed into the uniform polyphenylene sulfide mixture of quality, handling later with 30%wt through β vinyl three ('beta '-methoxy oxyethyl group) silane (A-172) surface treatment agents then, single fiber diameter is the spun glass input twin screw extruder of 30um; Form the finished product alloy through the mixing extrusion molding of twin screw extruder, cooling, pelletizing, pack at last, put in storage, use.
The various physicalies of the polyphenyl thioether composite material that obtains with aforesaid method will show in Fig. 2.
Embodiment 3
With weight-average molecular weight is 3.9 ten thousand; Melt flow index be 700g/10min and MWD coefficient be 2.3 and the cladodification degree be 0.1%mol; Percent crystallinity is 70% branched chain type polyphenylene sulfide (in polyphenylene sulfide, containing the trichlorobenzene of 0.05%mol, the tetrachlorobenzene of 0.01%mol, the pentachlorobenzene of 0.015%mol and 0.025% branched chain type structures such as Perchlorobenzene); Add in the impeller; Its add-on is that 47.5%wt polyphenylene sulfide, 0.5%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, 18%wt granularity are high-speed stirring 3h behind polymeric amide (PA1010) resin of 35um; Make it be mixed into the uniform polyphenylene sulfide mixture of quality; Single fiber diameter is the spun glass input twin screw extruder of 30um after handling through 0.33%wt vinyl three ('beta '-methoxy oxyethyl group) silane (A-172) surface treatment agents with 34%wt then, forms the finished product alloy through the mixing extrusion molding of twin screw extruder, cooling, pelletizing, packs at last, puts in storage, uses.
The various physicalies of the polyphenyl thioether composite material that obtains with aforesaid method will show in table one.
Embodiment 4
With weight-average molecular weight is 4.1 ten thousand; Melt flow index be 630g/10min and MWD coefficient be 2.5 and the cladodification degree be 0.1%mol; Percent crystallinity is 70% branched chain type polyphenylene sulfide (in polyphenylene sulfide, containing the trichlorobenzene of 0.05%mol, the tetrachlorobenzene of 0.01%mol, the pentachlorobenzene of 0.015%mol and 0.025% branched chain type structures such as Perchlorobenzene); Add in the impeller; Its add-on is that 48.3%wt polyphenylene sulfide, 0.7%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, 20%wt granularity are high-speed stirring 3h behind polymeric amide (PA1010) resin of 35um; Make it be mixed into the uniform polyphenylene sulfide mixture of quality; Single fiber diameter is the spun glass input twin screw extruder of 30um after handling through 0.33%wt vinyl three ('beta '-methoxy oxyethyl group) silane (A-172) surface treatment agents with 31%wt then, forms the finished product alloy through the mixing extrusion molding of twin screw extruder, cooling, pelletizing, packs at last, puts in storage, uses.
The various physicalies of the polyphenyl thioether composite material that obtains with aforesaid method will show in Fig. 2.
Embodiment 5
With weight-average molecular weight is 4.0 ten thousand; Melt flow index be 690g/10min and MWD coefficient be 2.8 and the cladodification degree be 0.1%mol; Percent crystallinity is 70% branched chain type polyphenylene sulfide (in polyphenylene sulfide, containing the trichlorobenzene of 0.05%mol, the tetrachlorobenzene of 0.01%mol, the pentachlorobenzene of 0.015%mol and 0.025% branched chain type structures such as Perchlorobenzene); Add in the impeller; Its add-on is that 48.6%wt polyphenylene sulfide, 0.4%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, 21%wt granularity are high-speed stirring 3h behind polymeric amide (PA1010) resin of 35um; Make it be mixed into the uniform polyphenylene sulfide mixture of quality; Single fiber diameter is the spun glass input twin screw extruder of 30um after handling through 0.33%wt vinyl three ('beta '-methoxy oxyethyl group) silane (A-172) surface treatment agents with 30%wt then, forms the finished product alloy through the mixing extrusion molding of twin screw extruder, cooling, pelletizing, packs at last, puts in storage, uses.
The comparative example 2
With weight-average molecular weight is 50,000; Melt flow index is that 324g/10min and MWD coefficient are 2.0 polyphenylene sulfide; Add in the impeller; Stir 2h after wherein adding 98.5%wt polyphenylene sulfide, 1.5%wt phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems oxidation inhibitor, make it be mixed into the uniform polyphenylene sulfide mixture of quality, handling later with 35%wt through supervinyi three ('beta '-methoxy oxyethyl group) silane (A-172) surface treatment agent then, single fiber diameter is the spun glass input twin screw extruder of 30um; Form the finished product alloy through the mixing extrusion molding of twin screw extruder, cooling, pelletizing, pack at last, put in storage, use.
The various physicalies of the polyphenyl thioether composite material that obtains with aforesaid method will show in Fig. 2.
Can see through tabulation among Fig. 2: behind polymeric amide (PA1010) resin compound; The melt strength of polyphenylene sulfide (PPS) matrix material has obviously improved; Overlap length obviously reduces; Impact resistance, toughness, anti-bent pleat intensity, tensile strength obviously strengthen, and elongation at break also increases significantly with same type of material.
Owing to melt mixed very even with polyphenylene sulfide after adding polymeric amide (PA1010) resin compound and phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems compound; Can not produce parcel phenomenon or particle shape; Improved the use characteristics of material, the so just balanced technology intensity index that has improved polyphenylene sulfide.
Product each item index and employed detection method among Fig. 2:
Tensile strength and elongation are all carried out by GB/T1040-1992, and test speed is 10mm/min; Bent pleat intensity is pressed GB/T9341-1988 and is carried out, and resistance to impact shock is pressed GB/T1843-1996 and carried out, and heat-drawn wire is pressed the regulation of GB/T1634-1979 (1989) and carried out.
Performance index by Fig. 2 can be found out; The thermostability of product improves, and commercially available Japanese firm is contained spun glass 40% like product parallel laboratory test, and its tensile strength, elongation, the bent pleat intensity of glass, resistance to impact shock are respectively 281Mpa; 3.7%, 315Mpa and 18.4j/m
2
After also finding in the experiment to add thicker spun glass, for example single fiber diameter 35um parallel laboratory test, its resistance to impact shock has tangible enhancing.The adding of polymeric amide (PA1010) resin, also tensile strength and the elongation at break to product of the present invention significantly improves the help that forward is provided.
After adding polymeric amide (PA1010) resin compound and phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems compound, polyphenylene sulfide (PPS) matrix material is when thermostability obviously improves, and product overlap length is reduction trend.Since after adding polymeric amide (PA1010) resin compound and phosphorous acid triphenylmethyl methacrylate in ninth of the ten Heavenly Stems compound, molten mixed very even with polyphenylene sulfide, can not produce parcel phenomenon or particle shape yet.The improvement of all these processing condition makes some physical propertiess of product and use characteristics obtain comprehensive improvement.
Though embodiments of the invention with hexamethylene six alkane methyl alcohol polyoxy vinylbenzene ether phosphate amine salt (diethyl, three second), glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt for providing; Also can consider wider Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate compounds in the actual production, for example: one or more compounds of phosphate ester salts such as aliphatic alcohol polyoxyvinethene phosphate sodium salt, hexamethylene six alkane methyl alcohol polyoxy vinylbenzene ether phosphate amine salt (diethyl, three second), fatty alcohol-ether (7) SULPHOSUCCINIC ACID ESTER triethanolamine salt, fatty alcohol-ether (9) SULPHOSUCCINIC ACID ESTER triethanolamine salt, octanol SULPHOSUCCINIC ACID ESTER MCPH, octanol polyoxyethylene phosphate OPEK, nonyl phenol phosphate sylvite, NP ether phosphoric acid monoesters ethanolamine salt, Nonyl pheno (7) ether phosphoric acid, single, double ester Nonyl pheno (4-10) ether phosphoric acid, single, double ester, glycerin polyoxyethylene ether SULPHOSUCCINIC ACID ESTER, glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt, PAPE, higher alcohols phosphoric acid ester sodium and phosphorylation Viscotrol C sodium salt, Stearinsaeure, sulfuric ester of glycerol sodium salt, Viscotrol C phosphate ester salt, phosphorous acid triphenylmethyl methacrylate in the ninth of the ten Heavenly Stems.
Polymeric amide (PA1010) the resin resin compound that adds in the present invention; Can reduce the overlap (burr) that the polyphenylene sulfide alloy produces when the injection mould goods are shaped; Make the surface smoothness height of its molded article and the toughness of injection molded goods; These organoalkoxysilane resins can be one or more in the organoalkoxysilanes such as vinyltrimethoxy silane, vinyltriethoxysilane, styryl triethoxyl silane, styryl Trimethoxy silane, 3 monomethyl propenyloxy group propyl group methyl dimethoxysilanes, 3 monomethyl propenyloxy group propyl trimethoxy silicanes, 3 monomethyl propenyloxy group propyl group methyldiethoxysilane, 3 monomethyl propenyloxy group propyl-triethoxysilicanes, 3-propenyloxy group propyl trimethoxy silicane; Especially serving as better with vinyltrimethoxy silane, vinyltriethoxysilane, styryl triethoxyl silane, styryl Trimethoxy silane, polymeric amide (PA1010) resin, is best with styryl triethoxyl silane, styryl Trimethoxy silane, polymeric amide (PA1010) resin.
The objectionable impurities trapping agent that the present invention can also add is inclined to one side zincic acid/zincic acid or its esters compound, and they are: zincic acid, zincic acid, zincic acid calcium partially partially; Inclined to one side zincic acid magnesium, inclined to one side zincic acid barium, zincic acid calcium, zincic acid magnesium; Zincic acid barium, zinc carbonate, etc. zinciferous compound, with zincic acid; Partially zincic acid is best, and they not only can suppress the generation of corrosives and impurity, can also replenish among the pellet as mineral filler.
Employed fiberglass surface treating agent is to adopt well-known vinyl three ('beta '-methoxy oxyethyl group) silane (A-172) surface treatment agent among the present invention.
The mineral filler that can also add among the present invention reduces the overlap (burr) of polyphenylene sulfide resin composite material model when injection forming, and these mineral fillers can be silicate, red stone, Nano titanium dioxide, zinc oxide, aluminum oxide, light calcium carbonate, nanometer grade calcium carbonate, magnesiumcarbonate, plaster stone, permanent white, silit, silicon nitride, SP 1 etc. such as carbon black, nanometer grade silica, nanometer order quartz sand, glass microballon, nanometer glass powder, Calucium Silicate powder, pure aluminium silicate, talcum, clay, mica, zeyssatite, wollastonite.
Claims (1)
1. the method for manufacture of a high ferro insulating material polyphenylene sulfide alloy; Weight percent in the polyphenylene sulfide alloy between PPS and spun glass and polyamide resin and the oxidation inhibitor is=45.8～49.2: 30～40: 24～10: 0.2～0.8; Said polyphenylene sulfide cladodification degree is 0.1%mol; Percent crystallinity is 70%, and melt flow rate is 600～800g/10min, adopts following process step:
1) it is even to add behind oxidation inhibitor, the polyamide resin weighting agent in impeller thorough mixing in the polyphenylene sulfide, obtains polyphenylene sulfide Preblend with this;
2) with 1) Preblend of gained polyphenylene sulfide again with handle the twin screw extruder of spun glass input later through 0.33%wt vinyl three ('beta '-methoxy oxyethyl group) silane surface treatment agent, form the finished product alloy through the mixing extrusion molding of twin screw extruder, cooling, pelletizing.
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| CN2012101204153A CN102675878A (en) | 2012-04-23 | 2012-04-23 | Manufacturing method for polyphenyl thioether alloy as insulating material of high-speed railway |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224706A (en) * | 2013-04-09 | 2013-07-31 | 浙江俊尔新材料股份有限公司 | Polyphenylene sulfide composite material, preparation method and molding method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253149A (en) * | 1998-10-29 | 2000-05-17 | 住友胶木株式会社 | Polyphenylene sulfoether resin compound material |
| CN101619168A (en) * | 2009-08-12 | 2010-01-06 | 深圳市华力兴工程塑料有限公司 | Modified polyphenylene sulfide resin and preparation method thereof |
-
2012
- 2012-04-23 CN CN2012101204153A patent/CN102675878A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253149A (en) * | 1998-10-29 | 2000-05-17 | 住友胶木株式会社 | Polyphenylene sulfoether resin compound material |
| CN101619168A (en) * | 2009-08-12 | 2010-01-06 | 深圳市华力兴工程塑料有限公司 | Modified polyphenylene sulfide resin and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224706A (en) * | 2013-04-09 | 2013-07-31 | 浙江俊尔新材料股份有限公司 | Polyphenylene sulfide composite material, preparation method and molding method thereof |
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Application publication date: 20120919 |