CN101275015A - Preparation for fiberglass-containing polyphenyl thioether composite granulates - Google Patents
Preparation for fiberglass-containing polyphenyl thioether composite granulates Download PDFInfo
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- CN101275015A CN101275015A CNA2007100487510A CN200710048751A CN101275015A CN 101275015 A CN101275015 A CN 101275015A CN A2007100487510 A CNA2007100487510 A CN A2007100487510A CN 200710048751 A CN200710048751 A CN 200710048751A CN 101275015 A CN101275015 A CN 101275015A
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- polyphenylene sulfide
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Abstract
The invention discloses a preparation method of polyphenylene sulfide (PPS) composite granules containing fiber glass. The preparation method comprises the following steps: (1) PPS resin material is oxidized and thermo-crosslinked; (2) the PPS resin prepared from step (1) is added with a heat stabilizer, a corrosion resistant inhibitor and such filling agents as a nanoscale inorganic stuffing, and well mixed in a high speed mixer; the weight ratio between cyclohexane-methanol polyoxystyreneether phosphate and PPS resin in the heat stabilizer is 1 to 5: 100, and the prepared product is a premix material of PPS resin, which is mixed with fiber glass processed with KH550 surface treating agent, blended, extruded and molded in a double screw extruder, and cooled and pelletized, finally formed into the finished composite granules. The composite granules of the invention have the advantages of high thermal denaturation stability and tensile strength, and low metal corrosion rate, and can be widely applied to such fields as electronic and electric products, machinery, chemical engineering, petroleum, war industry, and aeronautics and astronautics.
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 composite granule 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 manufacture method 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, easily forms the parcel phenomenon when producing under the general technology level, thereby directly have influence on high-temperature mechanical property in pellet.
Introduced among the Chinese patent CN:1253149A and a kind ofly added epoxy silane compounds and high component is inorganic, the manufacture method 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 provide a kind of polyphenyl thioether composite material with good processing properties, physical strength, 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 manufacture method that employing zinc oxide palpus crystalline substance and glass fibre or carbon fiber 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, 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 making (PPS) matrix material injection forming decrease, and its resistance to impact shock also decreases.
Summary of the invention:
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 glass fibre low to metallic corrosion, good processability.Its main technique comprises:
Polyphenylene sulfide Preblend thorough mixing in homogenizer behind glass fibre and the adding auxiliary agent is even, pass through the mixing extrusion molding of parallel dual-screw extruding machine again, form composite granule through cooling, pelletizing, adopt following processing step: (1) sulfide resin raw material is made heat of oxidation crosslinking Treatment, and treatment temp is 200-260 ℃; The crosslinked 2-8 of the heat of oxidation hour; (2) it is even to add behind the weighting agents such as thermo-stabilizer, anticorrosive inhibitor and nano grade inorganic filler in homogenizer thorough mixing with (1) gained polyphenylene sulfide, and the weight ratio of used thermo-stabilizer Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate salt and polyphenylene sulfide is 1-5: 100; The weight ratio of anticorrosive inhibitor and polyphenylene sulfide is 1-5: 100, and adopt anticorrosive inhibitor by one of following material or all constitute: zincic acid, zincic acid partially; Obtain polyphenylene sulfide Preblend with this; Handle glass fibre uniform mixing later with the Preblend of (2) gained polyphenylene sulfide and through the KH550 surface treatment agent, form the finished product composite granule through the mixing extrusion molding of twin screw extruder, cooling, pelletizing.
The composite granule that adopts as above method to make has high stabile against thermal denaturation and tensile strength, and is low to the metallic corrosion rate.Can be widely used in electronic apparatus, machinery, chemical industry, oil, military project, field of aerospace.
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
Embodiment 1
: with molecular weight is in the polyphenylene sulfide 200kg adding heat cross-linking machine of 2-8 ten thousand, temperature is controlled at 200 ℃, with the heat of oxidation crosslinked 8 hours, add 0.2kg (0.1%) hexamethylene six alkane methyl alcohol polyoxy vinylbenzene ether phosphate amine salt (diethyl, three second) and the styryl triethoxyl silane of 50kg (25%) and the inclined to one side zincic acid of 0.2kg (0.1%) again, and 30kg (15%) nanometer grade calcium carbonate, 1kg (0.5%) antioxidant GK-1098, stirring in homogenizer obtains polyphenylene sulfide Preblend.
Utilize 100% Preblend 1 to add 20,30,40,50,60,70% process KH550 surface treatment agent processing glass fibre mixing later respectively, extrude cooling, pelletizing, packing through parallel dual-screw extruding machine is mixing.
The various physicalies of the polyphenyl thioether composite material that obtains with aforesaid method will show in Table 1, and it is 15um that single fiber diameter is adopted in experiment respectively.
Embodiment 2
Crosslinking temperature is controlled at 260 ℃, crosslinked 2 hours of the heat of oxidation, and other working condition is with embodiment 1.
After the polyphenylene sulfide crosslinking Treatment, add 0.2kg (0.1%) glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt and the styryl Trimethoxy silane of 50kg (25%) and the inclined to one side zincic acid of 0.2kg (0.1%), and 30kg (15%) nanometer grade silica, 1kg (0.5%) antioxidant GK-1098, stirring in homogenizer obtains polyphenylene sulfide Preblend.Other working condition is with embodiment 1.
Crosslinking temperature is controlled at 260 ℃, crosslinked 2 hours of the heat of oxidation, and other working condition is with embodiment 3.
After the polyphenylene sulfide crosslinking Treatment, add 0.2kg (0.1%) glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt and the styryl Trimethoxy silane of 50kg (25%) and the inclined to one side zincic acid of 0.2kg (0.1%), and 30kg (15%) Nano titanium dioxide, 1kg (0.5%) antioxidant GK-1098, stirring in homogenizer obtains polyphenylene sulfide Preblend.Other working condition is with embodiment 1.
Crosslinking temperature is controlled at 260 ℃, crosslinked 2 hours of the heat of oxidation.After the polyphenylene sulfide crosslinking Treatment, add 10kg (5%) glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt and the styryl Trimethoxy silane of 2kg (1%) and the inclined to one side zincic acid of 10kg (5%), and 30kg (15%) Nano titanium dioxide, 5kg (2.5%) antioxidant GK-1098, stirring in homogenizer obtains polyphenylene sulfide Preblend.Other working condition is with embodiment 5.
Can see by tabulation one among Fig. 2: after adding polyoxy vinylbenzene ether phosphate salt compound and polyoxy vinylbenzene alkoxy silane compound, the thermostability of polyphenylene sulfide (PPS) matrix material has obviously improved, overlap length obviously reduces, impact resistance, 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 Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate compounds and polyoxy vinylbenzene alkoxy silane compound, can not produce parcel phenomenon or particle shape, improved the processing performance of material, the so just balanced technology intensity index that has improved polyphenylene sulfide.
Every index of product and employed detection method in the table:
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 glass fibre 40% like product parallel laboratory test, and its tensile strength, elongation, the bent pleat intensity of glass, resistance to impact shock are respectively 181Mpa, 3.7%, 215Mpa and 13.4j/m
2
After also finding in the experiment to add thicker glass fibre, for example single fiber diameter 25um parallel laboratory test, its resistance to impact shock has tangible enhancing.The adding of nano level weighting agent, also tensile strength and the elongation at break to product of the present invention significantly improves the help that forward is provided.
After adding Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate compounds and polyoxy vinylbenzene alkoxy silane compound, polyphenylene sulfide (PPS) matrix material is when thermostability obviously improves, and product overlap length is reduction trend.Since after adding Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate compounds and polyoxy vinylbenzene alkoxy silane 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 processing performance obtain comprehensive improvement.
Though embodiments of the invention are with hexamethylene six alkane methyl alcohol polyoxy vinylbenzene ether phosphate amine salt (diethyls, three second), glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt is what provide, also can consider wider Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate compounds in the actual production, for example: the aliphatic alcohol polyoxyvinethene phosphate sodium salt, hexamethylene six alkane methyl alcohol polyoxy vinylbenzene ether phosphate amine salt (diethyls, three second), fatty alcohol-ether (7) phosphoric acid ester triethanolamine salt, fatty alcohol-ether (9) phosphoric acid ester triethanolamine salt, octanol phosphoric acid ester MCPH, octanol polyoxyethylene phosphate OPEK, nonyl phenol phosphate sylvite, nonyl phenol ether phosphoric acid monoesters ethanolamine salt, Nonyl pheno (7) ether phosphoric acid, single, dibasic acid esters Nonyl pheno (4-10) ether phosphoric acid, single, dibasic acid esters, the glycerin polyoxyethylene ether phosphoric acid ester, glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt, PAPE, higher alcohols phosphoric acid ester sodium and phosphorylation Viscotrol C sodium salt, Stearinsaeure, the sulfuric ester of glycerol sodium salt, one or more compounds of phosphate ester salts such as Viscotrol C phosphate ester salt.
The ethene organoalkoxysilane resin compound of Jia Ruing in the present invention, can reduce the overlap (burr) that polyphenyl thioether composite granulates 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 vinyltrimethoxy silanes, vinyltriethoxysilane, the styryl triethoxyl silane, the 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, in the organoalkoxysilanes such as 3-propenyloxy group propyl trimethoxy silicane one or more, especially with vinyltrimethoxy silane, vinyltriethoxysilane, the styryl triethoxyl silane, the styryl Trimethoxy silane is better, with the styryl triethoxyl silane, the styryl Trimethoxy silane is best.
The objectionable impurities trapping agent that the present invention added is inclined to one side zincic acid/zincic acid or its esters compound, and they are: zincic acid, zincic acid partially, inclined to one side zincic acid calcium, zincic acid magnesium, zincic acid barium partially partially, 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 KH540, KH550, KH560 type surface treatment agent among the present invention.
The mineral filler of adding among the present invention also can reduce the overlap (burr) of polyphenylene sulfide resin composite material model when injection forming, these mineral fillers can be carbon blacks, nanometer grade silica, nanometer order quartz sand, glass microballon, the nanometer glass powder, Calucium Silicate powder, pure aluminium silicate, talcum, clay, mica, diatomite, silicate such as wollastonite, ferric oxide, Nano titanium dioxide, zinc oxide, aluminum oxide, light calcium carbonate, nanometer grade calcium carbonate, magnesiumcarbonate, plaster stone, barium sulfate, silicon carbide, silicon nitride, boron nitride etc. are especially with nanometer grade calcium carbonate, nanometer grade silica, Nano titanium dioxide is best.
Claims (6)
1. the manufacture method that contains the polyphenyl thioether composite granulates of glass fibre, polyphenylene sulfide Preblend thorough mixing in homogenizer behind glass fibre and the adding auxiliary agent is even, pass through the mixing extrusion molding of parallel dual-screw extruding machine again, form composite granule through cooling, pelletizing, it is characterized in that, adopt following processing step:
(1) the polyphenylene sulfide resin fat raw material is made heat of oxidation crosslinking Treatment, and treatment temp is 200-260 ℃; The crosslinked 2-8 of the heat of oxidation hour;
(2) it is even to add behind the weighting agents such as thermo-stabilizer, anticorrosive inhibitor and nano grade inorganic filler in homogenizer thorough mixing with (1) gained polyphenylene sulfide, and the weight ratio of used thermo-stabilizer Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate salt and polyphenylene sulfide is 1-5: 100; The weight ratio of anticorrosive inhibitor and polyphenylene sulfide is 1-5: 100, and adopt anticorrosive inhibitor by one of following material or all constitute: zincic acid, zincic acid partially; Obtain polyphenylene sulfide Preblend with this;
(3) handle glass fibre uniform mixing later with the Preblend of (2) gained polyphenylene sulfide and through the KH550 surface treatment agent, form the finished product composite granule through the mixing extrusion molding of twin screw extruder, cooling, pelletizing.
2. according to the manufacture method of the described polyphenyl thioether composite granulates that contains glass fibre of claim 1, it is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate salt is a kind of in the following material: hexamethylene six alkane methyl alcohol polyoxy vinylbenzene ether phosphate amine salt, glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt.
3. according to the manufacture method of the described polyphenyl thioether composite granulates that contains glass fibre of claim 2, it is characterized in that, in polyphenylene sulfide Preblend manufacturing processed, need to add vinylbenzene organoalkoxysilane resinoid, to reduce finning.
4. according to the manufacture method of the described polyphenyl thioether composite granulates that contains glass fibre of claim 2, it is characterized in that described nano grade inorganic filler is one of lime carbonate, silicon-dioxide, titanium dioxide.
5. according to the manufacture method of the described polyphenyl thioether composite granulates that contains glass fibre of claim 1, it is characterized in that the attach most importance to linear high molecular weight PPS resin of average molecular weight 2-8 ten thousand of described polyphenylene sulfide resin fat raw material.
6. according to the manufacture method of the described polyphenyl thioether composite granulates that contains glass fibre of claim 1, it is characterized in that the glass fibre single fiber diameter is 15-25um.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100487510A CN101275015A (en) | 2007-03-28 | 2007-03-28 | Preparation for fiberglass-containing polyphenyl thioether composite granulates |
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| CNA2007100487510A CN101275015A (en) | 2007-03-28 | 2007-03-28 | Preparation for fiberglass-containing polyphenyl thioether composite granulates |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276983A (en) * | 2011-08-09 | 2011-12-14 | 德阳科吉高新材料有限责任公司 | Method for manufacturing polyphenylene sulfide blow molding alloy |
| CN102719098A (en) * | 2011-06-03 | 2012-10-10 | 湖北孚龙管业科技有限公司 | Composite modified polyphenylene sulfide material for water supply pipe insert and preparation method thereof |
| CN103436015A (en) * | 2013-08-30 | 2013-12-11 | 四平市德嘉电子仪表有限公司 | Material for manufacturing wheel speed sensor and manufacturing method of wheel speed sensor |
| CN105802224A (en) * | 2016-05-16 | 2016-07-27 | 苏州新区华士达工程塑胶有限公司 | Modified polyphenylene sulfide plastic |
| CN114350149A (en) * | 2021-12-01 | 2022-04-15 | 金发科技股份有限公司 | Polyphenylene sulfide resin composition and preparation method and application thereof |
-
2007
- 2007-03-28 CN CNA2007100487510A patent/CN101275015A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719098A (en) * | 2011-06-03 | 2012-10-10 | 湖北孚龙管业科技有限公司 | Composite modified polyphenylene sulfide material for water supply pipe insert and preparation method thereof |
| CN102719098B (en) * | 2011-06-03 | 2014-02-19 | 湖北孚龙管业科技有限公司 | Composite modified polyphenylene sulfide material for water supply pipe insert and preparation method thereof |
| CN102276983A (en) * | 2011-08-09 | 2011-12-14 | 德阳科吉高新材料有限责任公司 | Method for manufacturing polyphenylene sulfide blow molding alloy |
| CN102276983B (en) * | 2011-08-09 | 2013-03-13 | 德阳科吉高新材料有限责任公司 | Method for manufacturing polyphenylene sulfide blow molding alloy |
| CN103436015A (en) * | 2013-08-30 | 2013-12-11 | 四平市德嘉电子仪表有限公司 | Material for manufacturing wheel speed sensor and manufacturing method of wheel speed sensor |
| CN105802224A (en) * | 2016-05-16 | 2016-07-27 | 苏州新区华士达工程塑胶有限公司 | Modified polyphenylene sulfide plastic |
| CN114350149A (en) * | 2021-12-01 | 2022-04-15 | 金发科技股份有限公司 | Polyphenylene sulfide resin composition and preparation method and application thereof |
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Open date: 20081001 |