CN101397405A - Method for manufacturing high toughness polyphenyl thioether composite pellets - Google Patents
Method for manufacturing high toughness polyphenyl thioether composite pellets Download PDFInfo
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- CN101397405A CN101397405A CNA200710050119XA CN200710050119A CN101397405A CN 101397405 A CN101397405 A CN 101397405A CN A200710050119X A CNA200710050119X A CN A200710050119XA CN 200710050119 A CN200710050119 A CN 200710050119A CN 101397405 A CN101397405 A CN 101397405A
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- polyphenylene sulfide
- preblend
- polyphenyl thioether
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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Abstract
The invention discloses a manufacturing method of high-tenacity polyphenyl thioether composite granules. The polyphenyl thioether resin premix added with an addition agent is fully evenly mixed in a homo-mixer, and then the granule product is manufactured by subsequent extrusion and mixing processing. The granule comprises a proportion of polyphenyl thioether resin treated with oxidized thermal crosslinking, and is added with 5-35% of toughening modifier, 0.1-1 percent of anticorrosion inhibitor and 0.1-5 percent of thermal forming stabilizer fatty alcohol polyoxy styrene ether phosphoester amine salt; the premix obtained by fully evenly mixing all the materials in the homo-mixer and the fiber glass with the weight of 30-35 percent of that of the premix are mixed together and extruded for forming and chopping by an equidirectional double screw extruder. Finally, the high-tenacity polyphenyl thioether composite granules which have resistance to shock, stable thermotropy and excellent tensile strength are obtained.
Description
Affiliated technical field
The invention belongs to the macromolecular material Application Areas
Background technology
High-performance polyphenylene sulfide (PPS) has the excellent thermostability that gets under chemical proofing and the high temperature, and has high flame retardant, high electric insulation, radiation hardness and favorable mechanical performance.
Polyphenylene sulfide (PPS) chemical-resistant stability is good, and it has outstanding chemical stability extremely still keeping its original performance under the harsh conditions, is only second to tetrafluoroethylene.At high temperature, the component of polyphenylene sulfide manufacturing are placed in the different inorganic reagents and can keep original tensile strength after the week.It also has the performance of good organic solvent-resistant, except 93 ℃ toluene to its intensity slightly influential, in organic solvents such as tetracol phenixin, chloroform, even its intensity still can not change place a week under boiling point after, temperature is that 93 ℃ formic acid, acetic acid does not influence its intensity yet.Component by the polyphenylene sulfide manufacturing have good solidity to corrosion in 93 ℃ 50% sulfuric acid, strength retention does not make significant difference.Placed for two weeks in 93 ℃, 10% sodium hydroxide solution after, its intensity does not have obvious variation yet.
Polyphenylene sulfide (PPS) good heat stability, it has outstanding high thermal resistance, and fusing point reaches 285 ℃, is higher than other special engineering plastics of present suitability for industrialized production, so dimensional stabilizing.Its limiting oxygen index(LOI) can reach 35%-45%, can not burn under normal atmospheric condition.The polyphenylene sulfide thermotolerance also shows: it is about 40% when the resistance to impact shock conservation rate is 60%, 250 ℃ in the time of 200 ℃.Below 250 ℃ the time, its tensile strength remains unchanged substantially.If the component of polyphenylene sulfide (PPS) resin manufacture are placed 200 ℃ High Temperature Furnaces Heating Apparatus, resistance to impact shock remains unchanged substantially after 54 days.Tensile strength is reduced to 50% of initial tensile strength; Under 260 ℃ after 48 hours, still can remain on 60% of initial strength, tensile strength is to 50% of initial tensile strength.Go out outside this, polyphenylene sulfide (PPS) composite granule has good injection processing characteristics, can be processed into polyphenylene sulfide (PPS) composite product of all size, different shape.
In China Patent No. CN:1620480A, introduced under the situation that a kind of employing containing a certain amount of oligopolymer, the segmented copolymer that adds conjugated diolefine hydrocarbon compound and aromatic ethylene based compound, the moulded product of the polyphenylene sulfide that makes like this (PPS) resin composite materials has good toughness and heat seal strength, but the toughness of this kind polyphenylene sulfide (PPS) resin composite materials is good inadequately.
The objective of the invention is to study a kind of production technique that contains polyphenylene sulfide (PPS) composite granule of toughner, improve the molecular structure of resin by choose reasonable prescription and operational path, make the manufacturing in later stage obtain the PPS composite product that is made into all size, different shape of better properties index then.
Summary of the invention
The manufacture method of high toughness polyphenyl thioether composite pellets, the polyphenylene sulfide Preblend thorough mixing in homogenizer that adds behind the auxiliary agent is even, extrude the mixing product pellet that is processed into by follow-up again.Comprise in the described Preblend:, add: the plasticized modifier of 5-35%, the anticorrosive inhibitor of 0.1-1%, 0.1-5% thermoforming stablizer Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate amine salt through the polyphenylene sulfide portion of heat of oxidation crosslinking Treatment.Described polyphenylene sulfide is that weight-average molecular weight is the linear polymeric polyphenylene sulfide of 6-8 ten thousand, and resin is through heat of oxidation crosslinking Treatment, and treatment temp is 200-260 ℃, the crosslinked 2-8 of the heat of oxidation hour.One or more of the following material of described toughner: 3 penta different third glue, phenyl alkylsulf, polystyrene, clorafin thing.Preblend that obtains after above raw material thorough mixing in homogenizer is even and glass fibre are through the mixing extrusion molding pelletizing of parallel dual-screw extruding machine.The add-on of described glass fibre is the 30-35% of Preblend weight.
Among the present invention employed polyphenylene sulfide (PPS) be with-(Ar-S)-the linear high molecular weight PPS resin that forms for main repeat unit structure.Its molecular weight is 2-8 ten thousand, foreign matter contents such as metal ion that contains in the resin and organic solvent are below 100-900ppm, it is best being preferably in the following effect of 200ppm, with such polyphenylene sulfide (PPS) resin under the condition that oxygenant or oxygen are arranged, when temperature is 200-260C heat cross-linking 2-8 hour, weighting agent such as thermo-stabilizer, nanometer grade calcium carbonate mixes under the stirring of homogenizer, adds parallel dual-screw extruding machine again and glass fibre is mixing; In order to reduce overflowing of when forming process etchant gas, often in resin, add the chemical substance that can absorb etchant gas, these materials generally are zinc salt or zinc oxide, therefore, the anticorrosive inhibitor that the present invention added (objectionable impurities trapping agent) is inclined to one side zincate or zincate, and they are: zincic acid, zincic acid partially, inclined to one side zincic acid calcium, inclined to one side zincic acid magnesium, inclined to one side zincic acid barium, zincic acid calcium, zincic acid magnesium, zinciferous compounds such as zincic acid barium, with zincic acid, zincic acid is best partially, they not only can suppress the generation of corrosives and impurity, can also replenish among the pellet as mineral filler.
Must add toughner among the present invention, purpose is to improve polyphenylene sulfide resin composite material after injection molding, at a certain temperature, dimensional stabilizing when moulded product is subjected to impacting, employed for this reason toughner have 3 penta different third glue, acrylic copolymer, the own ester of phthalic acid two (2-ethyl), dibutyl phthalate, diisobutyl phthalate, dimixo-octyl phthalate, di-sec-octyl phthalate, triphenylphosphate, Tritolyl Phosphate, octyl epoxy stearate, butyl epoxy stearate, clorafin, phenyl alkylsulf, polycarbonate, polyvinyl alcohol and derivative thereof, derivatived cellulose, polymeric amide, polyester acrylic resin, polystyrene, fluoro-containing plastic; Serve as better wherein with 3 penta different third glue, clorafin, phenyl alkylsulf, polycarbonate, polyvinyl alcohol and derivative thereof, derivatived cellulose, polymeric amide, polyester acrylic resin, polystyrene, fluoro-containing plastic.
With 3 penta different third glue, clorafin, phenyl alkylsulf, polystyrene etc. is best, can select for use wherein one or more for used herein.
If its content of employed toughner was less than 5% o'clock among the present invention, can not obtain toughness reinforcing and shock proof modified effect, on the contrary, if the content of toughner greater than 35% o'clock, the thermostability of being not only polyphenylene sulfide reduces greatly, but also be that tensile strength reduces greatly, the extensibility phenomenal growth, simultaneously, when its melting mixing, viscosity increases greatly, produces mobile infringement.Therefore these two kinds of toughner content are not preferred objects.
Can also add mineral filler among the present invention, its objective is the overlap (burr) that can reduce 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 nano level carbonic acid magnesium, barium sulfate, carbon black, nanometer order quartz sand is best
The antioxidant purpose of Tian Jiaing is to reduce the oxygenolysis of polyphenylene sulfide (PPS) resin in polyphenylene sulfide (PPS) composite material manufacturing process in the present invention, the antioxidant that is added among the present invention can be GK-1010, GK-1098, GK-1024, GK-697, is best with GK-1098 especially.
The single fiber diameter of employed glass fibre is at 15um-25um in the present invention, purpose is to improve the thermotolerance of polyphenylene sulfide (PPS) matrix material, improve its shock proof ability simultaneously, in order to achieve the above object, and other physical propertys that improve polyphenylene sulfide (PPS) matrix material, can also add crystal nucleating agent therein, releasing agent, lubricant, ultraviolet protecting agent, staining agent, even add auxiliary agents such as fire retardant or plastics toughening agent.
Every index of product and employed detection method are among the present invention:
Every index among the present invention is all with reference to polyphenylene sulfide product performance index requirement in the world; Wherein 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.
Description of drawings
Fig. 1 is an embodiment of the invention experimental result repertory.
Fig. 2 is a process route chart of the present invention.
Embodiment
The present invention is with following technical process as shown in Figure 2, is divided into mainly that polyphenylene sulfide Preblend is produced and extrudes two key steps with glass fibre through parallel dual-screw extruding machine is mixing.
1, Preblend production
Preblend 1:: with molecular weight is that 20,000 polyphenylene sulfide 200kg adds in the heat cross-linking machine, temperature is controlled at 200 ℃, with the heat of oxidation crosslinked 8 hours, add the styryl triethoxyl silane of 0.2kg (0.1%) Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate amine salt (diethyl, three second) and 10kg (5%) the 3 penta different third glue 50kg (25%) and the inclined to one side zincic acid of 0.2kg (0.1%) again, and 20kg (10%) nano level carbonic acid magnesium, 1kg (0.5%) antioxidant GK-1098, it is stand-by to stir in homogenizer.
Preblend 2: with molecular weight is that 80,000 polyphenylene sulfide 200kg adds in the heat cross-linking machine, temperature is controlled at 260 ℃, with the heat of oxidation crosslinked 2 hours, add 10kg (5%) Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate amine salt (diethyl, three second) and 70kg (35%) 3 penta different third glue again, the inclined to one side zincic acid of the styryl triethoxyl silane of 2kg (1%) and 10kg (5%), and 60kg (30%) nano level carbonic acid magnesium, 5kg (2.5%) antioxidant GK-1098, it is stand-by to stir in homogenizer.
Preblend 3:: with molecular weight is that 20,000 polyphenylene sulfide 200kg adds in the heat cross-linking machine, temperature is controlled at 200 ℃, with the heat of oxidation crosslinked 8 hours, add 0.2kg (0.1%) glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt and 10kg (5%) phenyl alkylsulf again, the inclined to one side zincic acid of the styryl Trimethoxy silane of 50kg (25%) and 0.2kg (0.1%), and 20kg (10%) nanometer order quartz sand, 1kg (0.5%) antioxidant GK-1098, it is stand-by to stir in homogenizer.
Preblend 4: with molecular weight is that 20,000 polyphenylene sulfide 200kg adds in the heat cross-linking machine, temperature is controlled at 260 ℃, with the heat of oxidation crosslinked 2 hours, add 10kg (5%) glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt and 70kg (35%) phenyl alkylsulf again, the inclined to one side zincic acid of the styryl Trimethoxy silane of 2kg (1%) and 10kg (5%), and 60kg (30%) nanometer order quartz sand, 5kg (2.5%) antioxidant GK-1098, it is stand-by to stir in homogenizer.
Preblend 5:: with molecular weight is that 20,000 polyphenylene sulfide 200kg adds in the heat cross-linking machine, temperature is controlled at 200 ℃, with the heat of oxidation crosslinked 8 hours, add 0.2kg (0.1%) glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt and 10kg (5%) clorafin again, the inclined to one side zincic acid of the styryl Trimethoxy silane of 50kg (25%) and 0.2kg (0.1%), and 20kg (10%) nano level carbon black, 1kg (0.5%) antioxidant GK-1098, it is stand-by to stir in homogenizer.
Preblend 6: with molecular weight is that 20,000 polyphenylene sulfide 200kg adds in the heat cross-linking machine, temperature is controlled at 260 ℃, with the heat of oxidation crosslinked 2 hours, add 10kg (5%) glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt and 70kg (35%) clorafin again, the inclined to one side zincic acid of the styryl Trimethoxy silane of 2kg (1%) and 10kg (5%), and 60kg (30%) nano level carbon black, 5kg (2.5%) antioxidant GK-1098, it is stand-by to stir in homogenizer.
Preblend 7: with molecular weight is that 20,000 polyphenylene sulfide 200kg adds in the heat cross-linking machine, temperature is controlled at 200 ℃, with the heat of oxidation crosslinked 8 hours, add 0.2kg (0.1%) glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt and 10kg (5%) polystyrene again, the inclined to one side zincic acid of the styryl Trimethoxy silane of 50kg (25%) and 0.2kg (0.1%), and 20kg (10%) barium sulfate, 1kg (0.5%) antioxidant GK-1098, it is stand-by to stir in homogenizer.
Preblend 8: with molecular weight is that 20,000 polyphenylene sulfide 200kg adds in the heat cross-linking machine, temperature is controlled at 260 ℃, with the heat of oxidation crosslinked 2 hours, add 10kg (5%) glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt and 70kg (35%) polystyrene again, the inclined to one side zincic acid of the styryl Trimethoxy silane of 2kg (1%) and 10kg (5%), and 60kg (30%) barium sulfate, 5kg (2.5%) antioxidant GK-1098, it is stand-by to stir in homogenizer.
2, extrude through parallel dual-screw extruding machine is mixing with glass fibre
Embodiment 1:
Utilize 100% Preblend 1 add 30% through the KH550 surface treatment agent handle single fiber diameter later for the glass fibre of 15um and, extrude cooling, pelletizing, packing through parallel dual-screw extruding machine is mixing.
Embodiment 2:
Other adopts technical process, the processing condition of embodiment 1.Utilize 100% Preblend 1 to add 35% process KH550 surface treatment agent processing glass fibre later, the single fiber diameter of glass fibre is 25um.
Embodiment 3:
Other adopts technical process, the processing condition of embodiment 1.What utilize 100% Preblend, 2 interpolations 30% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 4:
Other adopts technical process, the processing condition of embodiment 1, and what utilize 100% Preblend, 2 interpolations 35% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 5:
Other adopts technical process, the processing condition of embodiment 1, and what utilize 100% Preblend, 3 interpolations 30% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 6:
Other adopts technical process, the processing condition of embodiment 1, and what utilize 100% Preblend, 3 interpolations 35% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 7:
Other adopts technical process, the processing condition of embodiment 1, and what utilize 100% Preblend, 4 interpolations 30% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 8:
Other adopts technical process, the processing condition of embodiment 1, and what utilize 100% Preblend, 4 interpolations 35% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 9:
Other adopts technical process, the processing condition of embodiment 1, and what utilize 100% Preblend, 5 interpolations 30% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 10:
Technical process, the processing condition of other employing embodiment 1 are removed the technical process, the processing condition that adopt example 1, and what utilize 100% Preblend, 5 interpolations 35% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 11:
Other adopts technical process, the processing condition of embodiment 1, and what utilize 100% Preblend, 6 interpolations 30% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 12:
Other adopts technical process, the processing condition of embodiment 1, and what utilize 100% Preblend, 6 interpolations 35% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 13:
Other adopts technical process, the processing condition of embodiment 1, and what utilize 100% Preblend, 7 interpolations 30% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 14:
Other adopts technical process, the processing condition of embodiment 1, and what utilize 100% Preblend, 7 interpolations 35% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 15:
Other adopts technical process, the processing condition of embodiment 1, and what utilize 100% Preblend, 8 interpolations 30% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
Embodiment 16:
Other adopts technical process, the processing condition of embodiment 1, and what utilize 100% Preblend, 8 interpolations 35% is the glass fibre of 15um through KH550 surface treatment agent processing single fiber diameter later.
The polyphenyl thioether composite material physicals that each embodiment obtains shows in Fig. 1.
Adopting molecular weight in the present invention respectively is that 80,000 polyphenylene sulfide, aliphatic alcohol polyoxyvinethene phosphate amine salt (diethyl, three second), glycerine polyoxy vinylbenzene ether phosphate triethanolamine salt are thermo-stabilizer and styryl Trimethoxy silane, and zincic acid, with nanometer grade calcium carbonate, silicon-dioxide, titanium dioxide be the composite granule that inorganic additives and glass fibre constitute, all can obtain similar result.
Claims (2)
1, the manufacture method of high toughness polyphenyl thioether composite pellets, polyphenylene sulfide Preblend thorough mixing in homogenizer behind the adding auxiliary agent is even, extrude the mixing product pellet that is processed into by follow-up again, comprise in the described Preblend: through the polyphenylene sulfide portion of heat of oxidation crosslinking Treatment, add: the plasticized modifier of 5-35%, the anticorrosive inhibitor of 0.1-1%, 0.1-5% thermoforming stablizer Fatty Alcohol(C12-C14 and C12-C18) polyoxy vinylbenzene ether phosphate amine salt; Described polyphenylene sulfide is that weight-average molecular weight is the linear polymeric polyphenylene sulfide of 2-8 ten thousand, and resin is through heat of oxidation crosslinking Treatment, and treatment temp is 200-260 ℃, the crosslinked 2-8 of the heat of oxidation hour; One or more of the following material of described toughner: 3 penta different third glue, phenyl alkylsulf, polystyrene, clorafin thing; Preblend that obtains after above raw material thorough mixing in homogenizer is even and glass fibre are through the mixing extrusion molding pelletizing of parallel dual-screw extruding machine; The add-on of described glass fibre is the 30-35% of Preblend weight.
According to the manufacture method of the described high toughness polyphenyl thioether composite pellets of claim 1, it is characterized in that 2, the anticorrosive inhibitor of adding is inclined to one side zincic acid or zincic acid.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634209A (en) * | 2012-04-20 | 2012-08-15 | 陈逊 | Preparation method of polyphenylene sulfide modified composite aggregate |
| CN102702747A (en) * | 2012-06-14 | 2012-10-03 | 南京同辉新型材料科技有限公司 | Insulating and heat-conducting high polymer and preparation method thereof |
| CN102888110A (en) * | 2011-07-18 | 2013-01-23 | 四川得阳特种新材料有限公司 | Manufacturing method of polyphenylene sulfide composite granulate containing toughening materials |
| CN104974525A (en) * | 2015-07-22 | 2015-10-14 | 广州高八二塑料有限公司 | Polyvinyl-alcohol-fiber-reinforced polyphenyl thioether composite material and preparation method thereof |
| CN105498363A (en) * | 2015-12-22 | 2016-04-20 | 苏州协泰科技有限公司 | Production technology for modified PPS fiber filtering material |
| CN105544183A (en) * | 2015-12-22 | 2016-05-04 | 苏州协泰科技有限公司 | A PPS fiber modification process |
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2007
- 2007-09-27 CN CNA200710050119XA patent/CN101397405A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888110A (en) * | 2011-07-18 | 2013-01-23 | 四川得阳特种新材料有限公司 | Manufacturing method of polyphenylene sulfide composite granulate containing toughening materials |
| CN102888110B (en) * | 2011-07-18 | 2024-03-22 | 四川得阳特种新材料有限公司 | Manufacturing method of polyphenylene sulfide composite granules containing toughening material |
| CN102634209A (en) * | 2012-04-20 | 2012-08-15 | 陈逊 | Preparation method of polyphenylene sulfide modified composite aggregate |
| CN102702747A (en) * | 2012-06-14 | 2012-10-03 | 南京同辉新型材料科技有限公司 | Insulating and heat-conducting high polymer and preparation method thereof |
| CN104974525A (en) * | 2015-07-22 | 2015-10-14 | 广州高八二塑料有限公司 | Polyvinyl-alcohol-fiber-reinforced polyphenyl thioether composite material and preparation method thereof |
| CN104974525B (en) * | 2015-07-22 | 2017-07-04 | 广州高八二塑料有限公司 | Vinal enhancing polyphenyl thioether composite material and preparation method thereof |
| CN105498363A (en) * | 2015-12-22 | 2016-04-20 | 苏州协泰科技有限公司 | Production technology for modified PPS fiber filtering material |
| CN105544183A (en) * | 2015-12-22 | 2016-05-04 | 苏州协泰科技有限公司 | A PPS fiber modification process |
| CN105498363B (en) * | 2015-12-22 | 2017-08-11 | 苏州协泰科技有限公司 | MODIFIED PP S fiber filter material production technologies |
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