CN102276983B - Method for manufacturing polyphenylene sulfide blow molding alloy - Google Patents
Method for manufacturing polyphenylene sulfide blow molding alloy Download PDFInfo
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- CN102276983B CN102276983B CN2011102271377A CN201110227137A CN102276983B CN 102276983 B CN102276983 B CN 102276983B CN 2011102271377 A CN2011102271377 A CN 2011102271377A CN 201110227137 A CN201110227137 A CN 201110227137A CN 102276983 B CN102276983 B CN 102276983B
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- polyphenylene sulfide
- blow molding
- elastomerics
- molding alloy
- vinylbenzene
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 113
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 113
- 238000000071 blow moulding Methods 0.000 title claims abstract description 46
- 239000000956 alloy Substances 0.000 title claims abstract description 44
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 13
- 239000012756 surface treatment agent Substances 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000005453 pelletization Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- -1 4-epoxycyclohexyl Chemical group 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000007493 shaping process Methods 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- QMBQNKZNTNORAY-UHFFFAOYSA-N ethyl(trimethoxy)silane;styrene Chemical compound C=CC1=CC=CC=C1.CC[Si](OC)(OC)OC QMBQNKZNTNORAY-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 abstract description 13
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 239000000806 elastomer Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000004925 denaturation Methods 0.000 abstract description 3
- 230000036425 denaturation Effects 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000000945 filler Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- 201000007651 Brooke-Spiegler syndrome Diseases 0.000 description 39
- 239000011159 matrix material Substances 0.000 description 13
- 239000008188 pellet Substances 0.000 description 9
- 238000007664 blowing Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920006389 polyphenyl polymer Polymers 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
-
- 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
- B29C48/92—Measuring, controlling or regulating
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for manufacturing polyphenylene sulfide blow molding alloy. The method comprises the following steps of: adding an antioxidant, a styrene alkoxy silane elastomer, a styrene-styrene-butadiene (SBS) elastomer processed by a beta-(3,4-epoxy cyclohexyl) ethyl trimethoxy silane (A-168) surface finishing agent and a filling agent, and mixing in a high-speed stirrer fully and uniformly to obtain a polyphenylene sulfide resin premix; and loading the polyphenylene sulfide resin premix into a double-screw extruder, mixing, extruding for forming, cooling, and granulating to form a finished product of the polyphenylene sulfide blow molding alloy. The polyphenylene sulfide blow molding alloy is stable in high thermal denaturation and high in tensile strength, tenacity and chemical corrosivity resistance, and can be widely applied in fields of machines, chemical industry, petroleum, war industry and space flight and aviation.
Description
Affiliated technical field
The invention belongs to the speciality polymer material and make the field
Background technology
Polyphenylene sulfide (PPS) good heat stability, has outstanding high thermal resistance, fusing point reaches 285 ℃, other special engineering plastics that are higher than present suitability for industrialized production, the PPS polyphenylene sulfide blow molding alloy has good injection processing characteristics, can be processed into the PPS composite product of all size, different shape.But in the more harsh field of some application conditions, explore and find that the more good PPS matrix material of performance is still the target that people pursue.
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 this matrix material at the overlap of blow molding.Thereby provide a kind of have good processing characteristics, the polyphenyl thioether composite material of physical strength, although the overlap behind the packing materials such as adding epoxy silane compounds when being injected into part reduces, and has but reduced 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, 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.
Introduced a kind of production method that adds the sulphur polyphenylene sulfide blow molding alloy of thermo-stabilizer and mineral filler in Chinese patent application number NO:2007100487510, this patent is to adopt very common method poly-p-phenylene sulfide ether resin to carry out modification to strengthen in fact.
Production has the elastomeric xtel series alloy of adding in U.S. snow furlong Philips company, is widely used in and makes blowing tubing and section bar.
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.
Summary of the invention:
A kind of manufacture method of polyphenylene sulfide blow molding alloy, with oxidation inhibitor, polyphenylene sulfide, polystyrene-type thermoplastic elastomers SBS, the mol ratio of its vinylbenzene and vinyl monomer is 6: 1, the mixed polyphenylene sulfide Preblend of vinylbenzene organoalkoxysilane elastomerics fully mixes in homogenizer, be shaped, form polyphenylene sulfide blow molding alloy through cooling, pelletizing by the parallel dual-screw extruding machine mixing extrusion again, it is characterized in that, adopt following processing step:
1) prescription of polyphenylene sulfide blow molding alloy is:
Extrusion grade polyphenylene sulfide 40-60%wt
Surface treated SBS 55-35%wt
Vinylbenzene organoalkoxysilane elastomerics 5%wt
2) 1) prescription add antioxidant 1,3,5-three-(3,5-, two-tetrabutyl-4-hydroxybenzene-propione hydroxyethyl) vulcabond in again; The weight ratio of antioxidant and polyphenylene sulfide is 1.5-2.0: 100; All materials fully mix in homogenizer, obtain polyphenylene sulfide Preblend;
3) with 2) gained polyphenylene sulfide Preblend input twin screw extruder, form the finished product polyphenylene sulfide blow molding alloy through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing.
The polyphenylene sulfide blow molding alloy that adopts as above method to make, it is high to have high stabile against thermal denaturation, tensile strength and high tenacity chemicals-resistant corrodibility.Can be widely used in electronic apparatus, machinery, chemical industry, oil, military project, field of aerospace.
Adding the elastomeric purpose of vinylbenzene organoalkoxysilane in the process of the present invention is the burr (overlap) that reduces on the one hand the blowing part, improve on the other hand the melt strength of matrix material in the blowing process, the 3rd, reduce the degree of crystallinity of matrix material and the crystallization velocity of raising matrix material, can reduce so the various losses of matrix material in the blowing process, improve the yield rate of blowing part.
Melt strength refers to that polymkeric substance supports the ability of sole mass under molten state. macromolecule melt intensity (Melt Strength), sometimes be also referred to as melt elasticity (Melt Elasticity), approximately measuring polymer melting elongational viscosity (Elongational Viscosity) on the engineering, itself and molecular weight of polymers (MW), molecular weight distribution (MWD), branch chain (Branching) what/length etc. is relevant.Be exactly the degree of entanglement (Degree of Polymer Chain Entanglement at MelT) that depends under the polymer molten state in fact in the final analysis, degree of entanglement is high, and melt strength is just high.So can improve macromolecule melt intensity by branch chain or crosslinked (Cross-linking).
In general, the product that melt strength is high relatively is fit to extrude, and the product that melt strength is low relatively is fit to blowing; It is rightabout that melt strength and molten finger numerically are into, that is to say that melt strength is higher, and molten finger is lower.But whether be fit to extrude or blowing less than obviously distinguishing, and relevant with processing condition.In addition, the melt strength of blowing is embodied under the high-shear, and melt strength is not only relevant with molecular weight, and is very large with quantity and the length relation of side chain in the molecule.
In the manufacture method of polyphenylene sulfide blow molding alloy of the present invention, the melt strength of matrix material is to measure under the condition that does not strengthen with fortifying fibre.
Technical process brief introduction of the present invention:
In homogenizer, the linear polyphenylene sulfide resin, oxidation inhibitor, the vinylbenzene organoalkoxysilane elastomerics and process β-(3 that add prescription per-cent, the 4-epoxycyclohexyl) ethyl trimethoxy silane (A-168) surface treatment agent is processed SBS elastomerics later, stir therein 2-3h, form polyphenylene sulfide blow molding alloy Preblend, it is inputted twin screw extruder, become the polyphenylene sulfide blow molding alloy pellet through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing, pack at last, put in storage, use.The polyphenylene sulfide blow molding alloy pellet is just obtaining required polyphenylene sulfide blow molding section bar through blow molding process.
Description of drawings:
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is the product performance table that embodiment of the invention experiment obtains.
Embodiment
Embodiment 1
The prescription of polyphenylene sulfide blow molding alloy:
Extrusion grade polyphenylene sulfide 40%wt
SBS 55％wt
Vinylbenzene organoalkoxysilane elastomerics 5%wt
The linear high molecular weight extrusion grade PPS resin of the weight-average molecular weight 50,000 of polyphenylene sulfide wherein, the molecular weight distribution coefficient is 1.71, melt flow rate is 30g/10min.
Antioxidant be 1,3,5-three-(3,5-, two-tetrabutyl-4-hydroxybenzene-propione hydroxyethyl) vulcabond (the domestic trade mark is: RC3125, the external trade mark is: Goodrite3125) weight ratio with polyphenylene sulfide is 1.5: 100;
The elastomeric synthesizing formula of SBS is vinylbenzene 6mol, 1, the 3-divinyl is the mol ratio of 1mol, adopt the polymerization of block polymerization technique to become the SBS elastomerics, then the β-(3 that incites somebody to action, the 4-epoxycyclohexyl) ethyl trimethoxy silane (A-168) surface treatment agent adds the spirituous solution that is mixed with 0.25%wt in the raw spirit, then is that the SBS powder of 0.15un soaks in the spirituous solution of A-168 with particle diameter.Soaking temperature is 10 ℃, and soak time is 45min, and the drying treatment temperature is 105 ℃, and be 3h time of drying, and air flow rate is 28m when dry
3/ min, it is stand-by to have obtained the SBS powder with regard to processing like this.
Vinylbenzene organoalkoxysilane elastomerics be with vinylbenzene ethyl trimethoxy silane monomer through polyreaction, aggregate into the polymerization degree and be 20 elastomerics.
The Heating temperature of twin screw extruder is 300 ℃, and rate of extrusion is 10kg/min.
In homogenizer, the linear polyphenylene sulfide resin, oxidation inhibitor, the vinylbenzene organoalkoxysilane elastomerics and process β-(3 that add prescription per-cent, the 4-epoxycyclohexyl) ethyl trimethoxy silane (A-168) surface treatment agent is processed SBS elastomerics later, stir therein 3h, form polyphenylene sulfide blow molding alloy Preblend, it is inputted twin screw extruder, become the polyphenylene sulfide blow molding alloy pellet through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing, pack at last, put in storage, use.
Embodiment 2
The prescription of polyphenylene sulfide blow molding alloy:
Extrusion grade polyphenylene sulfide 60%wt
SBS 35％wt
Vinylbenzene organoalkoxysilane elastomerics 5%wt
The linear high molecular weight extrusion grade PPS resin of the weight-average molecular weight 80,000 of polyphenylene sulfide wherein, the molecular weight distribution coefficient is 1.71, melt flow rate is 15g/10min.
Antioxidant be 1,3,5-three-(3,5-, two-tetrabutyl-4-hydroxybenzene-propione hydroxyethyl) vulcabond (the domestic trade mark is: RC3125, the external trade mark is: Goodrite3125) weight ratio with polyphenylene sulfide is 2.0: 100;
The elastomeric synthesizing formula of SBS is vinylbenzene 6mol, 1, the 3-divinyl is the mol ratio of 1mol, adopt the polymerization of block polymerization technique to become the SBS elastomerics, then the β-(3 that incites somebody to action, the 4-epoxycyclohexyl) ethyl trimethoxy silane (A-168) surface treatment agent adds the spirituous solution that is mixed with 0.3%wt in the raw spirit, then is that 0.25 SBS powder soaks in the spirituous solution of A-168 with particle diameter.Soaking temperature is 15 ℃, and soak time is 30min, and the drying treatment temperature is 120 ℃, and be 2h time of drying, and air flow rate is 30m when dry
3/ min, it is stand-by to have obtained the SBS powder with regard to processing like this.
Vinylbenzene organoalkoxysilane elastomerics be with vinylbenzene ethyl trimethoxy silane monomer through polyreaction, aggregate into the polymerization degree and be 30 elastomerics.
The Heating temperature of twin screw extruder is 320 ℃, and rate of extrusion is 10kg/min.
In homogenizer, the linear polyphenylene sulfide resin, oxidation inhibitor, the vinylbenzene organoalkoxysilane elastomerics and process β-(3 that add prescription per-cent, the 4-epoxycyclohexyl) ethyl trimethoxy silane (A-168) surface treatment agent is processed SBS elastomerics later, stir therein 2h, form polyphenylene sulfide blow molding alloy Preblend, it is inputted twin screw extruder, become the polyphenylene sulfide blow molding alloy pellet through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing, pack at last, put in storage, use.
The comparative example 1
The prescription of polyphenylene sulfide blow molding alloy:
Extrusion grade polyphenylene sulfide 40%wt
SBS 55％wt
Vinylbenzene organoalkoxysilane elastomerics 5%wt
The linear high molecular weight extrusion grade PPS resin of the weight-average molecular weight 50,000 of polyphenylene sulfide wherein, the molecular weight distribution coefficient is 1.73, melt flow rate is 30g/10min.
Antioxidant be 1,3,5-three-(3,5-, two-tetrabutyl-4-hydroxybenzene-propione hydroxyethyl) vulcabond (the domestic trade mark is: RC3125, the external trade mark is: Goodrite3125) weight ratio with polyphenylene sulfide is 1.5: 100;
The SBS elastomerics does not carry out surface treatment.
Vinylbenzene organoalkoxysilane elastomerics be with vinylbenzene ethyl trimethoxy silane monomer through polyreaction, aggregate into the polymerization degree and be 20 elastomerics.
The Heating temperature of twin screw extruder is 300 ℃, and rate of extrusion is 10kg/min.
In homogenizer, the linear polyphenylene sulfide resin, oxidation inhibitor, the SBS elastomerics that add prescription per-cent, stir therein 3h, form polyphenylene sulfide blow molding alloy Preblend, it is inputted twin screw extruder, become the polyphenylene sulfide blow molding alloy pellet through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing, pack at last, put in storage, use.
Embodiment 3
The prescription of polyphenylene sulfide blow molding alloy:
Extrusion grade polyphenylene sulfide 50%wt
SBS 45％wt
Vinylbenzene organoalkoxysilane elastomerics 5%wt
The linear high molecular weight extrusion grade PPS resin of the weight-average molecular weight 60,000 of polyphenylene sulfide wherein, the molecular weight distribution coefficient is 1.72, melt flow rate is 18g/10min.
Antioxidant be 1,3,5-three-(3,5-, two-tetrabutyl-4-hydroxybenzene-propione hydroxyethyl) vulcabond (the domestic trade mark is: RC3125, the external trade mark is: Goodrite3125) weight ratio with polyphenylene sulfide is 1.8: 100;
The elastomeric synthesizing formula of SBS is vinylbenzene 6mol, 1, the 3-divinyl is the mol ratio of 1mol, adopt the polymerization of block polymerization technique to become the SBS elastomerics, then the β-(3 that incites somebody to action, the 4-epoxycyclohexyl) ethyl trimethoxy silane (A-168) surface treatment agent adds the spirituous solution that is mixed with 0.25-0.3%wt in the raw spirit, then is that 0.2 SBS powder soaks in the spirituous solution of A-168 with particle diameter.Soaking temperature is 13 ℃, and soak time is 40min, and the drying treatment temperature is 110 ℃, and be 2.5h time of drying, and air flow rate is 29m when dry
3/ min, it is stand-by to have obtained the SBS powder with regard to processing like this.
Vinylbenzene organoalkoxysilane elastomerics be with vinylbenzene ethyl trimethoxy silane monomer through polyreaction, aggregate into the polymerization degree and be 25 elastomerics.
The Heating temperature of twin screw extruder is 310 ℃, and rate of extrusion is 10kg/min.
In homogenizer, the linear polyphenylene sulfide resin, oxidation inhibitor, the vinylbenzene organoalkoxysilane elastomerics and process β-(3 that add prescription per-cent, the 4-epoxycyclohexyl) ethyl trimethoxy silane (A-168) surface treatment agent is processed SBS elastomerics later, stir therein 2.5h, form polyphenylene sulfide blow molding alloy Preblend, it is inputted twin screw extruder, become the polyphenylene sulfide blow molding alloy pellet through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing, pack at last, put in storage, use.
Embodiment 4
The prescription of polyphenylene sulfide blow molding alloy:
Extrusion grade polyphenylene sulfide 55%wt
SBS 40％wt
Vinylbenzene organoalkoxysilane elastomerics 5%wt
The linear high molecular weight extrusion grade PPS resin of the weight-average molecular weight 70,000 of polyphenylene sulfide wherein, the molecular weight distribution coefficient is 1.71, melt flow rate is 17g/10min.
Antioxidant be 1,3,5-three-(3,5-, two-tetrabutyl-4-hydroxybenzene-propione hydroxyethyl) vulcabond (the domestic trade mark is: RC3125, the external trade mark is: Goodrite3125) weight ratio with polyphenylene sulfide is 1.7: 100;
The elastomeric synthesizing formula of SBS is vinylbenzene 6mol, 1, the 3-divinyl is the mol ratio of 1mol, adopt the polymerization of block polymerization technique to become the SBS elastomerics, then the β-(3 that incites somebody to action, the 4-epoxycyclohexyl) ethyl trimethoxy silane (A-168) surface treatment agent adds the spirituous solution that is mixed with 0.28%wt in the raw spirit, then is that 0.18 SBS powder soaks in the spirituous solution of A-168 with particle diameter.Soaking temperature is 12 ℃, and soak time is 40min, and the drying treatment temperature is 115 ℃, and be 2.8h time of drying, and air flow rate is 30m when dry
3/ min, it is stand-by to have obtained the SBS powder with regard to processing like this.
Vinylbenzene organoalkoxysilane elastomerics be with vinylbenzene ethyl trimethoxy silane monomer through polyreaction, aggregate into the polymerization degree and be 28 elastomerics.
The Heating temperature of twin screw extruder is 315 ℃, and rate of extrusion is 10kg/min.
In homogenizer, the linear polyphenylene sulfide resin, oxidation inhibitor, the vinylbenzene organoalkoxysilane elastomerics and process β-(3 that add prescription per-cent, the 4-epoxycyclohexyl) ethyl trimethoxy silane (A-168) surface treatment agent is processed SBS elastomerics later, stir therein 2.3h, form polyphenylene sulfide blow molding alloy Preblend, it is inputted twin screw extruder, become the polyphenylene sulfide blow molding alloy pellet through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing, pack at last, put in storage, use.
The comparative example 2
The prescription of polyphenylene sulfide blow molding alloy:
Extrusion grade polyphenylene sulfide 60%wt
Vinylbenzene organoalkoxysilane elastomerics 5%wt
The linear high molecular weight extrusion grade PPS resin of the weight-average molecular weight 80,000 of polyphenylene sulfide wherein, the molecular weight distribution coefficient is 1.71, melt flow rate is 15g/10min.
Antioxidant be 1,3,5-three-(3,5-, two-tetrabutyl-4-hydroxybenzene-propione hydroxyethyl) vulcabond (the domestic trade mark is: RC3125, the external trade mark is: Goodrite3125) weight ratio with polyphenylene sulfide is 2.0: 100;
The SBS elastomerics does not carry out surface treatment.
Vinylbenzene organoalkoxysilane elastomerics be with vinylbenzene ethyl trimethoxy silane monomer through polyreaction, aggregate into the polymerization degree and be 30 elastomerics.
The Heating temperature of twin screw extruder is 320 ℃, and rate of extrusion is 10kg/min.
In homogenizer, the linear polyphenylene sulfide resin, oxidation inhibitor, the SBS elastomerics that add prescription per-cent, stir therein 2h, form polyphenylene sulfide blow molding alloy Preblend, it is inputted twin screw extruder, become the polyphenylene sulfide blow molding alloy pellet through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing, pack at last, put in storage, use.
Can see by tabulation among Fig. 2: by adding vinylbenzene organoalkoxysilane elastomer compounds and SBS elastomerics after treatment the melt strength of polyphenylene sulfide (PPS) matrix material has obviously been improved, overlap length obviously reduces, impact resistance, anti-bent pleat intensity, tensile strength obviously strengthens, elongation at break also increases significantly with same type of material, if but not only certain surface treatment of SBS elastomerics, the consistency that will find SBS elastomerics and polyphenylene sulfide reduces, thereby has influence on each performance index of polyphenylene sulfide blow molding alloy.
Owing to add vinylbenzene organoalkoxysilane elastomer compounds and fine through SBS elastomerics and polyphenylene sulfide consistency after the surface treatment, can not produce parcel phenomenon or particle shape, improved the processing performance of material, so just the balanced technique intensity index that has improved polyphenylene sulfide.
Product indices 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 281Mpa, 3.7%, 315Mpa and 18.4j/m
2
After also finding in the experiment to add thicker glass fibre, for example single fiber diameter 35um parallel laboratory test, its resistance to impact shock has obvious enhancing.The elastomeric adding of vinylbenzene organoalkoxysilane also significantly improves the help that forward is provided to tensile strength and the elongation at break of product of the present invention.
After adding vinylbenzene organoalkoxysilane elastomer compounds and oxidation inhibitor RC3125 compound, polyphenylene sulfide (PPS) matrix material is when thermostability obviously improves, and product overlap length is reduction trend.Owing to add vinylbenzene organoalkoxysilane elastomer compounds and oxidation inhibitor RC3125 and molten mixed very even through the SBS elastomerics after the surface treatment and polyphenylene sulfide, also can not produce parcel phenomenon or particle shape.The improvement of all these processing condition makes some physical propertiess of product and processing performance obtain comprehensive improvement.
Employed SBS surface treatment agent is to adopt well-known β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (A-168) surface treatment agent among the present invention.
Claims (5)
1. the manufacture method of a polyphenylene sulfide blow molding alloy, oxidation inhibitor, polyphenylene sulfide, polystyrene-type thermoplastic elastomers SBS, the mixed polyphenylene sulfide Preblend of vinylbenzene organoalkoxysilane elastomerics are fully mixed in homogenizer, be shaped, form polyphenylene sulfide blow molding alloy through cooling, pelletizing by the parallel dual-screw extruding machine mixing extrusion again, it is characterized in that, adopt following processing step:
1) prescription of polyphenylene sulfide blow molding alloy is:
Extrusion grade polyphenylene sulfide 40-60%wt
SBS 55-35%wt through surface treatment agent A-168 processing
Vinylbenzene organoalkoxysilane elastomerics 5%wt
2) 1) prescription add antioxidant 1,3,5-three-(3,5-, two-tertiary butyl-4-hydroxy benzene-propione hydroxyethyl) vulcabond in again; The weight ratio of antioxidant and polyphenylene sulfide is 1.5-2.0:100; All materials fully mix in homogenizer, obtain polyphenylene sulfide Preblend;
3) with 2) gained polyphenylene sulfide Preblend input twin screw extruder, form the finished product polyphenylene sulfide blow molding alloy through the shaping of twin screw extruder mixing extrusion, cooling, pelletizing.
2. the manufacture method of described a kind of polyphenylene sulfide blow molding alloy according to claim 1, it is characterized in that, the attach most importance to linear high molecular weight extrusion grade PPS resin of average molecular weight 5-8 ten thousand of described polyphenylene sulfide resin fat raw material, the molecular weight distribution coefficient is 1.71-1.73, and melt flow rate is 15-30g/10min.
3. the manufacture method of described a kind of polyphenylene sulfide blow molding alloy according to claim 1, it is characterized in that, described vinylbenzene organoalkoxysilane elastomerics is with vinylbenzene ethyl trimethoxy silane monomer process polyreaction, aggregates into the elastomerics that the polymerization degree is 20-30.
4. the manufacture method of described a kind of polyphenylene sulfide blow molding alloy according to claim 1, it is characterized in that, the mol ratio of vinylbenzene and divinylic monomer is 6:1 in the described SBS elastomerics, its powder diameter is 0.15-0.25 μ m, adopt following surface treatment: at the β-(3 of 0.25-0.3%wt, the 4-epoxycyclohexyl) soak in the raw spirit solution of ethyl trimethoxy silane A-168 surface treatment agent: the immersion treatment temperature is 10-15 ℃, soak time is 30-45min, then temperature is 105-120 ℃ of drying treatment, be 2-3h time of drying, and air flow rate is 28-30m when dry
3/ min.
5. the manufacture method of described a kind of polyphenylene sulfide blow molding alloy according to claim 1 is characterized in that the Heating temperature of described twin screw extruder is 300-320 ℃, and rate of extrusion is 10kg/min.
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| CN1718635A (en) * | 2005-07-27 | 2006-01-11 | 广州金发科技股份有限公司 | High toughness packing reinforced polyphenyl thioether composite material and its preparation method |
| CN101275015A (en) * | 2007-03-28 | 2008-10-01 | 四川得阳化学有限公司 | Preparation for fiberglass-containing polyphenyl thioether composite granulates |
| 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 |
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| CN1718635A (en) * | 2005-07-27 | 2006-01-11 | 广州金发科技股份有限公司 | High toughness packing reinforced polyphenyl thioether composite material and its preparation method |
| CN101275015A (en) * | 2007-03-28 | 2008-10-01 | 四川得阳化学有限公司 | Preparation for fiberglass-containing polyphenyl thioether composite granulates |
| 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 |
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