CN114262519B - Polyphenylene sulfide fiber reinforced polyphenylene sulfide composite material and preparation method thereof - Google Patents
Polyphenylene sulfide fiber reinforced polyphenylene sulfide composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114262519B CN114262519B CN202111680680.2A CN202111680680A CN114262519B CN 114262519 B CN114262519 B CN 114262519B CN 202111680680 A CN202111680680 A CN 202111680680A CN 114262519 B CN114262519 B CN 114262519B
- Authority
- CN
- China
- Prior art keywords
- phenylene sulfide
- composite material
- heat
- poly
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 239000000835 fiber Substances 0.000 title claims abstract description 55
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000004734 Polyphenylene sulfide Substances 0.000 title abstract description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 54
- 238000002844 melting Methods 0.000 claims abstract description 47
- 230000008018 melting Effects 0.000 claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000010439 graphite Substances 0.000 claims abstract description 45
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 45
- 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 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 239000000155 melt Substances 0.000 claims description 29
- 238000001125 extrusion Methods 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 12
- SOHCOYTZIXDCCO-UHFFFAOYSA-N 6-thiabicyclo[3.1.1]hepta-1(7),2,4-triene Chemical compound C=1C2=CC=CC=1S2 SOHCOYTZIXDCCO-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- GVZXUFKETYNKBJ-UHFFFAOYSA-N 6-thiabicyclo[3.1.1]hepta-1(7),2,4-triene;7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1.C=1C2=CC=CC=1S2 GVZXUFKETYNKBJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Landscapes
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of heat conduction polyphenylene sulfide, in particular to a polyphenylene sulfide fiber reinforced polyphenylene sulfide composite material and a preparation method thereof. The heat-conducting composite material comprises 30-85 parts of m-phenylene sulfide-p-phenylene sulfide copolymer, 5-30 parts of poly-p-phenylene sulfide fiber and 10-60 parts of acidified graphite. The preparation method comprises the steps of firstly mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite to obtain a premix, then adding the poly-p-phenylene sulfide fiber into the premix, and carrying out blending, melting and granulating to obtain a granulated product, namely the heat-conducting composite material. And (3) melting and extruding the heat-conducting composite material, and cooling and forming to obtain the heat-conducting composite material pipe. The invention utilizes the good interface compatibility of the poly-p-phenylene sulfide fiber, the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite to obtain the heat conduction composite material pipe with good mechanical property, few defects and good air tightness.
Description
Technical Field
The invention relates to the technical field of heat conduction polyphenylene sulfide, in particular to a polyphenylene sulfide fiber reinforced polyphenylene sulfide composite material and a preparation method thereof.
Background
At present, industrial fuel used in chemical production can generate corrosive acid gas in the combustion process, condensate formed after the industrial fuel is mixed with water vapor and condensed can corrode metal pipe fittings of a metal heat exchanger, so that the traditional metal heat exchanger is difficult to meet the requirements of certain chemical fields, and although a few alloy metal or special metal heat exchangers capable of resisting chemical corrosion exist, the use of the metal heat exchanger is severely restricted due to high price. The high-molecular heat-conducting composite material has the advantages of chemical corrosion resistance, excellent mechanical property, good processing property, light weight, low cost and the like, and is gradually applied to the heat exchange industry.
Polyphenylene Sulfide (PPS) is a thermoplastic resin having a phenylthio group in a molecular main chain, is one of resins having the highest stability among thermoplastic polymer materials, has chemical resistance considered to be inferior to polytetrafluoroethylene, has excellent heat resistance, chemical resistance, flame retardancy, physical mechanical properties, and the like, can be used for preparing a heat conductive material, and is widely used in fields of electronics, chemical engineering, automobile transportation, and the like.
The current heat conduction composite material system is mainly prepared by adding other reinforcements into a polyphenylene sulfide resin matrix.
The Chinese patent application CN108727819A discloses a preparation method of a carbon fiber reinforced polyphenylene sulfide nanocomposite, wherein the formula comprises 35-45wt% of polyphenylene sulfide, 5-15wt% of carbon fiber, 25-40wt% of conductive graphite and 5-35wt% of other additives. When the formula is used in heat exchange tube extrusion, partial auxiliary agent is decomposed to generate gas because the melt lasts for a long time above 280 ℃, and the interface binding force between the carbon fiber and the polyphenylene sulfide is poor, so that the prepared heat exchange tube has poor air tightness and is easy to generate pinholes. The Chinese patent application CN109206908A discloses a preparation method of a high-heat-conductivity graphite/plastic composite material, wherein the formula comprises 5-50% of expandable acidified graphite and 50-95% of polyphenylene sulfide, and the heat conduction pipe prepared by using the formula has obviously improved heat conduction performance, but the mechanical performance and pressure resistance of the prepared heat conduction pipe are poor because no reinforcing body is added.
Chinese patent application CN111349340a discloses a polyphenylene sulfide resin composition and a molded article thereof, comprising 100 parts by mass of a poly (p-phenylene sulfide) -m-phenylene sulfide random copolymer, and 5 to 150 parts by mass of an inorganic filler. The invention mainly aims to improve the wet heat resistance and simultaneously maintain high mechanical strength. The formula adds silane compound for improving the interfacial binding force between the inorganic filler and the resin matrix, but if the formula is used for extruding the pipe, the added silane compound is easy to decompose to generate gas in the processing process, thereby affecting the air tightness of the product.
Although the mechanical properties of the reinforced body can be improved by adding glass fiber or carbon fiber and other reinforcing bodies into the polyphenylene sulfide resin matrix, the interface binding force between the reinforced body and the polyphenylene sulfide resin matrix is weak, sliding friction can occur, interface stress is caused, cracks are generated, and the air tightness of the pipe product is poor. In order to avoid the generation of cracks, auxiliaries such as a coupling agent and the like are generally added to improve the compatibility of the reinforcing body and the polyphenylene sulfide matrix, but the auxiliaries such as the coupling agent and the like are easy to decompose to generate gas in the processing process, so that the quality of a product is influenced. There is still a need to develop a high thermal conductivity polyphenylene sulfide composite material to meet the excellent mechanical properties and excellent air tightness of the heat transfer tube.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the heat conduction composite material pipe, which utilizes good interface compatibility of poly-p-phenylene sulfide fiber, m-phenylene sulfide-p-phenylene sulfide copolymer and acidified graphite to obtain the heat conduction composite material pipe with good mechanical property, few defects and good air tightness.
The technical scheme of the invention is realized by the following technical scheme:
the heat conducting composite material consists of m-phenyl sulfide-p-phenyl sulfide copolymer 30-85 weight portions, p-phenyl sulfide fiber 5-30 weight portions and acidified graphite 10-60 weight portions.
Preferably, the intermediate benzene structure mass content of the m-phenylene sulfide-p-phenylene sulfide copolymer is in the range of 10-30%. The intermediate benzene content of the m-phenyl sulfide-p-phenyl sulfide copolymer is too low, and the processing interval is too narrow due to the higher melting point; too high an m-benzene content and a low melting point result in difficult processing. Further preferably, the intermediate benzene structure mass content of the m-phenylene sulfide-p-phenylene sulfide copolymer is in the range of 10-20%.
Preferably, the m-phenylene sulfide-p-phenylene sulfide copolymer has a melt flow rate of 500 to 2500g/10min, and more preferably, 800 to 1200g/10min.
Preferably, the poly (p-phenylene sulfide) fibers are uncrimped staple fibers of 0.8-3.0D and have a length of 2-10cm. The poly-p-phenylene sulfide fiber has poor mechanical properties when the length is too short; if the length is too long, the dispersibility is poor and the heat conduction property is poor. Further preferably, the poly (p-phenylene sulfide) fibers are uncrimped staple fibers of 1.4 to 2.0D and have a length of 3 to 5cm.
Preferably, the mesh number of the acidified graphite is in the range of 100 to 1500 mesh. The smaller the mesh number of the acidified graphite is, the larger the particle size is, and the poorer the mechanical property of the composite material is; the larger the mesh number of the acidified graphite, the smaller the particle size, and the poorer the heat conducting property of the composite material. Further preferably, the mesh number of the acidified graphite is 500-1000 mesh.
The invention also provides a preparation method of the heat-conducting composite material, which comprises the following steps:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite to obtain a premix;
(2) Adding poly-p-phenylene sulfide fibers into the premix, and carrying out blending, melting and granulating to obtain a granulated product;
preferably, the mixing in step (1) takes from 10 to 180 minutes.
Preferably, the blending and melting in the step (2) is double-screw melting blending, the poly-p-phenylene sulfide fibers are added into the premix by side feeding of a double-screw extruder, and each section of the double-screw extruder from a hopper to a die head is between the melting point of the m-phenylene sulfide-p-phenylene sulfide copolymer and the melting point of the poly-p-phenylene sulfide fibers.
Preferably, the temperature of the double-screw extruder from the hopper to the die head is seven intervals, wherein the temperature of one interval is 0-30 ℃ higher than the melting point of the m-phenylene sulfide-p-phenylene sulfide copolymer, the temperature of two intervals is 10-30 ℃ higher than the melting point of the m-phenylene sulfide-p-phenylene sulfide copolymer, the temperature of three intervals is 10-40 ℃ higher than the melting point of the m-phenylene sulfide-p-phenylene sulfide copolymer, the temperature of four intervals is 10-40 ℃ higher than the melting point of the m-phenylene sulfide-p-phenylene sulfide copolymer, the temperature of five intervals is 5-30 ℃ higher than the melting point of the m-phenylene sulfide-p-phenylene sulfide copolymer, the temperature of six intervals is 5-30 ℃ higher than the melting point of the m-phenylene sulfide-p-phenylene sulfide copolymer.
Preferably, the temperature of the twin screw extruder from the hopper to the die head is divided into seven stages, and the seven stages are 205-260 ℃, 215-265 ℃, 220-270 ℃, 210-260 ℃ and 210-260 ℃ in sequence.
Preferably, the screw speed of the twin-screw extruder in step (2) is 345-355rpm and the side feed speed is 245-255rpm.
The heat-conducting composite material can be used for preparing a heat-conducting pipe, the granulating product is melted and extruded, and cooling and forming are carried out to obtain the heat-conducting composite material pipe, wherein a single screw extruder is adopted for extrusion, and the melt temperature during extrusion is 10-40 ℃ higher than the melting point of m-phenylene sulfide-p-phenylene sulfide copolymer but not higher than the melting point of poly-p-phenylene sulfide fiber; the die temperature is lower than the melting point of the m-phenylene sulfide-p-phenylene sulfide copolymer by 40-80 ℃.
Preferably, a single screw extruder is adopted for extrusion, the melt temperature during extrusion is 220-270 ℃, and the die temperature is 150-200 ℃.
The polyphenylene sulfide composite material pipe prepared by the invention has excellent mechanical properties and air tightness, and can be used in the fields of chemical industry, petroleum, water supply and drainage engineering and the like with higher requirements on the air tightness of the heat-conducting pipe.
The invention has the beneficial effects that:
(1) The invention adopts the m-phenylene sulfide-p-phenylene sulfide copolymer resin as a matrix material, ensures the fluidity of the composite material, and adopts the acidified graphite as a main heat conducting filler and the poly-p-phenylene sulfide fiber as a main supporting material for enhancing the mechanical property.
(2) The surface of the poly-p-phenylene sulfide fiber and the interface of the m-phenylene sulfide-p-phenylene sulfide copolymer resin matrix have good compatibility, the interface combination is firm, the surface of the acidified graphite contains hydroxyl, carbonyl, carboxyl and other functional groups, the surface activity is improved, and the bonding force with the resin matrix is good, so that the product prepared by the composite material has good air tightness due to good interface compatibility among the components. And the melting temperature of the m-phenylene sulfide-p-phenylene sulfide copolymer is lower than that of the poly-p-phenylene sulfide, the melting point of the m-phenylene sulfide-p-phenylene sulfide copolymer (the m-phenylene content is 10%) is 245-258 ℃, the melting point of the poly-p-phenylene sulfide fiber is 282-285 ℃ along with the increase of the m-phenylene structure, and the sufficient melting point difference exists between the m-phenylene sulfide and the poly-p-phenylene sulfide, so that the retention length of the fiber can be ensured, and the mechanical property and the pressure resistance of a processed product are ensured.
Detailed Description
The invention is described below in connection with specific embodiments.
The preparation method of the intermediate phenyl sulfide-p-phenyl sulfide copolymer comprises the following specific embodiments: dichlorobenzene (DCB, including p-dichlorobenzene and m-dichlorobenzene, wherein the m-dichlorobenzene content is 10% -40% depending on the content of intermediate phenylene sulfide of the m-phenylene sulfide-p-phenylene sulfide copolymer to be prepared in the embodiment) and anhydrous sodium sulfide (Na 2 S) as a reactive monomer, anhydrous trisodium phosphate (Na 3 PO 4 ) As an auxiliary agent, the polycondensation reaction is carried out in an organic solvent hexamethylphosphoric triamide. Wherein DCB: na (Na) 2 S：Na 3 PO 4 =1.00: 1.02:1.20, the reaction temperature is 230-240 ℃, the reaction time is 6 hours, and the catalyst is obtained after precipitation, filtration, washing and drying.
Acidifying graphite: mixing graphite with strong oxidizing acid, stirring, washing, and drying to obtain the final product or commercially available product.
The polyphenylene sulfide uncrimped staple fiber: melting poly (p-phenylene sulfide) powder (melt flow rate 100-300g/10 min) below 350deg.C, spinning to obtain undrawn yarn via spinneret, hot-stretching the undrawn yarn by 3-4 times, heat-setting at 180deg.C, and cutting into specified length.
Example 1
A heat-conducting composite material pipe is prepared from 35 parts of m-phenylene sulfide-p-phenylene sulfide copolymer (the m-phenylene sulfide structure content is 10%, the melting point is 250 ℃, the melt flow rate is 1000g/10 min), 45 parts of acidified graphite (800 meshes) and 20 parts of poly-p-phenylene sulfide fibers (2.0D, 5 cm).
The preparation method comprises the following steps:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite for 120min by a three-dimensional stirrer to obtain a premix;
(2) Putting the premix obtained in the step (1) into a main feeding hopper of a double-screw extruder, adding the poly-p-phenylene sulfide fibers into a side feeding hopper, and dividing the temperature of the double-screw extruder from the hopper to a die head into seven sections, wherein the seven sections of temperatures are as follows: the materials are blended, melted, extruded and pelletized at the temperature of 250 ℃, 260 ℃, 265 ℃, 255 ℃ and the screw speed of a main machine of 350rpm and the side feeding speed of 250 rpm;
(3) And (3) introducing the pelleting product obtained in the step (2) into a single screw extruder, extruding by a tubular die of a head of the extruder, and cooling and forming to obtain the heat-conducting composite pipe with the outer diameter of 19mm and the wall thickness of 2 mm. The rotation speed and the temperature of a single screw extruder are controlled when the pipe is extruded, the temperature of a melt is controlled to be 265 ℃, and the temperature of a die is controlled to be 200 ℃.
Example 2
A heat-conducting composite material pipe is prepared from (by weight parts) m-phenylene sulfide-p-phenylene sulfide copolymer (m-phenylene sulfide structural content 10%, melting point 258 ℃, melt flow rate 500g/10 min) 85 parts, acidified graphite (100 meshes) 10 parts, and poly-p-phenylene sulfide fiber (3.0D, 10 cm) 5 parts.
The preparation method comprises the following steps:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite for 120min by a three-dimensional stirrer to obtain a premix;
(2) Putting the premix obtained in the step (1) into a main feeding hopper of a double-screw extruder, adding the poly-p-phenylene sulfide fibers into a side feeding hopper, and dividing the temperature of the double-screw extruder from the hopper to a die head into seven sections, wherein the seven sections of temperatures are as follows: 260 ℃, 265 ℃, 260 ℃ and the screw speed of the main machine is 350rpm, the side feeding speed is 250rpm, and the materials are blended, melted, extruded and pelletized;
(3) And (3) introducing the pelleting product obtained in the step (2) into a single screw extruder, extruding by a tubular die of a head of the extruder, and cooling and forming to obtain the heat-conducting composite pipe with the outer diameter of 19mm and the wall thickness of 2 mm. The rotation speed and the temperature of a single screw extruder are controlled when the pipe is extruded, the temperature of a melt is controlled to be 265 ℃, and the temperature of a die is controlled to be 200 ℃.
Example 3
A heat-conducting composite material pipe is prepared from 30 parts of m-phenylene sulfide-p-phenylene sulfide copolymer (the m-phenylene sulfide structure content is 10%, the melting point is 245 ℃, the melt flow rate is 2500g/10 min), 40 parts of acidified graphite (800 meshes) and 30 parts of poly-p-phenylene sulfide fiber (2.0D, 5 cm).
The preparation method comprises the following steps:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite for 120min by a three-dimensional stirrer to obtain a premix;
(2) Putting the premix obtained in the step (1) into a main feeding hopper of a double-screw extruder, adding the poly-p-phenylene sulfide fibers into a side feeding hopper, and dividing the temperature of the double-screw extruder from the hopper to a die head into seven sections, wherein the seven sections of temperatures are as follows: 245 ℃, 250 ℃, 260 ℃, 250 ℃ and the screw speed of a main machine is 350rpm, the side feeding speed is 250rpm, and the materials are blended, melted, extruded and pelletized;
(3) And (3) introducing the pelleting product obtained in the step (2) into a single screw extruder, extruding by a tubular die of a head of the extruder, and cooling and forming to obtain the heat-conducting composite pipe with the outer diameter of 19mm and the wall thickness of 2 mm. The rotation speed and the temperature of a single screw extruder are controlled when the pipe is extruded, the temperature of a melt is controlled to be 260 ℃, and the temperature of a die is controlled to be 195 ℃.
Example 4
A heat-conducting composite material pipe is prepared from 30 parts of m-phenylene sulfide-p-phenylene sulfide copolymer (with the m-phenylene sulfide structure content of 30%, the melting point of 205 ℃ and the melt flow rate of 1000g/10 min), 60 parts of acidified graphite (1500 meshes) and 10 parts of polyphenylene sulfide fibers (0.8D, 2 cm).
The preparation method comprises the following steps:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite for 120min by a three-dimensional stirrer to obtain a premix;
(2) Putting the premix obtained in the step (1) into a main feeding hopper of a double-screw extruder, adding the poly-p-phenylene sulfide fibers into a side feeding hopper, and dividing the temperature of the double-screw extruder from the hopper to a die head into seven sections, wherein the seven sections of temperatures are as follows: 205 ℃, 215 ℃, 220 ℃, 210 ℃, the screw speed of the main machine is 350rpm, the side feeding speed is 250rpm, and the materials are blended, melted, extruded and pelletized;
(3) And (3) introducing the pelleting product obtained in the step (2) into a single screw extruder, extruding by a tubular die of a head of the extruder, and cooling and forming to obtain the heat-conducting composite pipe with the outer diameter of 19mm and the wall thickness of 2 mm. The rotation speed and the temperature of a single screw extruder are controlled when the pipe is extruded, the temperature of a melt is controlled to be 220 ℃, and the temperature of a die is controlled to be 150 ℃.
Example 5
A heat-conducting composite material pipe is prepared from 35 parts of m-phenylene sulfide-p-phenylene sulfide copolymer (the m-phenylene sulfide structure content is 10%, the melting point is 248 ℃, the melt flow rate is 1200g/10 min), 45 parts of acidified graphite (1000 meshes) and 20 parts of poly-p-phenylene sulfide fibers (2.0D, 3 cm).
The preparation method comprises the following steps:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite for 120min by a three-dimensional stirrer to obtain a premix;
(2) Putting the premix obtained in the step (1) into a main feeding hopper of a double-screw extruder, adding the poly-p-phenylene sulfide fibers into a side feeding hopper, and dividing the temperature of the double-screw extruder from the hopper to a die head into seven sections, wherein the seven sections of temperatures are as follows: the materials are blended, melted, extruded and pelletized at the temperature of 250 ℃, 260 ℃, 265 ℃, 255 ℃ and the screw speed of a main machine of 350rpm and the side feeding speed of 250 rpm;
(3) And (3) introducing the pelleting product obtained in the step (2) into a single screw extruder, extruding by a tubular die of a head of the extruder, and cooling and forming to obtain the heat-conducting composite pipe with the outer diameter of 19mm and the wall thickness of 2 mm. The rotation speed and the temperature of a single screw extruder are controlled when the pipe is extruded, the temperature of a melt is controlled to be 265 ℃, and the temperature of a die is controlled to be 200 ℃.
Example 6
A heat-conducting composite material pipe is prepared from 35 parts of m-phenylene sulfide-p-phenylene sulfide copolymer (the m-phenylene sulfide structure content is 20%, the melting point is 230 ℃, the melt flow rate is 800g/10 min), 45 parts of acidified graphite (500 meshes) and 20 parts of poly-p-phenylene sulfide fiber (1.4D, 3 cm).
The preparation method comprises the following steps:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite for 120min by a three-dimensional stirrer to obtain a premix;
(2) Putting the premix obtained in the step (1) into a main feeding hopper of a double-screw extruder, adding the poly-p-phenylene sulfide fibers into a side feeding hopper, and dividing the temperature of the double-screw extruder from the hopper to a die head into seven sections, wherein the seven sections of temperatures are as follows: mixing, melting, extruding and granulating the materials at 230 ℃, 240 ℃, 245 ℃, 235 ℃ and 355rpm of screw speed of a main machine and 255rpm of side feeding speed;
(3) And (3) introducing the pelleting product obtained in the step (2) into a single screw extruder, extruding by a tubular die of a head of the extruder, and cooling and forming to obtain the heat-conducting composite pipe with the outer diameter of 19mm and the wall thickness of 2 mm. The rotation speed and the temperature of a single screw extruder are controlled when the pipe is extruded, the temperature of a melt is controlled to 245 ℃, and the temperature of a die is controlled to 180 ℃.
Example 7
A heat-conducting composite material pipe is prepared from 30 parts of m-phenylene sulfide-p-phenylene sulfide copolymer (with the m-phenylene sulfide structure content of 10%, the melting point of 250 ℃ and the melt flow rate of 1000g/10 min), 40 parts of acidified graphite (800 meshes) and 30 parts of poly-p-phenylene sulfide fibers (2.0D, 5 cm).
The preparation method comprises the following steps:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite for 120min by a three-dimensional stirrer to obtain a premix;
(2) Putting the premix obtained in the step (1) into a main feeding hopper of a double-screw extruder, adding the poly-p-phenylene sulfide fibers into a side feeding hopper, and dividing the temperature of the double-screw extruder from the hopper to a die head into seven sections, wherein the seven sections of temperatures are as follows: the materials are blended, melted, extruded and pelletized at the temperature of 250 ℃, 260 ℃, 265 ℃, 255 ℃ and the screw speed of a host machine of 345rpm and the side feeding speed of 245 rpm;
(3) And (3) introducing the pelleting product obtained in the step (2) into a single screw extruder, extruding by a tubular die of a head of the extruder, and cooling and forming to obtain the heat-conducting composite pipe with the outer diameter of 19mm and the wall thickness of 2 mm. The rotation speed and the temperature of a single screw extruder are controlled when the pipe is extruded, the temperature of a melt is controlled to be 265 ℃, and the temperature of a die is controlled to be 200 ℃.
Comparative example 1
The difference from example 1 is that glass fibers are used instead of polyphenylene sulfide fibers, and the concrete steps are as follows:
a heat-conducting composite material pipe is prepared from (by weight parts) 35 of m-phenylene sulfide-p-phenylene sulfide copolymer (with m-phenylene sulfide structure content of 10%, melting point of 250 ℃, melt flow rate of 1000g/10 min), 45 parts of acidified graphite (800 meshes), and 20 parts of glass fiber (13 μm,5 cm).
The preparation method is the same as in example 1.
Comparative example 2
The difference from example 1 is that the polyphenylene sulfide resin is substituted for the m-phenylene sulfide-p-phenylene sulfide copolymer.
A heat-conducting composite material pipe is prepared from 35 parts of poly (p-phenylene sulfide) resin (melting point 280 ℃, melt flow rate 1000g/10 min), 45 parts of acidified graphite (800 meshes) and 20 parts of poly (p-phenylene sulfide) fiber (2.0D, 5 cm).
Preparation method step (1) was the same as in example 1.
Since the melting point of the poly (p-phenylene sulfide) resin is 280 ℃, the steps 2 and 3 are as follows:
(2) Putting the premix obtained in the step (1) into a main feeding hopper of a double-screw extruder, adding the poly-p-phenylene sulfide fibers into a side feeding hopper, and dividing the temperature of the double-screw extruder from the hopper to a die head into seven sections, wherein the seven sections of temperatures are as follows: 280 ℃, 290 ℃, 295 ℃, 285 ℃ and the screw speed of a main machine is 350rpm and the side feeding speed is 250rpm, and the materials are blended, melted, extruded and pelletized;
(3) And (3) introducing the pelleting product obtained in the step (2) into a single screw extruder, extruding by a tubular die of a head of the extruder, and cooling and forming to obtain the heat-conducting composite pipe with the outer diameter of 19mm and the wall thickness of 2 mm. The rotation speed and the temperature of a single screw extruder are controlled when the pipe is extruded, the temperature of a melt is controlled to 295 ℃, and the temperature of a die is controlled to 200 ℃.
Comparative example 3
The difference from example 1 is that graphite replaces the acidified graphite.
A heat-conducting composite material pipe is prepared from 35 parts of m-phenylene sulfide-p-phenylene sulfide copolymer (the m-phenylene sulfide structure content is 10%, the melting point is 250 ℃, the melt flow rate is 1000g/10 min), 45 parts of graphite (800 meshes) and 20 parts of poly-p-phenylene sulfide fiber (2.0D, 5 cm).
The preparation method is the same as in example 1.
Comparative example 4
The difference from example 1 is the temperature settings of the sections of the twin-screw extruder from the hopper to the die in step (2) of the preparation process. The specific preparation process is as follows:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite for 120min by a three-dimensional stirrer to obtain a premix;
(2) Putting the premix obtained in the step (1) into a main feeding hopper of a double-screw extruder, adding the poly-p-phenylene sulfide fibers into a side feeding hopper, and dividing the temperature of the double-screw extruder from the hopper to a die head into seven sections, wherein the seven sections of temperatures are as follows: 280 ℃, 290 ℃, 295 ℃, 285 ℃ and the screw speed of a main machine is 350rpm and the side feeding speed is 250rpm, and the materials are blended, melted, extruded and pelletized;
(3) And (3) introducing the pelleting product obtained in the step (2) into a single screw extruder, extruding by a tubular die of a head of the extruder, and cooling and forming to obtain the heat-conducting composite pipe with the outer diameter of 19mm and the wall thickness of 2 mm. The rotation speed and the temperature of a single screw extruder are controlled when the pipe is extruded, the temperature of a melt is controlled to be 265 ℃, and the temperature of a die is controlled to be 180 ℃.
Comparative example 5
The difference from example 1 is the melt temperature in the single screw extrusion process of step (3) of the preparation method. The specific preparation process is as follows:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite for 120min by a three-dimensional stirrer to obtain a premix;
(2) Putting the premix obtained in the step (1) into a main feeding hopper of a double-screw extruder, adding the poly-p-phenylene sulfide fibers into a side feeding hopper, and dividing the temperature of the double-screw extruder from the hopper to a die head into seven sections, wherein the seven sections of temperatures are as follows: the materials are blended, melted, extruded and pelletized at the temperature of 250 ℃, 260 ℃, 265 ℃, 255 ℃ and the screw speed of a main machine of 350rpm and the side feeding speed of 250 rpm;
(3) And (3) introducing the pelleting product obtained in the step (2) into a single screw extruder, extruding by a tubular die of a head of the extruder, and cooling and forming to obtain the heat-conducting composite pipe with the outer diameter of 19mm and the wall thickness of 2 mm. The rotation speed and the temperature of a single screw extruder are controlled when the pipe is extruded, the temperature of a melt is controlled to 295 ℃, and the temperature of a die is controlled to 180 ℃.
Comparative example 6
The difference from example 1 is that the intermediate benzene structure content of the m-phenylene sulfide-p-phenylene sulfide copolymer is 40%, the melt flow rate is 1000g/10min, the melting point is 90 ℃, the pipe can be formed by reducing the processing temperature, but the melting point of the pipe is too low, and the use condition is harsh.
Comparative example 7
A heat-conducting composite material pipe is prepared from 25 parts of m-phenylene sulfide-p-phenylene sulfide copolymer (the m-phenylene sulfide structure content is 10%, the melting point is 245 ℃, the melt flow rate is 2500g/10 min), 40 parts of acidified graphite (800 meshes) and 35 parts of poly-p-phenylene sulfide fiber (2.0D, 5 cm).
The preparation method comprises the following steps:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite for 120min by a three-dimensional stirrer to obtain a premix;
(2) Putting the premix obtained in the step (1) into a main feeding hopper of a double-screw extruder, adding the poly-p-phenylene sulfide fibers into a side feeding hopper, and dividing the temperature of the double-screw extruder from the hopper to a die head into seven sections, wherein the seven sections of temperatures are as follows: 245 ℃, 250 ℃, 260 ℃, 250 ℃, and 250 ℃, wherein the screw speed of a main machine is 350rpm, the side feeding speed is 250rpm, and the materials are blended, melted, extruded and pelletized;
(3) And (3) introducing the pelleting product obtained in the step (2) into a single screw extruder, extruding by a tubular die of a head of the extruder, and cooling and forming to obtain the heat-conducting composite pipe with the outer diameter of 19mm and the wall thickness of 2 mm. The rotation speed and the temperature of a single screw extruder are controlled when the pipe is extruded, the temperature of a melt is controlled to be 260 ℃, and the temperature of a die is controlled to be 195 ℃.
Effect example Performance test results
The test method of the heat conductive composite pipes of examples 1 to 7 and comparative examples 1 to 7 according to the present invention is as follows:
flexural strength: pellets were prepared according to step (1) and step (2) of examples and comparative examples, injection molded and extruded into standard bending test specimens using an injection molding machine, and tested according to ISO-178-2010.
Blasting pressure: a1 m pipe was prepared according to the conditions of examples and comparative examples, and burst pressure test was performed according to GB/T6111-2003.
Air tightness qualification rate: 10 pipes of 3m were prepared under the conditions of examples and comparative examples, and air tightness was examined according to GB/T20801.5-2006.
The test results are shown in Table 1 below.
TABLE 1 Performance test results
The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.
Claims (12)
1. The heat-conducting composite material is characterized by comprising, by weight, 30-85 parts of m-phenylene sulfide-p-phenylene sulfide copolymer, 5-30 parts of poly-p-phenylene sulfide fibers and 10-60 parts of acidified graphite; the mass content range of the intermediate benzene structure of the m-phenyl sulfide-p-phenyl sulfide copolymer is 10-30%;
the preparation method of the heat-conducting composite material comprises the following steps:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite to obtain a premix;
(2) Adding poly-p-phenylene sulfide fibers into the premix, and carrying out blending, melting and granulating to obtain a granulated product, namely the heat-conducting composite material;
the blending and melting in the step (2) are double-screw melting and blending, the poly-p-phenylene sulfide fibers are added into the premix by side feeding of a double-screw extruder, the temperature from a hopper to a die head of the double-screw extruder is divided into seven sections, and the seven sections are 205-260 ℃, 215-265 ℃, 220-270 ℃, 210-260 ℃ and 210-260 ℃ in sequence.
2. The thermally conductive composite of claim 1, wherein the m-phenylene sulfide-p-phenylene sulfide copolymer intermediate benzene structure mass content is in the range of 10-20%.
3. The thermally conductive composite of claim 1, wherein the m-phenylene sulfide-p-phenylene sulfide copolymer has a melt flow rate of 500-2500g/10min.
4. The thermally conductive composite of claim 1, wherein the m-phenylene sulfide-p-phenylene sulfide copolymer has a melt flow rate of 800-1200g/10min.
5. The thermally conductive composite of claim 1, wherein the poly (p-phenylene sulfide) fibers are uncrimped staple fibers of 0.8-3.0D and have a length of 2-10cm.
6. The thermally conductive composite of claim 1, wherein the poly (p-phenylene sulfide) fibers are 1.4-2.0D uncrimped staple fibers having a length of 3-5cm.
7. The thermally conductive composite of claim 1, wherein the acidified graphite has a mesh size of from 100 to 1500 mesh.
8. The thermally conductive composite of claim 1, wherein the acidified graphite has a mesh size of 500 to 1000 mesh.
9. A method of preparing a thermally conductive composite material as claimed in any one of claims 1 to 8, comprising the steps of:
(1) Mixing the m-phenylene sulfide-p-phenylene sulfide copolymer and the acidified graphite to obtain a premix;
(2) Adding poly-p-phenylene sulfide fibers into the premix, and carrying out blending, melting and granulating to obtain a granulated product, namely the heat-conducting composite material;
the blending and melting in the step (2) are double-screw melting and blending, the poly-p-phenylene sulfide fibers are added into the premix by side feeding of a double-screw extruder, the temperature from a hopper to a die head of the double-screw extruder is divided into seven sections, and the seven sections are 205-260 ℃, 215-265 ℃, 220-270 ℃, 210-260 ℃ and 210-260 ℃ in sequence.
10. The method according to claim 9, wherein the twin-screw extruder in step (2) has a screw speed of 345-355rpm and a side feed speed of 245-255rpm.
11. Use of a thermally conductive composite material as claimed in any one of claims 1 to 8 for the manufacture of a heat pipe; the preparation of the heat-conducting pipe comprises the steps of carrying out melt extrusion on a pelleting product, and cooling and forming to obtain a heat-conducting composite material pipe, wherein a single screw extruder is adopted for extrusion, and the melt temperature during extrusion is 10-40 ℃ higher than the melting point of m-phenylene sulfide-p-phenylene sulfide copolymer but not higher than the melting point of poly-p-phenylene sulfide fibers; the die temperature is lower than the melting point of the m-phenylene sulfide-p-phenylene sulfide copolymer by 40-80 ℃.
12. Use according to claim 11, wherein the melt temperature at extrusion is 220-270 ℃ and die temperature is 150-200 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111680680.2A CN114262519B (en) | 2021-12-30 | 2021-12-30 | Polyphenylene sulfide fiber reinforced polyphenylene sulfide composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111680680.2A CN114262519B (en) | 2021-12-30 | 2021-12-30 | Polyphenylene sulfide fiber reinforced polyphenylene sulfide composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114262519A CN114262519A (en) | 2022-04-01 |
| CN114262519B true CN114262519B (en) | 2023-11-07 |
Family
ID=80832577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111680680.2A Active CN114262519B (en) | 2021-12-30 | 2021-12-30 | Polyphenylene sulfide fiber reinforced polyphenylene sulfide composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114262519B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013100615A (en) * | 2011-11-08 | 2013-05-23 | Toray Monofilament Co Ltd | Polyphenylene sulfide monofilament having flat cross section, and industrial fabric |
| CN111349340A (en) * | 2018-12-24 | 2020-06-30 | 东丽先端材料研究开发（中国）有限公司 | Polyphenylene sulfide resin composition and molded article thereof |
| WO2020135200A1 (en) * | 2018-12-24 | 2020-07-02 | 东丽先端材料研究开发（中国）有限公司 | Polyphenylene sulfide resin composition and molded product thereof |
-
2021
- 2021-12-30 CN CN202111680680.2A patent/CN114262519B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013100615A (en) * | 2011-11-08 | 2013-05-23 | Toray Monofilament Co Ltd | Polyphenylene sulfide monofilament having flat cross section, and industrial fabric |
| CN111349340A (en) * | 2018-12-24 | 2020-06-30 | 东丽先端材料研究开发（中国）有限公司 | Polyphenylene sulfide resin composition and molded article thereof |
| WO2020135200A1 (en) * | 2018-12-24 | 2020-07-02 | 东丽先端材料研究开发（中国）有限公司 | Polyphenylene sulfide resin composition and molded product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114262519A (en) | 2022-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112322039B (en) | High-thermal-conductivity reinforced polyphenylene sulfide composite material and preparation method thereof | |
| CN101113240A (en) | Highly heat conductive polyphenylene sulfide composite material and method for making same | |
| CN111073274B (en) | Heat-conducting insulating glass fiber reinforced PA66/HDPE alloy material and preparation method thereof | |
| CN113105727B (en) | Weather-resistant high-glowing filament polyester composite material and preparation method thereof | |
| CN114773836A (en) | Anti-fatigue high-gloss nylon heat insulation strip flame-retardant material and preparation method thereof | |
| CN111925649A (en) | Low-water-absorption enhanced high-temperature nylon resin and preparation method thereof | |
| CN110746777A (en) | Preparation method of polyphenylene sulfide and high-temperature nylon composite material | |
| CN111073258A (en) | Polyphenyl ether composite material and preparation method thereof | |
| CN114262519B (en) | Polyphenylene sulfide fiber reinforced polyphenylene sulfide composite material and preparation method thereof | |
| ES2528152T3 (en) | Thermoplastic moldable doughs with high hydrolysis stability | |
| CN115322567B (en) | Non-buckling-deformation reinforced heat-conducting nylon material and preparation method thereof | |
| CN111073278A (en) | Polyamide composite material and preparation method thereof | |
| CN111849163A (en) | High-performance polyphenylene sulfide/polyamide electromagnetic shielding composite material and preparation method thereof | |
| CN116285213A (en) | High-strength antistatic polyether-ether-ketone (PEEK) pipe and preparation method thereof | |
| CN114395242B (en) | High-heat-conductivity POK composite material and preparation method and application thereof | |
| CN110240805B (en) | Graphene modified polyphenylene sulfide material, preparation method thereof and heat-conducting plastic pipe | |
| CN113372647A (en) | Polypropylene compound with high-precision FDM printing performance and preparation method thereof | |
| CN1401682A (en) | Semi-continuous direct polycondensation preparation of p-aramid pulp | |
| CN110655787A (en) | Conductive polyphenylene ether/polyamide 66 composition and preparation method thereof | |
| CN111454571A (en) | Preparation method of glass fiber reinforced PA56/PP alloy material | |
| CN110684347A (en) | Conductive polyamide 6/polyphenyl ether composition and preparation method thereof | |
| CN113583439B (en) | Permanent antistatic semi-aromatic polyamide material capable of being used under high-pressure condition | |
| CN112225993B (en) | Basalt fiber reinforced polypropylene composition of flame-retardant material and preparation method thereof | |
| US8865279B2 (en) | Reinforced polyphthalamide/poly(phenylene ether) composition | |
| CN117603524B (en) | High-mechanical-property high-density polyethylene composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |