CN116790122A - Hydrophobic high CTI polyphenylene sulfide composition and preparation method thereof - Google Patents
Hydrophobic high CTI polyphenylene sulfide composition and preparation method thereof Download PDFInfo
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- CN116790122A CN116790122A CN202310604577.2A CN202310604577A CN116790122A CN 116790122 A CN116790122 A CN 116790122A CN 202310604577 A CN202310604577 A CN 202310604577A CN 116790122 A CN116790122 A CN 116790122A
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- polyphenylene sulfide
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 53
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003365 glass fiber Substances 0.000 claims abstract description 23
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000003607 modifier Substances 0.000 claims abstract description 8
- 229920002545 silicone oil Polymers 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920001897 terpolymer Polymers 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 239000006078 metal deactivator Substances 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000004609 Impact Modifier Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 30
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000001746 injection moulding Methods 0.000 abstract description 3
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 3
- 238000009736 wetting Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 101100386623 Mus musculus Amd2 gene Proteins 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The application discloses a hydrophobic high CTI polyphenylene sulfide composition and a preparation method thereof. The hydrophobic high CTI polyphenylene sulfide composition comprises the following components in parts by weight: 30-80 parts of polyphenylene sulfide, 10-60 parts of glass fiber, 0.2-2 parts of coupling agent, 0.2-2 parts of fluorosilicone oil, 0.5-2 parts of impact resistance modifier and 0.1-2 parts of antioxidant; the fluorosilicone oil is at 25 ℃. According to the hydrophobic high CTI polyphenylene sulfide composition provided by the application, the compatibility of PPS and glass fiber materials is improved through the coupling agent, the impact resistance modifier is added, so that the rigidity and toughness of the materials are further improved, meanwhile, the fluorosilicone oil is added, the low surface energy and super-hydrophobic characteristics of the fluorosilicone oil are utilized, the low surface energy can be accumulated on the surfaces of the materials in the injection molding process, and the rigidity of the materials is less influenced. Meanwhile, after the fluorosilicone oil is gathered on the surface, the wetting of the electrolyte to the PPS can be greatly reduced due to the characteristic of superhydrophobicity, so that the CTI of the PPS material can be obviously improved.
Description
Technical Field
The application relates to the technical field of plastics, in particular to a hydrophobic high CTI polyphenylene sulfide composition and a preparation method thereof.
Background
Polyphenylene Sulfide (PPS) is also known as polyphenylene sulfide, a novel special engineering plastic originally initiated and produced by philips petroleum co in the united states in 1968. Because of its molecular structure specificity it has many unique properties, the main expression is as follows: excellent thermal stability, chemical stability, dimensional stability, corrosion resistance, good adhesion performance, excellent flame retardance, good electrical performance, and blending modification. The method has wide application in the fields of automobile manufacture, electronic and electrical, chemical industry, instruments and meters, aerospace industry and the like. Because of the existence of a large number of benzene rings on the PPS main chain, the rigidity of the material is increased, so that the unmodified polyphenylene sulfide material has relatively high brittleness, relatively poor mechanical properties and relatively low heat-resistant temperature, and the application of the material is greatly limited. The mechanical property and heat resistance of the polyphenylene sulfide can be improved by adopting glass fiber or inorganic mineral filler to modify the polyphenylene sulfide, and the thermal deformation temperature can reach 260 ℃. However, the impact toughness of the material is not greatly improved, and the tracking index of the material is relatively low and is generally less than 150V, so that the impact performance and the tracking index of the material need to be improved in order to expand the application range of the material.
Through searching, for example, chinese patent with publication number of CN102924921A proposes to use a compounding technology of chopped glass fibers and superfine filler minerals to improve the CTI of polyphenylene sulfide, the CTI can reach more than 225V, but a large amount of filling can cause the toughness of the material to be greatly reduced. Aiming at the problem of reduced toughness of materials, the CTI is improved while toughness is mainly improved by adding a toughening agent. For example, in chinese patent publication No. CN104194337, it is proposed that the toughness is improved by using high-flow PPS resin, a blend of polyethylene and ethylene-methyl acrylate-glycidyl methacrylate random terpolymer or polyolefin elastic graft glycidyl ester, and the prepared PPS material has better toughness and CTI performance. Chinese patent publication No. CN109679345 proposes that the flowability and the tracking resistance of the polyphenylene sulfide composite material can be improved by compounding a low molecular weight polymer plasticizer and a modifier. Meanwhile, the same tracking resistance of the traditional high-filling-amount polyphenylene sulfide composite material is achieved by matching a small amount of conductive filler and polyamide resin, but the addition of the toughening agent can cause the reduction of the dimensional stability and rigidity of the material. The Chinese patent with publication number of CN112457670 proposes a hydrophobic high CTI polyphenylene sulfide composition, which improves the compatibility of PPS and glass fiber materials by a coupling agent, further improves the rigidity and toughness of the materials, and simultaneously utilizes the low surface energy and super-hydrophobic characteristic of the fluorosilicone oil by adding the fluorosilicone oil, the low surface energy can be accumulated on the surface of the materials in the injection molding process, and the rigidity of the materials is less affected. Meanwhile, after the fluorosilicone oil is gathered on the surface, the wetting of the electrolyte to the PPS can be greatly reduced due to the characteristic of superhydrophobicity, so that the CTI of the PPS material can be obviously improved. But the performance of the above PPS material still has room for improvement.
Therefore, there is a need to provide a hydrophobic high CTI polyphenylene sulfide composition and a preparation method thereof to solve the above technical problems.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the application provides the hydrophobic high CTI polyphenylene sulfide composition and the preparation method thereof, which have high CTI performance, good dimensional stability, toughness and high rigidity.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
the hydrophobic high CTI polyphenylene sulfide composition comprises the following components in parts by weight: 30-80 parts of polyphenylene sulfide, 10-60 parts of glass fiber, 0.2-2 parts of coupling agent, 0.2-2 parts of fluorosilicone oil, 0.5-2 parts of impact resistance modifier and 0.1-2 parts of antioxidant; the fluorosilicone oil is methyl-terminated polytrifluoropropyl silicone oil with the viscosity of 600-1800mPa.s, which is tested by a silicone oil viscometer at 25 ℃; the impact modifier is a blend of polyethylene and ethylene-methyl acrylate-glycidyl methacrylate random terpolymer or a polyolefin elastomer grafted glycidyl ester.
Preferably, the composition comprises the following components in parts by weight: 40-60 parts of polyphenylene sulfide, 30-50 parts of glass fiber, 0.5-1 part of coupling agent, 0.8-1.5 parts of fluorosilicone oil, 0.5-1 part of impact resistance modifier and 0.2-0.5 part of antioxidant.
Preferably, the coupling agent is at least one of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
Preferably, the fluorosilicone oil has a viscosity of 600-1400mpa.s at 25 ℃ as measured using a silicone oil viscometer.
Preferably, the antioxidant is at least one of phenolic antioxidant, phosphite antioxidant and metal deactivator.
Preferably, the polyphenylene sulfide resin consists of two resins with a melt flow rate of 200-500 g/10min and 800-1200 g/10min according to a weight ratio of 1-5:1, wherein the test condition is 312 ℃ and 10kg.
Meanwhile, the application also provides a preparation method of the hydrophobic high CTI polyphenylene sulfide composition, which comprises the following preparation steps: dispersing all components except glass fiber through a high-speed mixer according to the formula proportion, then feeding the components into a double-screw extruder, and performing side-feeding extrusion granulation on the glass fiber to obtain the hydrophobic high-CTI polyphenylene sulfide composition; wherein the rotating speed of the high-speed mixer is 300-450rpm/min; the feeding speed of the glass fiber is 100-300kg/h; the extrusion temperature was 280-320 ℃.
Compared with the prior art, the application has the following beneficial effects:
according to the application, the compatibility of PPS and glass fiber materials is improved through the coupling agent, the impact resistance modifier is added, the rigidity and toughness of the materials are further improved, meanwhile, the fluorosilicone oil is added, and the characteristics of low surface energy and super-hydrophobic property of the fluorosilicone oil are utilized, so that the low surface energy can be gathered on the surfaces of the materials in the injection molding process, and the rigidity of the materials is less influenced. Meanwhile, after the fluorosilicone oil is gathered on the surface, the wetting of the electrolyte to the PPS can be greatly reduced due to the characteristic of superhydrophobicity, so that the CTI of the PPS material can be obviously improved.
Detailed Description
The application will be further illustrated with reference to the following examples, which are included by way of illustration, but not limitation.
In the following examples and comparative examples, each performance test criteria is as follows:
flexural modulus: the bending rate was 2mm/min tested according to standard ISO 178:2019;
CTI: according to standard IE C601 12:2009 testing;
notched impact strength: testing is performed according to the standard ISO180:2000/Amd 2:2013;
shrinkage of material: according to standard ISO294-4: 2018.
The materials used in the examples and comparative examples are as follows: polyphenylene sulfide: PPS-A with melt flow rate of 3-400 g/10min.
PPS-B, the melt flow rate is 800-1200 g/10min;
glass fiber 1: the diameter of the glass fiber is 8-10mm;
glass fiber 2: the diameter of the glass fiber is 12-15mm;
coupling agent 1: an aminosilane coupling agent, KH550;
coupling agent 2: trimethoxysilane, WD-21;
coupling agent 3: titanate coupling agent, KR-TTS;
toughening agent: PTW;
fluorosilicone oil 1: methyl-terminated polytrifluoropropyl silicone oil having a viscosity of 500mpa.s, measured with a silicone oil viscometer, at 25 ℃;
fluorosilicone oil 2: methyl-terminated polytrifluoropropyl silicone oil having a viscosity of 1000mpa.s, measured with a silicone oil viscometer, at 25 ℃;
fluorosilicone oil 3: methyl-terminated polytrifluoropropyl silicone oil having a viscosity of 1500mpa.s as measured with a silicone oil viscometer at 25 ℃;
fluorosilicone oil 4: methyl-terminated polytrifluoropropyl silicone oil having a viscosity of 2000mpa.s, measured with a silicone oil viscometer, at 25 ℃;
fluorosilicone oil 5: polytrifluoropropyl silicone oil with viscosity of 10000mpa.s tested by a silicone oil viscometer at 25 ℃;
an antioxidant: the phenolic antioxidant Y-001, the phosphite antioxidant 412S and the metal deactivator MD1024 are combined according to the weight ratio: 1:2:2;
ethylene-methyl acrylate-glycidyl methacrylate random terpolymer: AX-8900.
Examples 1 to 13 and comparative examples 1 to 3 were set in the present application, and the content of each component in examples 1 to 8 is shown in Table 1; the contents of the components of examples 9 to 13 and comparative examples 1 to 3 are shown in Table 2; the preparation method of the hydrophobic high CTI polyphenylene sulfide composition comprises the following steps: dispersing all components except glass fiber through a high-speed mixer according to the formula proportion, then feeding the components into a double-screw extruder, and performing side-feeding extrusion granulation on the glass fiber to obtain the hydrophobic high-CTI polyphenylene sulfide composition; wherein the rotating speed of the high-speed mixer is 40 rpm/min; the feeding rate of the glass fiber is 300kg/h; the extrusion temperature was 300 degrees celsius.
TABLE 1 Components, content and Performance data for examples 1-8
TABLE 2 data on the composition, content and Property of examples 9 to 13 and comparative examples 1 to 3
As is evident from the comparison of the above examples with the comparative examples, the flexural modulus and notched impact strength shrinkage of the composite material of the present application are further improved, and the comparative tracking index of the material is also correspondingly improved, further improving the relevant performance index of PPS plastics.
The above embodiment is only one of the preferred embodiments of the present application, and should not be used to limit the scope of the present application, but all the insubstantial modifications or color changes made in the main design concept and spirit of the present application are still consistent with the present application, and all the technical problems to be solved are included in the scope of the present application.
Claims (7)
1. The hydrophobic high CTI polyphenylene sulfide composition is characterized by comprising the following components in parts by weight: 30-80 parts of polyphenylene sulfide, 10-60 parts of glass fiber, 0.2-2 parts of coupling agent, 0.2-2 parts of fluorosilicone oil, 0.5-2 parts of impact resistance modifier and 0.1-2 parts of antioxidant;
the fluorosilicone oil is methyl-terminated polytrifluoropropyl silicone oil with the viscosity of 600-1800mPa.s, which is tested by a silicone oil viscometer at 25 ℃;
the impact modifier is a blend of polyethylene and ethylene-methyl acrylate-glycidyl methacrylate random terpolymer or a polyolefin elastomer grafted glycidyl ester.
2. The hydrophobic high-CTI polyphenylene sulfide composition according to claim 1, which is characterized by comprising the following components in parts by weight: 40-60 parts of polyphenylene sulfide, 30-50 parts of glass fiber, 0.5-1 part of coupling agent, 0.8-1.5 parts of fluorosilicone oil, 0.5-1 part of impact resistance modifier and 0.2-0.5 part of antioxidant.
3. The hydrophobic high CTI polyphenylene sulfide composition according to claim 1, wherein the coupling agent is at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.
4. A hydrophobic high CTI polyphenylene sulfide composition in accordance with claim 1, wherein said fluorosilicone oil has a viscosity of 600-1400mpa.s as measured at 25 ℃ using a silicone oil viscometer.
5. The hydrophobic high CTI polyphenylene sulfide composition according to claim 1, wherein the antioxidant is at least one of a phenolic antioxidant, a phosphite antioxidant, and a metal deactivator.
6. The hydrophobic high CTI polyphenylene sulfide composition according to claim 1, wherein the polyphenylene sulfide resin is composed of two resins with a melt flow rate of 200-500 g/10min and 800-1200 g/10min in a weight ratio of 1-5:1, and the test condition is 312 ℃ and 10kg.
7. The method for preparing a hydrophobic high CTI polyphenylene sulfide composition according to any one of claims 1 to 6, comprising the steps of: dispersing all components except glass fiber through a high-speed mixer according to the formula proportion, then feeding the components into a double-screw extruder, and performing side-feeding extrusion granulation on the glass fiber to obtain the hydrophobic high-CTI polyphenylene sulfide composition; wherein the rotating speed of the high-speed mixer is 300-450rpm/min; the feeding speed of the glass fiber is 100-300kg/h; the extrusion temperature was 280-320 ℃.
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| CN112457670A (en) * | 2020-11-30 | 2021-03-09 | 金发科技股份有限公司 | Hydrophobic polyphenylene sulfide composition with high CTI (comparative tracking index) as well as preparation method and application thereof |
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| CN112457670A (en) * | 2020-11-30 | 2021-03-09 | 金发科技股份有限公司 | Hydrophobic polyphenylene sulfide composition with high CTI (comparative tracking index) as well as preparation method and application thereof |
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