CN115895261A - Polyphenylene sulfide composite material with high CTI performance and preparation method thereof - Google Patents
Polyphenylene sulfide composite material with high CTI performance and preparation method thereof Download PDFInfo
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- CN115895261A CN115895261A CN202211500521.4A CN202211500521A CN115895261A CN 115895261 A CN115895261 A CN 115895261A CN 202211500521 A CN202211500521 A CN 202211500521A CN 115895261 A CN115895261 A CN 115895261A
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- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title abstract description 11
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- 239000003607 modifier Substances 0.000 claims abstract description 30
- 238000003763 carbonization Methods 0.000 claims abstract description 29
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- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
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- 239000012745 toughening agent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims description 23
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 21
- 239000000347 magnesium hydroxide Substances 0.000 claims description 21
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 21
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- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
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- 238000002347 injection Methods 0.000 claims description 3
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- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 claims description 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 3
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- 239000007787 solid Substances 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 2
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011208 reinforced composite material Substances 0.000 description 3
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
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- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application discloses a polyphenylene sulfide composite material with high CTI performance and a preparation method thereof, relating to the field of modification of high polymer materials, wherein the composite material comprises the following components in percentage by mass: 20-42% of polyphenylene sulfide resin, 25-40% of glass fiber, 30-40% of carbonization inhibitor, 2-10% of flow modifier, 1-6% of compatible toughening agent, 0.1-0.75% of lubricant and 0.1-0.75% of antioxidant, wherein the mass flow rate of the polyphenylene sulfide resin is 80-380g/10min. The invention adopts the carbon inhibitor, the polyphenylene sulfide resin with low flow rate and the flow modifier to be matched for use, obtains the polyphenylene sulfide composite material with high fluidity, high impact resistance and high CTI, and is suitable for manufacturing electronic and electrical products, mechanical products and the like with higher performance requirements.
Description
Technical Field
The invention belongs to the field of modification of high polymer materials, relates to a polyphenylene sulfide composite material, and particularly relates to a polyphenylene sulfide composite material with high CTI (comparative tracking index) performance and a preparation method thereof.
Background
Polyphenylene Sulfide (PPS) is a crystalline thermoplastic engineering plastic with a molecular main chain containing phenylthio, has the characteristics of large density of main chain benzene ring arrangement, high flame retardance, high strength, aging resistance and the like, and is widely used in the field of electronic and electric appliances with heat resistance and flame retardance requirements. In the use process of the electric product, the electric product is affected by the environment, so that dirt and moisture exist on the surface of the insulating material to generate electric leakage, and corrosion can be induced to damage the insulating performance. The Comparative Tracking Index (CTI) is the highest voltage value of the material surface which can withstand 50 drops of electrolyte (0.1% ammonium chloride aqueous solution) without forming a tracking mark, and a unit test gradient is 25V, which is a test performed for simulating whether conductive substances deposited on the surface of an insulating material by different polarity charged parts of household electrical appliance products in actual use cause creepage, breakdown short circuit and fire risk on the surface of the insulating material. Due to the existence of a large number of benzene rings on the PPS main chain, the rigidity of the material is increased, and simultaneously, when the material is subjected to surface discharge, the benzene ring structure is broken to generate a large number of free radicals, and a conductive carbon layer is formed on the surface, so that the tracking index of the material is lower, generally less than 150V, and in order to expand the application range of the material, the electrical property of the material needs to be improved.
In the patent (CN 112457670A), a coupling agent is added to improve the compatibility of polyphenylene sulfide resin and glass fiber, and fluorosilicone oil is added to improve the tracking index of the material. The patent (CN 102924921A) discloses a polyphenylene sulfide reinforced composite material with high comparative tracking index and a preparation method thereof, and provides a method for improving the comparative tracking index of the polyphenylene sulfide reinforced composite material by using a mixed composite technology of chopped glass fibers and superfine filler minerals, wherein the Comparative Tracking Index (CTI) can reach more than 225V.
The patent (CN 112795191A) discloses a high CTI polyphenylene sulfide composite material and a preparation method thereof, which can improve the CTI of the polyphenylene sulfide composite material to 300V by adding a metal oxide, a carbonization inhibitor and a surface transfer agent, and has balanced mechanical properties and particularly high rigidity.
The patent (CN 113402885A) discloses a polyphenylene sulfide composite material with high CTI, and the polyphenylene sulfide composite material prepared by adding flat glass fiber, magnesium hydroxide and a metal passivator not only has excellent mechanical properties, but also has a relative tracking index (CTI) of more than 400V and as high as 475V.
Journal literature (glass fiber reinforced PPS tracking performance, zhang Jiang and the like, engineering plastic application, vol 48, no 7) researches the influence of different carbonization inhibitors, compatibilizers, black toner and the like on Comparative Tracking Index (CTI) of a PPS/glass fiber composite material, and finds that the addition of the carbonization inhibitors is beneficial to improving the CTI value of the PPS/glass fiber composite material, the addition of the compatibilizers can improve the notch impact strength of the PPS/glass fiber composite material, but has no improvement effect on the CTI, the excessively high content of the compatibilizers can reduce the flame retardance and the heat resistance of the PPS/glass fiber composite material, carbon black and organic aniline black are not suitable for the development of the PPS/glass fiber composite material with high CTI, 2 parts of iron black can be used, and the most preferred technical scheme can achieve the CTI value of 275.
Master thesis (preparation and performance research of chopped glass fiber reinforced polyphenylene sulfide composite material, li Fangzhou) researches the influence of the type of polyphenylene sulfide on the mechanical properties of the composite material, and results show that the polyphenylene sulfide has low mass flow rate and is not beneficial to molding processing, and the impact strength of the obtained composite material is reduced.
The patent (CN 114907696A) discloses a high CTI polyphenylene sulfide composite material and a preparation method thereof, wherein magnesium hydroxide is modified by adopting a silane coupling agent, and a modifying toughening agent is added, so that the prepared polyphenylene sulfide composite material has the CTI value as high as 600V, and has good tensile strength, bending modulus and impact strength, and the results of examples 1 and 2 show that the PPS resin with low melt index has obvious improvement effect on the tensile strength, the bending modulus and the impact strength of the composite material, but the processability of the material is relatively poor.
However, none of the above prior arts discloses a polyphenylene sulfide composite material having high moldability, impact resistance and tracking index resistance at the same time. Although the ways of improving the CTI of polyphenylene sulfide are numerous, the preparation of the high CTI polyphenylene sulfide composite material at present is generally realized by filling a large amount of inorganic fillers such as glass fiber, mineral filler, carbon inhibitor and the like, or simultaneously adding high CTI polyamide to reduce the proportion of polyphenylene sulfide.
Since the fluidity of the polyphenylene sulfide composite material is poor due to the large amount of the inorganic filler, which is not favorable for processing and molding, and the mechanical properties (especially impact properties) of the composite material are reduced due to the difficulty in dispersion caused by the large amount of the inorganic filler, it is difficult to obtain the polyphenylene sulfide composite material having high fluidity, high impact resistance and high CTI. With the expanding use of polyphenylene sulfide materials, especially the application in electronic and electrical appliances, the parts have higher requirements in the aspects of tracking index resistance, molding processing, impact strength, etc., so that the development of polyphenylene sulfide composite materials which can simultaneously meet higher molding processing property, impact resistance and tracking index resistance is required.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a polyphenylene sulfide composite material with high CTI performance and a preparation method thereof. The invention adopts the carbon inhibitor, the flow modifier and the polyphenylene sulfide resin to be matched for use, utilizes the carbonization inhibitor to inhibit resin carbonization and reduce carbon content, improves the fluidity of polyphenylene sulfide melt through the flow modifier, realizes the use of the polyphenylene sulfide resin with low mass flow rate (large molecular weight), improves the infiltration effect of the polyphenylene sulfide and inorganic fillers such as carbonization inhibitor inhibition, glass fiber and the like, further improves the mechanical property and CTI value of the composite material, obtains the polyphenylene sulfide composite material with high fluidity, high impact resistance and high CTI, is suitable for manufacturing electronic and electrical products, mechanical products and the like with higher requirements, can be added with toner, and obtains the colored polyphenylene sulfide composite material with high fluidity, high impact resistance and high CTI.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a polyphenylene sulfide composite material with high CTI performance, which comprises the following components in percentage by mass:
wherein the mass flow rate of the polyphenylene sulfide resin is in the range of 80-380g/10min.
In a preferred embodiment, the polyphenylene sulfide resin can be any art-recognized polyphenylene sulfide resin, preferably a linear polyphenylene sulfide, with a melt mass flow rate of preferably 80 to 350g/10min, more preferably 100 to 300g/10min. If the mass flow rate of the polyphenylene sulfide resin melt is too high and the molecular weight of the polyphenylene sulfide resin is too small, on one hand, the impurity content of polyphenylene sulfide with low molecular weight is higher, and defects are easily formed in the composite material, so that electric leakage (low tracking index) and poor mechanical properties are easily caused, and on the other hand, the molecular weight of the polyphenylene sulfide resin is too small and the melt strength is too low, so that the carbonization inhibitor and the glass fiber cannot be effectively coated, and the mechanical properties and the tracking index are also poor. If the mass flow rate of the polyphenylene sulfide resin melt is too low, the melt viscosity is too high, the uniform mixing of the composite material cannot be realized, and the composite material is well processed and formed, so that the mechanical property of the composite material is poor, and the tracking index is low.
In a preferred embodiment, the glass fibers may be any glass fiber commonly used in the art, preferably, the glass fibers are alkali-free chopped glass fibers having a filament diameter of 8 μm to 13 μm. The glass fiber can play a role in enhancing and improving the mechanical strength of the composite material.
In a preferred embodiment, the carbonation inhibitor is in the form of a solid, preferably one or more of magnesium hydroxide, aluminium hydroxide, calcium borate and zinc borate, having a particle size of 3 to 8 μm, more preferably magnesium hydroxide. The carbonization inhibitor can quickly absorb heat generated during conduction and release the heat, so that the resin carbonization is inhibited, the carbon content is kept not to rise, and meanwhile, the content of polyphenylene sulfide is reduced by adding the carbonization inhibitor, so that the carbon content is reduced, and the CTI (comparative tracking index) is improved.
In a preferred embodiment, the flow modifier is one or more of low molecular weight esters, low molecular weight polyolefins, and low molecular weight polyethers, preferably, the low molecular weight polyesters are unsaturated polyesters, the low molecular weight polyolefins are one or more of low molecular weight polypropylene, low molecular weight polyethylene, or low molecular weight polystyrene, the low molecular weight polyethers are one or more of polyethylene glycol ethers, polypropylene glycol ethers, polyethylene glycol monomethyl ethers, or polyethylene glycol monomethyl ethers, and more preferably, the flow modifier is one or more of low molecular weight unsaturated polyesters, low molecular weight polyethylene, low molecular weight polypropylene, or low molecular weight polystyrene.
In a more preferred embodiment, the flow modifier has a weight average molecular weight of 100 to 50000, preferably 400 to 6000, more preferably 1000 to 6000.
In a more preferred embodiment, the flow modifier has a molecular weight distribution of from 1 to 10 and an isotacticity of from 30% to 60%, more preferably, the flow modifier has a molecular weight distribution of from 1 to 2 and an isotacticity of from 35% to 45%.
In a more preferred embodiment, the flow modifier is present in an amount of 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 8% by mass.
The low molecular weight flow modifier can permeate between polyphenylene sulfide macromolecular chains at high temperature, reduce the friction between the polyphenylene sulfide macromolecular chains, delay the crystallization rate of polyphenylene sulfide, improve the fluidity of polyphenylene sulfide melt, and further improve the infiltration effect of a polyphenylene sulfide resin matrix, glass fiber and a carbonization inhibitor. The good compatibility among the carbonization inhibitor, the glass fiber and the polyphenylene sulfide resin can reduce the defects of the structure of the polyphenylene sulfide reinforced composite material, and the defects can cause the reduction of the tracking resistance of the material, so that the addition of the flow modifier not only improves the processing flow property of the material, but also enhances the tracking resistance of the material.
In a more preferred embodiment, the compatible toughening agent, lubricant and antioxidant may be any compatible toughening agent, lubricant and antioxidant commonly found in the art. Preferably, the compatible toughening agent is POE-g-MAH. The compatibility of the filler and the polyphenylene sulfide resin matrix can be improved simultaneously by adding the compatible toughening agent, and the toughening effect is achieved.
By adopting the scheme, on one hand, the carbonization inhibitor is added, so that the resin carbonization can be inhibited, the carbon content is reduced, and the CTI of the material is improved. On the other hand, through the matching use of the polyphenylene sulfide resin and the flow modifier, the polyphenylene sulfide resin can permeate between polyphenylene sulfide macromolecular chains through the flow modifier, the friction between the polyphenylene sulfide macromolecular chains is reduced, the crystallization rate of polyphenylene sulfide is delayed, and the fluidity of polyphenylene sulfide melt is improved, so that the polyphenylene sulfide resin with low mass flow rate (large molecular weight) can be used as matrix resin, the good processing fluidity of the composite material is realized, the better mechanical property is provided, and the impact resistance of the composite material can also be improved due to the plasticizing effect of the flow modifier. In addition, the addition of the flow modifier can improve the wetting effect of the polyphenylene sulfide resin matrix, the glass fiber and the carbonization inhibitor, improve the modification effect of the glass fiber and the carbonization inhibitor on the composite material, and further improve the mechanical property and CTI value of the composite material. Furthermore, under the condition of ensuring the same modification effect, the filling amount of the glass fiber and the carbonization inhibitor can be properly reduced, thereby further improving the fluidity of the composite material and the molding processability.
Further, the polyphenylene sulfide composite material with high CTI performance also comprises 0.2% -2% of toner.
In a more preferred embodiment, the toner is carbon black and/or iron black, and more preferably, the toner is carbon black.
In the prior art, after a toner is added, particularly after black toners such as carbon black, iron black and the like are added, the CTI performance is adversely affected due to the fact that the carbon black is conductive, the iron black shielding force is insufficient, the addition amount is large, and impurities are contained, so that the CTI performance is adversely affected. The carbon inhibitor, the polyphenylene sulfide with low flow rate and the flow modifier are matched for use, so that the black polyphenylene sulfide composite material with high fluidity, high impact resistance and high CTI can be prepared after the black toner is added.
In a second aspect, the present application further provides a preparation method of the polyphenylene sulfide composite material with high CTI performance, including the following steps:
weighing the raw materials according to the formula, uniformly mixing the raw materials except the glass fiber, adding the raw materials from a main feeding port of an extruder, adding the glass fiber from a side feeding port, and extruding and granulating through the extruder to obtain the polyphenylene sulfide composite material. The extrusion temperature is 280-300 ℃, and the screw revolution is 35-40Hz.
Finally, the invention also provides an injection molding product of a notebook computer shell, an automobile part and a precise electronic and electrical appliance structural part, which comprises any one of the polyphenylene sulfide composite materials. The polyphenylene sulfide composite material is obtained by drying the polyphenylene sulfide composite material obtained by extrusion granulation and then performing injection molding by using an injection molding machine.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the carbon inhibitor, the flow modifier and the polyphenylene sulfide resin to be matched for use, utilizes the carbonization inhibitor to inhibit resin carbonization and reduce carbon content, improves the fluidity of polyphenylene sulfide melt through the flow modifier, realizes the use of the polyphenylene sulfide resin with low mass flow rate (large molecular weight), improves the infiltration effect of the polyphenylene sulfide resin, the carbonization inhibitor, inorganic fillers such as glass fiber and the like, further improves the mechanical property and CTI value of the composite material, obtains the polyphenylene sulfide composite material with high fluidity, high impact resistance and high CTI, is suitable for manufacturing electronic and electrical products, mechanical products and the like with higher requirements, can be added with toner, and obtains the colored polyphenylene sulfide composite material with high fluidity, high impact resistance and high CTI.
2. The polyphenylene sulfide composite material prepared by the method has a high CTI value which can reach 600V; has good mechanical property, the tensile strength can reach 85MPa, the bending strength can reach 135MPa, and the impact strength can reach 5.21kJ/m 2 (ii) a Has good fluidity, the mass flow rate can reach 10.5g/10min (315 ℃,5 kg), and the processability is good.
Detailed Description
It should be noted that the raw materials used in the present invention are all common commercial products, and the sources thereof are not particularly limited.
The following sources of raw materials are exemplary:
polyphenylene sulfide resin: mass flow rates of 20, 100, 200, 350, 450g/10min, commercially available;
glass fiber: alkali-free chopped glass fiber with monofilament diameter of 8-13 μm;
carbonization inhibitor: magnesium hydroxide, particle size 3-8 μm,30-100nm, commercially available;
flow modifier: low molecular weight unsaturated polyester with weight average molecular weight of 3000-6000 and low molecular weight polyethylene with weight average molecular weight of 3000-6000;
compatible toughening agent: POE-g-MAH, commercially available;
toner: carbon black, iron black, commercially available;
lubricant: TAF, commercially available;
antioxidant: b215, commercially available.
Example 1
The polyphenylene sulfide composite material comprises the following components in percentage by mass: 26.4% of polyphenylene sulfide resin with the mass flow rate of 100g/10min,30% of glass fiber, 35% of magnesium hydroxide, 4% of low-molecular unsaturated polyester, 3% of POE-g-MAH,0.3% of lubricant, 0.3% of antioxidant and 1% of carbon black. Weighing the raw materials according to the formula with the total dosage of 1kg, uniformly mixing the raw materials except the glass fiber, adding the raw materials from a main feeding port of an extruder, adding the glass fiber from a side feeding port, and performing extrusion granulation through the extruder to obtain the polyphenylene sulfide composite material. The extrusion temperature is 280-300 ℃, and the screw revolution is 35-40Hz.
Example 2
The polyphenylene sulfide composite material comprises the following components in percentage by mass: 26.4% of polyphenylene sulfide resin with the mass flow rate of 200g/10min,30% of glass fiber, 35% of magnesium hydroxide, 4% of low-molecular unsaturated polyester, 3% of POE-g-MAH,0.3% of lubricant, 0.3% of antioxidant and 1% of carbon black. Weighing the raw materials according to the formula with the total dosage of 1kg, uniformly mixing the raw materials except the glass fiber, adding the raw materials from a main feeding port of an extruder, adding the glass fiber from a side feeding port, and performing extrusion granulation through the extruder to obtain the polyphenylene sulfide composite material. The extrusion temperature is 280-300 ℃, and the screw revolution is 35-40Hz.
Example 3
The polyphenylene sulfide composite material comprises the following components in percentage by mass: 26.4 percent of polyphenylene sulfide resin with the mass flow rate of 350g/10min,30 percent of glass fiber, 35 percent of magnesium hydroxide, 4 percent of low-molecular unsaturated polyester, 3 percent of POE-g-MAH,0.3 percent of lubricant, 0.3 percent of antioxidant and 1 percent of carbon black. Weighing the raw materials according to the formula with the total dosage of 1kg, uniformly mixing the raw materials except the glass fiber, adding the raw materials from a main feeding port of an extruder, adding the glass fiber from a side feeding port, and performing extrusion granulation through the extruder to obtain the polyphenylene sulfide composite material. The extrusion temperature is 280-300 ℃, and the screw revolution is 35-40Hz.
Example 4
The polyphenylene sulfide composite material comprises the following components in percentage by mass: 26.4% of polyphenylene sulfide resin with the mass flow rate of 350g/10min,30% of glass fiber, 35% of magnesium hydroxide, 5% of low-molecular unsaturated polyester, 3% of POE-g-MAH,0.3% of lubricant and 0.3% of antioxidant. Weighing the raw materials according to the formula with the total dosage of 1kg, uniformly mixing the raw materials except the glass fiber, adding the raw materials from a main feeding port of an extruder, adding the glass fiber from a side feeding port, and performing extrusion granulation through the extruder to obtain the polyphenylene sulfide composite material. The extrusion temperature is 280-300 ℃, and the screw revolution is 35-40Hz.
Example 5
The polyphenylene sulfide composite material comprises the following components in percentage by mass: 24.4% of polyphenylene sulfide resin with the mass flow rate of 100g/10min,30% of glass fiber, 35% of magnesium hydroxide, 6% of low-molecular unsaturated polyester, 3% of POE-g-MAH,0.3% of lubricant, 0.3% of antioxidant and 1% of carbon black. Weighing the raw materials according to the formula with the total dosage of 1kg, uniformly mixing the raw materials except the glass fiber, adding the raw materials from a main feeding port of an extruder, adding the glass fiber from a side feeding port, and extruding and granulating by using the extruder to obtain the polyphenylene sulfide composite material. The extrusion temperature is 280-300 ℃, and the screw revolution is 35-40Hz.
Example 6
The procedure of example 1 was repeated, except that low-molecular weight polyethylene was used instead of the low-molecular unsaturated polyester.
Comparative example 1
The same as example 1 was repeated except that the polyphenylene sulfide resin had a mass flow rate of 20g/10 min.
Comparative example 2
The procedure of example 1 was repeated, except that the polyphenylene sulfide resin had a mass flow rate of 450g/10 min.
Comparative example 3
The procedure of example 1 was repeated, except that a polyphenylene sulfide resin was used in place of the low-molecular unsaturated polyester.
Comparative example 4
The procedure of example 1 was repeated, except that polyphenylene sulfide resin was used in place of magnesium hydroxide.
Comparative example 5
The procedure of example 1 was repeated, except that a polyphenylene sulfide resin was used in place of the low-molecular unsaturated polyester and the magnesium hydroxide.
Comparative example 6
The same procedure as in example 1 was repeated, except that the nano-sized magnesium hydroxide was used instead of the micro-sized magnesium hydroxide.
Test examples
The composite materials prepared in the above examples and comparative examples were injection molded into test standard bars in standard sizes, wherein the notched impact strength test standard bar size: the length is 80mm, the width is 10mm, the thickness is 4mm, the residual width at the bottom of the gap is 8mm, and the radius at the bottom of the gap is 0.1mm; tensile strength test specimen size: 170mm in length, 10mm in width and 4mm in thickness; bending strength test bar size: the length is 80mm, the width is 10mm, and the thickness is 4mm; melt flow rate test: a sample of particles. The correlation performance was tested with reference to the following criteria:
1. the notch impact strength is tested according to the GB/T1043 standard;
2. the tensile strength was measured according to ISO 527 (10 mm/s tensile speed);
3. the bending strength was tested according to ISO 178 (2 mm/s press bending speed);
4. the melt flow rate was measured according to the GB/T3682 standard.
5. The comparative tracking index was tested according to GB/T4207.
The test results of the above examples and comparative examples are shown in the following table:
watch 1
As can be seen from examples 1-3 and comparative example 2, when the mass flow rate of the polyphenylene sulfide resin was changed from 450g/10min to 100g/10min in a system filled with a large amount of magnesium hydroxide as a carbonization inhibitor, using a low-molecular-weight unsaturated polyester as a flow modifier, the polyphenylene sulfide composite material had a comparative tracking index (450V → 600V) and a notched impact strength (3.86 kJ/m) 2 →5.37kJ/m 2 ) All had significant improvements, while the melt flow rate, tensile strength and flexural strength were not very different, especially comparative example 2 was significantly inferior to examples 1-3. The reason why the carbon inhibitor and the flow modifier are used together with the polyphenylene sulfide resin, the carbonization inhibitor is used for inhibiting the carbonization of the resin and reducing the carbon content, the fluidity of the polyphenylene sulfide melt is improved through the flow modifier, the use of the polyphenylene sulfide resin with low mass flow rate (high molecular weight) is realized, the infiltration effect of the polyphenylene sulfide resin, the carbonization inhibitor and inorganic fillers such as glass fibers and the like is improved, the mechanical property and the CTI value of the composite material are further improved, and the polyphenylene sulfide composite material with high fluidity, high impact resistance and high CTI is obtained. It can be seen from example 1 and comparative examples 3-5 that the use of the carbonization inhibitor and the flow modifier in combination with the polyphenylene sulfide resin also has significant advantages.
It can be seen from examples 1-3 and comparative example 1 that the smaller the mass flow rate of the polyphenylene sulfide resin, the better, the too small the mass flow rate of the polyphenylene sulfide resin, the too large melt viscosity, the inability to achieve uniform mixing of the composite material, and good processing and forming results in poor mechanical properties and low tracking index of the composite material.
From examples 1 and 4, it can be seen that the polyphenylene sulfide composite of the present invention has excellent overall properties regardless of the addition of carbon black.
It can be seen from examples 1 and 6 that the composite material has excellent overall properties after the low molecular weight polyethylene is used to replace the low molecular weight unsaturated polyester.
It can be seen from example 1 and comparative example 6 that, after the nano-scale magnesium hydroxide is used to replace the micro-scale magnesium hydroxide, the comparative tracking index, the impact strength, the bending strength, the tensile strength and the melt flow rate of the polyphenylene oxide composite material are greatly reduced, which indicates that in the technical scheme of the invention, the micro-scale magnesium hydroxide has better technical effect than the nano-scale magnesium hydroxide.
Furthermore, when micron-sized aluminum hydroxide, calcium borate and zinc borate having a comparable particle size are used as the carbonation inhibitor, there is a comparable/similar technical effect as when magnesium hydroxide is used as the carbonation inhibitor. When the low molecular weight polyether flow modifier with equivalent weight average molecular weight is adopted, the technical effect is equivalent/similar to that of the low molecular weight polyolefin and low molecular weight polyester flow modifier.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and do not limit the protection scope of the present invention, and those skilled in the art can make simple modifications or equivalent substitutions on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (14)
1. A polyphenylene sulfide composite material with high CTI performance is characterized in that: comprises the following components in percentage by mass:
20% -42% of polyphenylene sulfide resin;
25% -40% of glass fiber;
30% -40% of a carbonization inhibitor;
2% -10% of a flow modifier;
1% -6% of compatible toughening agent;
0.1 to 0.75 percent of lubricant;
0.1 to 0.75 percent of antioxidant;
wherein the mass flow rate of the polyphenylene sulfide resin is in the range of 80-380g/10min.
2. The polyphenylene sulfide composite material according to claim 1, wherein: the polyphenylene sulfide resin is linear polyphenylene sulfide resin, and the mass flow rate of the linear polyphenylene sulfide resin is in the range of 100-350g/10min.
3. The polyphenylene sulfide composite material according to claim 1, wherein: the glass fiber is alkali-free short glass fiber, and the diameter of each monofilament is 8-13 mu m.
4. The polyphenylene sulfide composite material according to claim 1, wherein: the carbonation inhibitor is in a solid form.
5. The polyphenylene sulfide composite material according to claim 4, wherein: the carbonization inhibitor is one or more of magnesium hydroxide, aluminum hydroxide, calcium borate and zinc borate.
6. The polyphenylene sulfide composite material according to claim 1, wherein: the flow modifier is one or more of low molecular weight esters, low molecular weight polyolefins and low molecular weight polyethers.
7. The polyphenylene sulfide composite material according to claim 1, wherein: the weight average molecular weight of the flow modifier is 100-50000.
8. The polyphenylene sulfide composite material of claim 7, wherein: the weight average molecular weight of the flow modifier is 400-6000.
9. The polyphenylene sulfide composite material of claim 6, wherein: the low molecular weight polyester is unsaturated polyester; the low molecular weight polyolefin is one or more of low molecular weight polypropylene, low molecular weight polyethylene or low molecular weight polystyrene; the low molecular weight polyether is one or more of polyethylene glycol ether, polypropylene glycol ether, polyethylene glycol monomethyl ether or polyethylene glycol dimethyl ether.
10. The polyphenylene sulfide composite material according to claim 1, wherein: the compatible toughening agent is POE-g-MAH.
11. The polyphenylene sulfide composite material according to claim 1, wherein: also comprises 0.2% -2% of toner.
12. The polyphenylene sulfide composite material of claim 11, wherein: the toner is carbon black or/and iron black.
13. A method for preparing the polyphenylene sulfide composite material according to any one of claims 1 to 12, characterized in that: the method comprises the following steps:
weighing the raw materials according to a formula, uniformly mixing the raw materials except the glass fiber, adding the raw materials from a main feeding port of an extruder, adding the glass fiber from a side feeding port, and extruding and granulating through the extruder to obtain the polyphenylene sulfide composite material; the extrusion temperature is 280-300 ℃, and the screw revolution is 35-40Hz.
14. An injection molded article comprising the polyphenylene sulfide composite material of any one of claims 1 to 12, wherein the injection molded article is selected from the group consisting of a housing for a notebook computer, an automobile part, and a precision electronic and electrical component part.
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| CN116574375A (en) * | 2023-04-24 | 2023-08-11 | 国材(苏州)新材料科技有限公司 | Polyphenylene sulfide resin with high CTI value and CTI value test method |
| CN117186643A (en) * | 2023-09-20 | 2023-12-08 | 浙江兄弟新材料有限公司 | Polyphenylene sulfide composite material with ultrahigh relative electric leakage tracking index and preparation method thereof |
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