CN116218217A - Polyphenylene sulfide composite material for capacitor packaging shell and preparation method thereof - Google Patents
Polyphenylene sulfide composite material for capacitor packaging shell and preparation method thereof Download PDFInfo
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- CN116218217A CN116218217A CN202211096870.4A CN202211096870A CN116218217A CN 116218217 A CN116218217 A CN 116218217A CN 202211096870 A CN202211096870 A CN 202211096870A CN 116218217 A CN116218217 A CN 116218217A
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- Prior art keywords
- polyphenylene sulfide
- composite material
- pps
- epoxy resin
- bisphenol
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 108
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000003990 capacitor Substances 0.000 title claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title abstract description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 62
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 52
- 239000003822 epoxy resin Substances 0.000 claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000003365 glass fiber Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 239000000314 lubricant Substances 0.000 claims abstract description 31
- 239000012745 toughening agent Substances 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 29
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 26
- 239000007822 coupling agent Substances 0.000 claims abstract description 24
- 229920001897 terpolymer Polymers 0.000 claims abstract description 16
- 239000004593 Epoxy Substances 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 17
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 8
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims 1
- 229920006351 engineering plastic Polymers 0.000 abstract description 3
- 238000005429 filling process Methods 0.000 abstract description 2
- 239000003292 glue Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 230000001070 adhesive effect Effects 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- CNJPFZOQZWIGIB-UHFFFAOYSA-N ethene;methyl prop-2-enoate;oxiran-2-ylmethyl 2-methylprop-2-enoate Chemical compound C=C.COC(=O)C=C.CC(=C)C(=O)OCC1CO1 CNJPFZOQZWIGIB-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 5
- 235000011132 calcium sulphate Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005011 phenolic resin 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
- 239000000049 pigment Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to the technical field of special engineering plastics, and particularly relates to a polyphenylene sulfide PPS composite material for a capacitor packaging shell and a preparation method thereof. The PPS composite material comprises the following components in percentage by weight: 30% -40% of polyphenylene sulfide resin, wherein the mass flow speed is 200-350g/10min;35% -45% alkali-free short glass fiber; 10% -20% of calcium carbonate; 3% -6% of bisphenol A type solid epoxy resin; 1% -3% of ethylene-methyl acrylate-glycidyl methacrylate terpolymer toughening agent; 0% -2% of color master; 0-0.5% lubricant; 0.1% -0.5% of coupling agent. According to the glass-ore reinforced polyphenylene sulfide composite material, the toughening agent containing GMA and bisphenol A type solid epoxy resin are added, so that the bonding force between a PPS base material and the epoxy resin is improved, the requirement of a glue filling process is met, and meanwhile, the higher strength and toughness of the material are maintained; meanwhile, the processing is smooth, and the loss is less.
Description
Technical Field
The invention belongs to the technical field of special engineering plastics, and particularly relates to a polyphenylene sulfide composite material for a capacitor packaging shell and a preparation method thereof.
Background
The capacitor is one of the most widely used electronic atomic elements in electronic equipment, and is mostly applied to the aspects of isolation communication, coupling, filtering, tuning loops, energy conversion, control and the like in a circuit. With the continuous improvement of the requirements of electronic and electrical equipment on products, the resistance to external impact and vibration is improved to strengthen the integrity of electronic devices; the insulation between the internal elements and the circuits is improved, which is beneficial to the miniaturization and the weight reduction of the device; the direct exposure of elements and circuits is avoided, the waterproof and moistureproof performances of devices are improved, and the use performance and stability parameters are improved, so that epoxy resin is mechanically poured into the devices with electronic elements and circuits by adopting the epoxy insulating pouring sealant technology, and the thermosetting polymer insulating material with excellent performance is obtained by curing under the normal temperature or heating condition. Therefore, the capacitor case is required to have not only high mechanical strength, high water vapor barrier property, and high flame retardancy, but also good adhesion to the epoxy resin.
Polyphenylene Sulfide (PPS) is used as special engineering plastic with highest cost performance, has large density of main chain benzene ring arrangement, and has the characteristics of high flame retardance, high strength, heat resistance and ageing resistance. The PPS modified by the glass ores has excellent heat resistance and hardness and rigidity, and meanwhile, the molding shrinkage is low, the creep resistance of products is good, the dimensional stability is good, and the PPS has natural advantages in the field of electronic and electric appliances due to excellent insulation and high temperature resistance. PPS is a weakly polar material, however, and has no reactive group capable of reacting with an epoxy group, resulting in weak bonding force with an epoxy resin. How to improve the binding force of PPS and epoxy resin is a difficulty existing at present.
Patent CN108084711a describes the use of a toughening agent to improve adhesion to an epoxy potting adhesive, but the addition of too much toughening agent affects the rigidity of the material. Patent CN 109535716A compounds epoxy resin and phenolic resin, but the addition of the epoxy resin and the phenolic resin is excessive, so that the production stability of the material is seriously affected, and the stable production is not facilitated. To solve the above problems, it is desired to develop a coating composition which has high adhesion to an epoxy potting adhesive while ensuring excellent mechanical properties of the material.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a polyphenylene sulfide composite material with a novel structure, which has excellent mechanical properties and high adhesive force with epoxy pouring sealant.
In order to achieve the above object, the present invention provides the following technical solutions:
30% -40% of polyphenylene sulfide resin, 200-350g/10min;
35% -45% alkali-free short glass fiber;
10% -20% of calcium carbonate;
3% -6% of bisphenol A type solid epoxy resin;
1% -3% of ethylene-methyl acrylate-glycidyl methacrylate terpolymer toughening agent;
0% -2% of color master;
0-0.5% lubricant;
0% -0.5% of coupling agent.
In the present invention, polyphenylene sulfide resin: the matrix portion, continuous phase, conveys the external effects received by the material. When the mass flow rate of the polyphenylene sulfide resin is less than 200-350g/10min or more than the range, the performance of the composite material is reduced.
The alkali-free short glass fiber plays a role in strengthening, improves the mechanical strength of the material, and is mainly composed of silicon dioxide and other inorganic minerals. Preferably, the length of the alkali-free chopped glass fiber is 3-7mm, and the monofilament short diameter is 1-10 mu m; more preferably 3 to 5mm, and the filament has a short diameter of 2 to 8. Mu.m.
The calcium carbonate plays a role in strengthening and improves the mechanical strength of the material. Preferably, the calcium carbonate has a particle size in the range of 1-50 μm; further preferably 5 to 10. Mu.m. However, experimental results show that not all materials used as "fillers" can achieve the objects of the present invention, such as the decrease in mechanical properties and adhesive strength of the composite when calcium sulfate is used in place of calcium carbonate.
The bisphenol A solid epoxy resin has the advantages of improving the binding force between the base material and the epoxy resin and improving the toughness of the material. Preferably, the bisphenol A type solid epoxy resin has a molecular weight ranging from 2000 to 10000 and an epoxy equivalent weight ranging from 1000 to 5000g/eq; further preferably, the molecular weight is 2500-7000 and the epoxy equivalent weight is 1500-3500g/eq.
Preferably, the ethylene-methyl acrylate-glycidyl methacrylate terpolymer toughening agent has a Glycidyl Methacrylate (GMA) content of 8%. The ethylene-methyl acrylate-glycidyl methacrylate terpolymer containing GMA can improve the toughness of the material and the binding force between the base material and the epoxy pouring sealant.
Experimental results show that the toughening agent containing GMA has important effects on the mechanical properties and the adhesive strength of the composite material, and when the content is less than 1-3% or exceeds 3%; or when the toughening agent with other structures is adopted, the mechanical strength and/or the bonding strength of the composite material are reduced to different degrees.
The lubricant has the advantages of improving the fluidity of the material and improving the processability of the composite material, but the effect on the mechanical strength and the adhesive property of the composite material is not substantially different when the addition content is controlled within 0.5 percent. Preferably, the lubricant is ethylene bis-stearamide or silicone powder; ethylene bis stearamide is more preferred.
The coupling agent has the function of improving the compatibility of the inorganic filler and the base material. Preferably, the coupling agent is at least one of Y-chloropropyl triethoxysilane, Y- (2, 3-glycidoxy) propyltrimethoxysilane and Y- (methacryloyloxy) propyltrimethyloxysilane.
The color master is used for adjusting the color of the material. For the kind of pigment, one of ordinary skill in the art will choose from the routine.
The invention also provides a preparation method of the polyphenylene sulfide composite material, which comprises the following steps:
weighing all materials except glass fibers according to a proportion, adding the materials into a high-speed mixer, uniformly mixing to obtain a premix, putting the premix into a double-screw extruder for melt mixing and granulating, adding the glass fibers from a side feeding port, and heating at the temperature: a region: 200-300 ℃, two regions: 200-300 ℃, three regions: 300-320 ℃, four regions: 300-320 ℃ and five regions: 300-320 ℃, six regions: 280-300 ℃, seven regions: 280-300 ℃, eight regions: 280-300 ℃, nine regions: 280-300 ℃, ten areas: 280-300 ℃, eleven zone: 290-320 deg.c, die head: 300-340 ℃ and main machine feeding frequency: 10-15Hz, side feeding frequency: 2-5Hz, screw rotation speed: 250-450rpm, wherein the host feed corresponds to raw materials except glass fibers and the side feed corresponds to glass fibers.
Preferably, the mixing time is 2-5min.
The PPS composite material provided by the invention is used for preparing a capacitor packaging shell.
Compared with the prior art, the invention has the following beneficial effects:
according to the glass-ore reinforced polyphenylene sulfide composite material, the toughening agent containing GMA and bisphenol A type solid epoxy resin are added, so that the bonding force between a PPS base material and the epoxy resin is improved, the requirement of a glue filling process is met, and meanwhile, the higher strength and toughness of the material are maintained; meanwhile, the production stability can be ensured, and the loss is reduced.
Detailed Description
The invention is further illustrated below with reference to examples, which are not intended to limit the invention in any way.
Example 1
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
36.7% of polyphenylene sulfide resin, and the mass flow rate range of the polyphenylene sulfide resin is 250-300g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium carbonate having a particle size in the range of 10 μm;
4% bisphenol A type solid epoxy resin with molecular weight of 5500 and epoxy equivalent of 3200g/eq;
2% ethylene methyl acrylate-glycidyl methacrylate terpolymer toughener, wherein Glycidyl Methacrylate (GMA) content is 8%;
1.5% color master;
0.5% of lubricant ethylene bis stearamide;
0.3% of coupling agent Y-chloropropyl triethoxysilane.
The preparation method of the polyphenylene sulfide composite material in the embodiment is as follows: weighing all materials except glass fibers according to a proportion, adding the materials into a high-speed mixer, uniformly mixing to obtain a premix, adding the premix into a double-screw extruder for melt mixing and granulating, and adding the glass fibers from a side feeding port, wherein the heating temperature is as follows: a region: 220 ℃, two areas: 250 ℃, three regions: 300 ℃, four regions: 320 ℃, five regions: 320 ℃, six regions: 280 ℃, seven regions: 280 ℃, eight regions: 280 ℃, nine regions: 300 ℃, ten areas: 300 ℃, eleven regions: 320 ℃, die head: 340 ℃, host feeding frequency: 10Hz, side feed frequency: 4Hz, screw rotation speed: 300rpm, wherein the host feed corresponds to the raw material except glass fibers and the side feed corresponds to glass fibers.
Example 2
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
36.7% of polyphenylene sulfide resin, and the mass flow rate range of the polyphenylene sulfide resin is 250-300g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium carbonate having a particle size in the range of 10 μm;
4% bisphenol A type solid epoxy resin with a molecular weight of 2100 and an epoxy equivalent of 2100g/eq;
2% ethylene methyl acrylate-glycidyl methacrylate terpolymer toughener, wherein Glycidyl Methacrylate (GMA) content is 8%;
1.5% color master;
0.5% lubricant;
0.3% of coupling agent.
This embodiment differs from embodiment 1 in that: the molecular weight of the bisphenol A type solid epoxy resin was 2100 and the epoxy equivalent was 2100g/eq.
Comparative example 1
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
36.7% of polyphenylene sulfide resin, and the mass flow rate range of the polyphenylene sulfide resin is 250-300g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium carbonate having a particle size in the range of 10 μm;
6% bisphenol A type solid epoxy resin with molecular weight of 5500 and epoxy equivalent weight of 3200g/eq;
1.5% color master;
0.5% lubricant;
0.3% of coupling agent.
This embodiment differs from embodiment 1 in that: no toughening agent is added, and the content of bisphenol A is 6 percent.
Comparative example 2
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
36.7% of polyphenylene sulfide resin, and the mass flow rate range of the polyphenylene sulfide resin is 250-300g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium carbonate having a particle size in the range of 10 μm;
6% bisphenol A type solid epoxy resin with molecular weight of 3800 and epoxy equivalent of 2800g/eq;
1.5% color master;
0.5% lubricant;
0.3% of coupling agent.
This embodiment differs from embodiment 1 in that: no toughening agent is added, the content of bisphenol A is 6%, the molecular weight is 3800, and the epoxy equivalent is 2800g/eq.
Comparative example 3
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
36.7% of polyphenylene sulfide resin, and the mass flow rate range of the polyphenylene sulfide resin is 350-400g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium carbonate having a particle size in the range of 10 μm;
4% bisphenol A type solid epoxy resin with molecular weight of 5500 and epoxy equivalent of 3200g/eq;
2% ethylene methyl acrylate-glycidyl methacrylate terpolymer toughener, wherein Glycidyl Methacrylate (GMA) content is 8%;
1.5% color master;
0.5% lubricant;
0.3% of coupling agent.
This embodiment differs from embodiment 1 in that: the mass flow rate of the polyphenylene sulfide resin is in the range of 350-400g/10min.
Comparative example 4
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
36.7% of polyphenylene sulfide resin, and the mass flow rate range of the polyphenylene sulfide resin is 350-400g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium carbonate having a particle size in the range of 10 μm;
6% bisphenol A type solid epoxy resin with molecular weight of 3800 and epoxy equivalent of 2800g/eq;
1.5% color master;
0.5% lubricant;
0.3% of coupling agent.
The difference between this embodiment and comparative example 3 is that: no toughening agent is added, the content of bisphenol A type solid epoxy resin is 6 percent, the molecular weight is 3800, and the epoxy equivalent is 2800g/eq.
Comparative example 5
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
36.7% of polyphenylene sulfide resin, and the mass flow rate range of the polyphenylene sulfide resin is 250-300g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium carbonate having a particle size in the range of 10 μm;
6% bisphenol A type solid epoxy resin with a molecular weight of 2100 and an epoxy equivalent of 2100g/eq;
1.5% color master;
0.5% lubricant;
0.3% of coupling agent.
This example differs from example 2 in that no toughening agent was added, and the bisphenol a epoxy resin content was 6%.
Comparative example 6
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
36.7% of polyphenylene sulfide resin, and the mass flow rate range of the polyphenylene sulfide resin is 250-300g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium carbonate having a particle size in the range of 10 μm;
6% bisphenol A type solid epoxy resin with a molecular weight of 2100 and an epoxy equivalent of 2400g/eq;
1.5% color master;
0.5% lubricant;
0.3% of coupling agent.
This example differs from example 2 in that the bisphenol A type solid epoxy resin, to which no toughening agent was added, had a content of 6%, a molecular weight of 2100, and an epoxy equivalent of 2400g/eq.
Example 3
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
37.2% of polyphenylene sulfide resin, wherein the mass flow rate range is 250-300g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium carbonate having a particle size in the range of 10 μm;
4% bisphenol A type solid epoxy resin with molecular weight of 5500 and epoxy equivalent of 3200g/eq;
2% ethylene methyl acrylate-glycidyl methacrylate terpolymer toughener, wherein Glycidyl Methacrylate (GMA) content is 8%;
1.5% color master;
0.3% of coupling agent.
This example differs from example 1 in that no lubricant is contained.
Example 4
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
36.7% of polyphenylene sulfide resin, and the mass flow rate range of the polyphenylene sulfide resin is 250-300g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium carbonate having a particle size in the range of 10 μm;
4% bisphenol A type solid epoxy resin with molecular weight of 5500 and epoxy equivalent of 3200g/eq;
2% ethylene methyl acrylate-glycidyl methacrylate terpolymer toughener, wherein Glycidyl Methacrylate (GMA) content is 8%;
1.5% color master;
0.5% of a lubricant, wherein the lubricant is silicone powder;
0.3% of coupling agent.
The present embodiment differs from embodiment 1 in that the lubricant is silicone powder.
Comparative example 7
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
37% polyphenylene sulfide resin with mass flow rate ranging from 250-300g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium carbonate having a particle size in the range of 10 μm;
4% bisphenol A type solid epoxy resin with molecular weight of 5500 and epoxy equivalent of 3200g/eq;
2% ethylene methyl acrylate-glycidyl methacrylate terpolymer toughener, wherein Glycidyl Methacrylate (GMA) content is 8%;
1.5% color master;
0.5% lubricant.
This example differs from example 1 in that no coupling agent is contained.
Comparative example 8
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
36.7% of polyphenylene sulfide resin, and the mass flow rate range of the polyphenylene sulfide resin is 250-300g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium carbonate having a particle size in the range of 10 μm;
4% bisphenol A type solid epoxy resin with molecular weight of 5500 and epoxy equivalent of 3200g/eq;
2% of toughening agent maleic anhydride grafting ethylene grafting olefin copolymer POE-g-MAH, and maleic anhydride grafting rate is 1.1%;
1.5% color master;
0.5% lubricant;
0.3% of coupling agent.
This example differs from example 1 in that the toughening agent is POE-g-MAH and the maleic anhydride grafting ratio is 1.1%.
Comparative example 9
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
46.7% of polyphenylene sulfide resin, wherein the mass flow rate range is 250-300g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
5% calcium carbonate having a particle size in the range of 10 μm;
4% bisphenol A type solid epoxy resin with molecular weight of 5500 and epoxy equivalent of 3200g/eq;
2% ethylene methyl acrylate-glycidyl methacrylate terpolymer toughener, wherein Glycidyl Methacrylate (GMA) content is 8%;
1.5% color master;
0.5% lubricant;
0.3% of coupling agent.
This example differs from example 1 in that the calcium carbonate is 5% and its particle size is in the range of 10. Mu.m.
Comparative example 10
The polyphenylene sulfide PPS composite material is prepared from the following components in percentage by mass:
36.7% of polyphenylene sulfide resin, and the mass flow rate range of the polyphenylene sulfide resin is 250-300g/10min;
40% alkali-free short glass fiber, the monofilament diameter range of which is 5 mu m;
15% calcium sulphate having a particle size in the range of 50 μm;
4% bisphenol A type solid epoxy resin with molecular weight of 5500 and epoxy equivalent of 3200g/eq;
2% ethylene methyl acrylate-glycidyl methacrylate terpolymer toughener, wherein Glycidyl Methacrylate (GMA) content is 8%;
1.5% color master;
0.5% lubricant;
0.3% of coupling agent.
This example differs from example 1 in that calcium sulfate is used instead of calcium carbonate.
Comparative example 11
The specific preparation method of the polyphenylene sulfide composite material provided in example 2 of patent CN 109651814a was referred to as the following composite material,
54.5% polyphenylene sulfide resin, the mass flow rate range of which is 400-500g/10min;
40% alkali-free short glass fiber is treated by a silane coupling agent KH 560;
4% PA6, the mass flow rate of which is in the range of 6-30g/10min;
1% of compatilizer 1 4% of epoxy resin A, and the epoxy value is 0.115-0.130;
0.1% antioxidant 1010;
0.1% antioxidant 9228;
0.5% lubricant silicone.
The preparation method comprises the following steps:
(1) The weight percentages are as follows: uniformly mixing 54.5% of polyphenylene sulfide, 4.0% of PA6, 1.0% of compatilizer 1, 0.1% of antioxidant 1010, 0.1% of antioxidant 9228 and 0.5% of silicone powder in a high-speed mixer to obtain a mixed material;
(2) Adding the mixed material prepared in the step (1) from a feed hopper of an extruder, adding 40% by weight of glass fiber 1 from a side feed hopper of the extruder, and carrying out melt extrusion, cooling, granulating and drying to prepare the high-strength and toughness-improving polyphenylene sulfide composite material.
Performance testing
1. Tensile Properties
The tensile strength of the composite materials provided in the examples above was tested with reference to the method of ISO 527 (10 mm/s tensile speed), the results of which are given in the following table. (in MPa).
2. Flexural Strength
The tensile strength of the composite materials provided in the examples above was tested with reference to the method of ISO 178 (2 mm/s bending speed) and the results are given in the following table. (in MPa)
3. Impact Strength
The impact properties of the composites provided in the examples above were tested with reference to the method of ISO 179 (type C notched) and the results are given in the table below. (in KJ/m) 2 )。
4. Flame retardant performance test standard
The flame retardancy of the composite materials provided in the examples above was tested with reference to the method prescribed in the standard UL-94 (1.6 mm).
5. Good adhesion with epoxy pouring sealant
Among them, the adhesive strength test (i.e., adhesion or bonding force with epoxy) is as follows: injection molding the test sample strip of the molding material by an injection molding machine, wherein the size (unit mm) of the sample strip is 170 x 10 x 4, and the bonding size of the interface between the sample strip and the epoxy resin is 300mm 2 The drawing force test was performed using a universal tensile tester, and the data thus obtained can be used as a criterion for the magnitude of the adhesion force between the sample and the epoxy resin member.
The performance statistics for each example and comparative example are shown in tables 1-2 below.
TABLE 1
In comparison with example 1, the materials prepared in comparative examples 1 and 2, in which no GMA-containing toughening agent was added, had lower tensile strength and lower adhesive strength than those of example 1;
in comparison with example 1, in comparative examples 3 and 4, PPS having a different melt index was replaced, and the adhesive strength of the resulting material was far lower than that of example 1, so that the adhesive strength of PPS having a different base material was affected to some extent with the epoxy resin;
in example 2, an epoxy resin having a relatively low epoxy equivalent and molecular weight was used, and the tensile strength and adhesive strength were slightly lowered as compared with example 1.
Compared with comparative example 5 and comparative example 6, no toughening agent is added, and the tensile strength and the adhesive strength are obviously reduced.
TABLE 2
In example 3, no lubricant was added as compared with example 1, and the properties of the material produced were not significantly changed, but the addition of the lubricant was advantageous in stably carrying out the production and reducing the friction between the material and the screw, so that preferably, not more than 0.5% of the lubricant could be added.
Compared with example 1, the tensile strength and the bonding strength of the material are reduced without adding the silane coupling agent in comparative example 7, and the addition of the coupling agent increases the compatibility of the filler and the base material, so that the bonding force of the material and the epoxy resin can be further improved.
As can be seen from example 4, when silicone powder is selected as the lubricant, the effect is substantially equivalent to that of ethylene bisstearamide, but the cost of ethylene bisstearamide is lower and the cost performance is higher, so ethylene bisstearamide is preferable as the lubricant.
As can be seen from comparative example 8, when POE-G-MAH is selected as the toughening agent, although the tensile strength and impact strength of the material are not very different, the adhesive strength of the material to epoxy is significantly reduced, mainly because POE-G-MAH contains less polar functional groups (MAH) than ethylene-methyl acrylate-Glycidyl Methacrylate (GMA) and therefore has a poor bonding force to epoxy.
In comparative example 9, the amount of calcium carbonate added was reduced, and although the tensile strength and impact strength of the material were both as high as those of example 1, the adhesive strength was far lower than that of example 1. Meanwhile, the reduction of the filler content also leads to the improvement of the material cost, which is not beneficial to the further popularization of the market.
In comparative example 4, the substitution of calcium carbonate with calcium sulfate whiskers occurred, and both the tensile strength and the cohesive strength of the material were reduced.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The polyphenylene sulfide PPS composite material for the capacitor packaging shell is characterized by being prepared from the following components in percentage by mass:
30% -40% of polyphenylene sulfide resin, wherein the mass flow speed is 200-350g/10min;
35% -45% alkali-free short glass fiber;
10% -20% of calcium carbonate;
3% -6% of bisphenol A type solid epoxy resin;
1% -3% of ethylene-methyl acrylate-glycidyl methacrylate terpolymer toughening agent;
0% -2% of color master;
0-0.5% lubricant;
0-0.5% of coupling agent.
2. The polyphenylene sulfide (PPS) composite material according to claim 1, which is characterized by comprising the following components in percentage by mass:
30% -40% of polyphenylene sulfide resin, wherein the mass flow speed is 200-350g/10min;
35% -45% alkali-free short glass fiber;
10% -20% of calcium carbonate;
3% -6% of bisphenol A type solid epoxy resin,
1% -3% of ethylene-methyl acrylate-glycidyl methacrylate terpolymer toughening agent;
0% -2% of color master;
0.1-0.5% lubricant;
0.1-0.5% of coupling agent.
3. The polyphenylene sulfide (PPS) composite material according to claim 1, which is characterized by comprising the following components in percentage by mass:
35% -40% of polyphenylene sulfide resin, wherein the mass flow speed is 200-350g/10min;
35% -40% of alkali-free short glass fiber;
15% -20% of calcium carbonate;
3% -6% of bisphenol A type solid epoxy resin,
1% -3% of ethylene-methyl acrylate-glycidyl methacrylate terpolymer toughening agent;
0% -2% of color master;
0.1-0.5% lubricant;
0.1-0.5% of coupling agent.
4. The polyphenylene sulfide PPS composite material according to any one of claim 1 to 3,
the molecular weight of the bisphenol A type solid epoxy resin ranges from 2000 to 10000, and the epoxy equivalent weight ranges from 1000 to 5000g/eq.
5. The polyphenylene sulfide (PPS) composite material according to claim 4, which is prepared from the following components in percentage by mass: the molecular weight of the bisphenol A type solid epoxy resin is 2500-7000, and the epoxy equivalent is 1500-3500g/eq.
6. The polyphenylene sulfide PPS composite material according to any one of claims 1 to 3, wherein the lubricant is ethylene bis stearamide or silicone.
7. The polyphenylene sulfide PPS composite material according to any one of claims 1 to 3, wherein the coupling agent is at least one of Y-chloropropyl triethoxysilane, Y- (2, 3-glycidoxy) propyltrimethoxysilane, and Y- (methacryloyloxy) propyltrimethyloxysilane.
8. The polyphenylene sulfide (PPS) composite material according to claim 1, characterized in that it is made of the following components in mass percent:
30% -40% of polyphenylene sulfide resin, wherein the mass flow speed is 250-300g/10min;
35% -45% alkali-free short glass fiber, wherein the length of the fiber is 3-7mm;
10% -20% of calcium carbonate, and the particle size range is 5-10 mu m;
3% -6% of bisphenol A type solid epoxy resin, wherein the molecular weight is 2500-7000, and the epoxy equivalent is 1500-3500g/eq;
1% -3% of ethylene-methyl acrylate-glycidyl methacrylate terpolymer toughening agent, wherein the content of glycidyl methacrylate is 8%;
0% -2% of color master;
0.1-0.5% of lubricant ethylene bis stearamide;
0.1-0.5% of coupling agent.
9. A method for preparing the polyphenylene sulfide PPS composite material according to any one of claims 1 to 8, comprising the steps of:
weighing all materials except glass fibers according to a proportion, adding the materials into a high-speed mixer, uniformly mixing to obtain a premix, putting the premix into a double-screw extruder for melt mixing and granulating, adding the glass fibers from a side feeding port, and heating at the temperature: a region: 200-300 ℃, two regions: 200-300 ℃, three regions: 300-320 ℃, four regions: 300-320 ℃ and five regions: 300-320 ℃, six regions: 280-300 ℃, seven regions: 280-300 ℃, eight regions: 280-300 ℃, nine regions: 280-300 ℃, ten areas: 280-300 ℃, eleven zone: 290-320 deg.c, die head: 300-340 ℃ and main machine feeding frequency: 10-15Hz, side feeding frequency: 2-5Hz, screw rotation speed: 250-450rpm, wherein the host feed corresponds to raw materials except glass fibers and the side feed corresponds to glass fibers.
10. Use of the polyphenylene sulfide PPS composite material of any of claims 1-8 in a capacitor package housing.
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