CN102181156B - Polyphenylene sulfide composite material and preparation method thereof - Google Patents
Polyphenylene sulfide composite material and preparation method thereof Download PDFInfo
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- CN102181156B CN102181156B CN2011101367245A CN201110136724A CN102181156B CN 102181156 B CN102181156 B CN 102181156B CN 2011101367245 A CN2011101367245 A CN 2011101367245A CN 201110136724 A CN201110136724 A CN 201110136724A CN 102181156 B CN102181156 B CN 102181156B
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- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 21
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000012545 processing Methods 0.000 claims abstract description 17
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 16
- 229920000728 polyester Polymers 0.000 claims abstract description 15
- 239000007822 coupling agent Substances 0.000 claims abstract description 11
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 87
- 150000003568 thioethers Chemical class 0.000 claims description 87
- 230000005294 ferromagnetic effect Effects 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 11
- 239000004615 ingredient Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 6
- -1 polybutylene terephthalate Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 230000005291 magnetic effect Effects 0.000 abstract description 27
- 238000001125 extrusion Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 4
- 239000006247 magnetic powder Substances 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000006185 dispersion Substances 0.000 description 15
- 239000003112 inhibitor Substances 0.000 description 15
- 239000000314 lubricant Substances 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 125000003003 spiro group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ULBTUVJTXULMLP-UHFFFAOYSA-N butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCC ULBTUVJTXULMLP-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- RVWOWEQKPMPWMQ-UHFFFAOYSA-N methyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OC RVWOWEQKPMPWMQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
Abstract
The invention discloses a polyphenylene sulfide composite material and a preparation method thereof. The polyphenylene sulfide composite material comprises the following formula components in part by weight: 72 to 92 parts of ferrite magnetic powder, 5 to 18 parts of polyphenylene sulfide, 2 to 8 parts of cyclic polyester and 0.5 to 2 parts of coupling agent. By interaction of the components in a proper content range in the extrusion process, the polyphenylene sulfide composite material has good processing flow property and mechanical performance and stable magnetic performance. The product can be obtained by mixing and extruding the components according to the formula in the preparation method of the polyphenylene sulfide composite material; and the preparation method is simple in process, low in cost, low in equipment requirement and suitable for industrialized production.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly a kind of polyphenyl thioether composite material and preparation method thereof.
Background technology
Magnetic device is the main auxiliary products of various electronic products, at daily necessities, and household electrical appliances, computer, communication equipment, automobile, and application is extremely extensive in the national defense industry, is the important basic substances of modern science and technology.Magnetic device is generally with the mode machine-shaping of magnetic powder by sintering or bonding, but the bonding magnetic device of injection moulding wherein, because physical strength is high, production is good, and manufacturing dimension is accurate, easy-formation opposite sex part, renewable advantage has obtained fast development in recent years.
Make the bonded ferrite magnetic-particle of carrier with polyphenylene sulfide, combine the advantage of the workability of ferritic high performance-price ratio and polyphenylene sulfide, occupy important share in injecting magnetic market.But, because ferritic addition large (the total amount ratio is greater than 80% usually), cause the flowability of matrix material excessively poor, cause the injection molding difficulty, the magnetic property loss is excessive, and magnetic is inhomogeneous, the shortcomings such as physical strength is low, service requirements on far away can not satisfying the market is limiting injecting magnetic especially in some structure relative complex, and magnetic is used in the demanding field.
Summary of the invention
The purpose of the embodiment of the invention is to overcome the above-mentioned deficiency of prior art, and the polyphenyl thioether composite material that a kind of processing flowability and mechanical property are good, magnetic property is stable is provided.
And, provide a kind of technique simple, be suitable for the polyphenyl thioether composite material preparation method of suitability for industrialized production.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of polyphenyl thioether composite material comprises the recipe ingredient of following parts by weight:
Described ferromagnetic oxide powder is that density is 3.0 ~ 6.0g/cm
3In the same way or/and incorgruous ferromagnetic oxide powder;
Cyclic polyester is that molecular weight is 1000 ~ 100000 ring-type polybutylene terephthalate compound.
And above-mentioned polyphenyl thioether composite material preparation method comprises the steps:
Prescription according to above-mentioned polyphenyl thioether composite material takes by weighing respectively each component;
With the mixing polyphenyl thioether composite material precursor that obtains of described each component;
Described polyphenyl thioether composite material precursor is extruded processing, obtain described polyphenyl thioether composite material.
Above-mentioned polyphenyl thioether composite material interacts in extrusion by each component of proper content scope, so that polyphenyl thioether composite material has good processing flowability and mechanical property, its magnetic property is stable.This polyphenyl thioether composite material preparation method only needs can obtain product by filling a prescription each component is mixing and extruding, and its preparation method technique is simple, and is with low cost, low for equipment requirements, is suitable for suitability for industrialized production.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is polyphenyl thioether composite material preparation method's of the present invention process flow diagram.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the invention provides a kind of processing flowability and mechanical property is good, magnetic property is stable polyphenyl thioether composite material.This polyphenyl thioether composite material comprises the recipe ingredient of following parts by weight:
Like this, above-mentioned polyphenyl thioether composite material interacts in extrusion by each component of proper content scope, so that polyphenyl thioether composite material has good processing flowability and mechanical property, its magnetic property is stable, numerical value in the table 1 that specifically vide infra.
Particularly, above-mentioned ferromagnetic oxide powder is that density is preferably 3.0 ~ 6.0g/cm
3In the same way or/and incorgruous ferromagnetic oxide powder.The trade names of producing such as Japanese TDK company are BPB-9, and the trade names that northern ore deposit magnetic material limited-liability company produces are BMXF-2S, and magnetic material company limited of the high section of Ma'an Mountain production trade names are MGC-C4n.This ferromagnetic oxide powder is as the basic components of polyphenyl thioether composite material, and the existence of this component is so that this polyphenyl thioether composite material has good magnetic property.
It is 1000 ~ 10000 PPS resin that above-mentioned polyphenylene sulfide is preferably molecular weight.This polyphenylene sulfide component is in extrusion, with other component generation compound actions, so that polyphenyl thioether composite material has good processing fluidity and physical mechanical strength.Simultaneously, the effect of playing binding agent is bonding magnetic effectively.Be somebody's turn to do the polyphenylene sulfide of preferred middle class, further improved polyphenyl thioether composite material processing fluidity and physical mechanical strength.
It is 1000 ~ 100000 macromole ring-type polybutylene terephthalate compound that above-mentioned cyclic polyester is preferably molecular weight.For example, this cyclic polyester can be that the trade names that U.S. Cyclics Corp produces are CBT100, or the trade names that the inferior macromolecular material of Dongguan high post company limited produces are AT-100 etc.This cyclic polyester component and above-mentioned polyphenylene sulfide component have splendid consistency, and the injection molding that can effectively improve polyphenyl thioether composite material is mobile, improve the dispersiveness of ferromagnetic oxide powder in moulding process, make this polyphenyl thioether composite material have excellent stable magnetic property.The cyclic polyester of this preferred kind can further improve the mobile and dispersiveness of ferromagnetic oxide powder in moulding process of injection molding of polyphenyl thioether composite material, makes this polyphenyl thioether composite material have more excellent stable magnetic property.
Above-mentioned coupling agent is preferably silane coupling agent, more preferably γ-methacryloxypropyl trimethoxy silane (KH-570).For example, this coupling agent can be that the trade names that U.S. combinating carbide company produces are that the trade names that A-174, chemical company of Japanese SHIN-ETSU HANTOTAI produce are that KBM-503 is or/and the trade names that Dow corning chemical company produces are SH-6030.This coupling agent component can make good complex role occurs in extrusion between ferromagnetic oxide powder, polyphenylene sulfide and cyclic polyester three components, in conjunction with firmly, significantly improves the physical mechanical strength of polyphenyl thioether composite material.The coupling agent of this preferred kind, particularly KH-570 coupling agent further improve the physical mechanical strength of polyphenyl thioether composite material more so that each component more effective generation complex role in extrusion.
Further preferably, also can comprise oxidation inhibitor in the above-mentioned polyphenyl thioether composite material, lubricant, dispersion agent are or/and components such as tinting materials.In 100 parts of polyphenyl thioether composite material gross weight umbers, this oxidation inhibitor, lubricant, dispersion agent, the gross weight umber of tinting material is preferably 1 part.This oxidation inhibitor, lubricant, dispersion agent does not have the restriction of parts by weight ratio between the components such as tinting material, according to the need of production adding of reality; This oxidation inhibitor, lubricant, dispersion agent, tinting material is the commercially available prod, is not specifically limited.Oxidation inhibitor is such as four [methyl-β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (1010), β-(3; the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid (1076), N; N'-pair-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (1098) is or/and 1; 3; 5-three (the 4-tertiary butyl-3-hydroxyl-2; the 6-dimethyl benzyl)-1,3,5-triazines-2; 4; 6 (1H, 3H, 5H)-triketones (1790) etc.Lubricant such as Zinic stearas, n-butyl stearate, amine hydroxybenzene, ethylenebisstearamide are or/and glyceryl monostearate etc.Dispersion agent such as whiteruss, oxidized polyethlene wax, methyl hydroxystearate are or/and polydimethylsiloxane etc.Tinting material such as carbon black, titanium dioxide white, iron oxide brown, ultramarine blue, permanent bordeaux are or/and phthalein viridescent etc.Participating in of this oxidation inhibitor given above-mentioned polyphenyl thioether composite material and had antioxidant property, thereby delayed the aging of this polyphenyl thioether composite material; Lubricant, dispersion agent can improve each component in extrusion, disperse more even so that this polyphenyl thioether composite material microtexture is more balanced and stable.
The embodiment of the invention also provides the preparation method of above-mentioned polyphenyl thioether composite material, and its technical process as shown in Figure 1.The method comprises the steps:
S1: the prescription according to above-mentioned polyphenyl thioether composite material takes by weighing respectively each component;
S2: with the mixing polyphenyl thioether composite material precursor that obtains of each component;
S3: the polyphenyl thioether composite material precursor is extruded processing, obtain described polyphenyl thioether composite material.
Particularly, among the above-mentioned polyphenyl thioether composite material preparation method step S1, ratio and kind between each component such as this ferromagnetic oxide powder, polyphenylene sulfide, cyclic polyester and coupling agent have all elaborated above-mentioned, in order to save length, repeat no more.Wherein, before taking by weighing each component, preferably corresponding component is carried out drying, such as ferromagnetic oxide powder, dry temperature should guarantee that chemical transformation does not occur each component.Dry mode can adopt conventional drying mode.
Further, in a preferred embodiment, taken by weighing oxidation inhibitor among this step S1, lubricant, dispersion agent be or/and during tinting material, this oxidation inhibitor, lubricant, dispersion agent or/and the consumption of tinting material and kind preferably as mentioned above.
Particularly, among the above-mentioned polyphenyl thioether composite material preparation method step S2, mixing purpose is that the mixing time is preferably 5 ~ 20 minutes so that each component is fully mixed, and temperature is preferably 260 ~ 330 ℃.Be somebody's turn to do preferred mixing condition, can further improve the mixture homogeneity of each component in the polyphenyl thioether composite material.This mixing equipment can be kneader, mill or Banbury mixer, preferred Banbury mixer.
Among this step S2, when having taken by weighing oxidation inhibitor in step S1, lubricant, dispersion agent be or/and during tinting material, this oxidation inhibitor, lubricant, dispersion agent form the mixture precursor or/and tinting material preferably is mixed together with ferromagnetic oxide powder, polyphenylene sulfide, cyclic polyester and coupling agent.
Among the above-mentioned polyphenyl thioether composite material preparation method step S3, preferably adopting twin screw extruder to extrude by the mixture precursor for preparing among the step S2, is CTE-35(L-D=48 such as the model of producing by Nanjing Ke Ya company) twin screw extruder etc.The temperature of mixture precursor each section in this twin screw extruder is respectively in expressing technique: 260 ~ 290 ℃ in a district, and 270 ~ 300 ℃ in two districts, 280 ~ 320 ℃ in three districts, 285 ~ 325 ℃ in four districts, head is 290 ~ 330 ℃; This is extruded the treatment time and is preferably 0.5 ~ 2 minute, and pressure is preferably 20 ~ 50MPa.This preferred procession parameters energy so that each component in extrusion, interact fully so that the polyphenyl thioether composite material mechanical property is better and stable.
In above-mentioned S1 ~ S3 step, when material is heating up rapidly under the high speed shear effect so that each material is intermolecular has an effect between mutually, thereby form the polyphenyl thioether composite material of the embodiment of the invention, and give the above-mentioned good mechanical property of this polyphenyl thioether composite material and processing characteristics, and good Magnetic stability, when containing antioxidant, this polyphenyl thioether composite material also has good antioxidant property.This polyphenyl thioether composite material preparation method only needs by prescription each component to be carried out mixing and extrude obtaining product, and its preparation method technique is simple, and is with low cost, low for equipment requirements, is suitable for suitability for industrialized production.
Now take the prescription of concrete this polyphenyl thioether composite material and preparation method as example, the present invention is further elaborated.
Embodiment 1
Polyphenyl thioether composite material parts by weight recipe ingredient is as follows, simultaneously referring to table 1:
Density is 3.0g/cm
374 parts of in the same way ferromagnetic oxide powders, molecular weight is 14 parts of 10000 PPS resins, molecular weight is 8 parts of 1000 cyclic polyesters, KH-5701 part, 0.25 part in oxidation inhibitor, 0.25 part of lubricant, 0.25 part of 0.25 part of dispersion agent and anti ultraviolet agent.
This polyphenyl thioether composite material preparation method comprises the steps:
S11: take by weighing each component by above-mentioned prescription;
S12: will carry out fully mixing 15 minutes in each component adding Banbury mixer, 280 ℃ of melting temperatures obtain the polyphenyl thioether composite material precursor;
S13: this polyphenyl thioether composite material precursor is put into the twin screw extruder melting mixing, extrude, granulation, the screw diameter of twin screw extruder is 35mm, the ratio of spiro rod length and diameter is 32:1, extrusion temperature is respectively: 270 ℃ in a district, 280 ℃ in two districts, 300 ℃ in three districts, 310 ℃ in four districts, 320 ℃ of heads, the time of extruding processing is 1min, extruding processing pressure is 15MPa.
Embodiment 2
Polyphenyl thioether composite material parts by weight recipe ingredient is as follows, simultaneously referring to table 1:
Density is 6.0g/cm
380 parts of incorgruous ferromagnetic oxide powders, molecular weight is 12 parts of 1000 PPS resins, molecular weight is 6 parts of 1000 cyclic polyesters, KH-5701 part, 0.05 part in oxidation inhibitor, 0.45 part of lubricant, 0.2 part of 0.3 part of dispersion agent and anti ultraviolet agent.
This polyphenyl thioether composite material preparation method comprises the steps:
S21: take by weighing each component by above-mentioned prescription;
S22: will carry out fully mixing 18 minutes in each component adding Banbury mixer, 235 ℃ of melting temperatures obtain the polyphenyl thioether composite material precursor;
S23: this polyphenyl thioether composite material precursor is put into the twin screw extruder melting mixing, extrude, granulation, the screw diameter of twin screw extruder is 35mm, and the ratio of spiro rod length and diameter is 40:1, and extrusion temperature is respectively: 275 ℃ in a district, 285 ℃ in two districts, 310 ℃ in three districts, 320 ℃ in four districts, 330 ℃ of heads; The time of extruding processing is 1min, and pressure is 13MPa.
Embodiment 3
Polyphenyl thioether composite material parts by weight recipe ingredient is as follows, simultaneously referring to table 1:
Density is 3.5g/cm
385 parts of incorgruous ferromagnetic oxide powders, molecular weight is 9 parts of 7000 PA12 resins, molecular weight is 4 parts of 10000 cyclic polyesters, KH-5701 part, 0.1 part in oxidation inhibitor, 0.4 part of lubricant, 0.2 part of 0.2 part of dispersion agent and anti ultraviolet agent.
This polyphenyl thioether composite material preparation method comprises the steps:
S31: take by weighing each component by above-mentioned prescription;
S32: will carry out fully mixing 15 minutes in each component adding Banbury mixer, 290 ℃ of melting temperatures obtain the polyphenyl thioether composite material precursor;
S33: this polyphenyl thioether composite material precursor is put into the twin screw extruder melting mixing, extrude, granulation, the screw diameter of twin screw extruder is 35mm, and the ratio of spiro rod length and diameter is 36:1, and extrusion temperature is respectively: 270 ℃ in a district, 280 ℃ in two districts, 300 ℃ in three districts, 310 ℃ in four districts, 320 ℃ of heads; The time of extruding processing is 1min, and pressure is 15MPa.
Embodiment 4
Polyphenyl thioether composite material parts by weight recipe ingredient is as follows, simultaneously referring to table 1:
Density is 4.0g/cm
390 parts of incorgruous ferromagnetic oxide powders, molecular weight is 5 parts of 5000 PA12 resins, molecular weight is 3 parts of 50000 cyclic polyesters, KH-5701 part, 0.1 part in oxidation inhibitor, 0.4 part of lubricant, 0.2 part of 0.2 part of dispersion agent and anti ultraviolet agent.
This polyphenyl thioether composite material preparation method comprises the steps:
S41: take by weighing each component by above-mentioned prescription;
S42: will carry out fully mixing 12 minutes in each component adding Banbury mixer, 285 ℃ of melting temperatures obtain the polyphenyl thioether composite material precursor;
S43: this polyphenyl thioether composite material precursor is put into the twin screw extruder melting mixing, extrude, granulation, the screw diameter of twin screw extruder is 35mm, and the ratio of spiro rod length and diameter is 44:1, and extrusion temperature is respectively: 275 ℃ in a district, 285 ℃ in two districts, 310 ℃ in three districts, 320 ℃ in four districts, 330 ℃ of heads; The time of extruding processing is 1min, and pressure is 13MPa.
The comparative example 1
Polyphenyl thioether composite material parts by weight recipe ingredient is as follows, simultaneously referring to table 1:
85 parts of ferromagnetic oxide powders, 14 parts of PPS resins, 0.1 part in oxidation inhibitor, 0.4 part of lubricant, 0.2 part of 0.2 part of dispersion agent and anti ultraviolet agent.
Embodiment of the invention polyphenyl thioether composite material preparation method comprises the steps:
This polyphenyl thioether composite material preparation method comprises the steps:
S11 ': take by weighing each component by above-mentioned prescription;
S12 ': will carry out fully mixing 18 minutes in each component adding Banbury mixer, 290 ℃ of melting temperatures obtain the polyphenyl thioether composite material precursor;
S13 ': this polyphenyl thioether composite material precursor is put into the twin screw extruder melting mixing, extrude, granulation, the screw diameter of twin screw extruder is 35mm, and the ratio of spiro rod length and diameter is 40:1, and extrusion temperature is respectively: 275 ℃ in a district, 285 ℃ in two districts, 310 ℃ in three districts, 320 ℃ in four districts, 330 ℃ of heads; The time of extruding processing is 1min, and pressure is 13MPa.
The performance test experiment:
The polyphenyl thioether composite material that makes among above-described embodiment 1 to embodiment 4 and the comparative example 1 is carried out respectively following performance test:
With the particle finished as stated above in 100 ℃ convection oven dry 3-6 hour in advance, and then the particulate material that drying is good carried out the injection molding sample preparation in injector, and the injection mold temperature control is at 100 ℃.
Density is undertaken by ASTM D792 standard, and specimen size 30mm * 30mm bending property test is undertaken by ASTM D790 standard, and specimen size is 128mm * 13mm * 3.2mm, and rate of bending is 3mm/min, and span is 64mm.
Melting index is pressed ASTM D1238 standard, adopts 316 ℃, and the load of 5kg is tested.
Cantilever beam impact strength is undertaken by ASTM D256 standard, and specimen size is 63.5mm * 12.7mm * 4.2mm, and notch size is 1/5th of sample thickness.
Residual magnetic flux density, the magnetic strength coercive force, HCJ and the test of maximum magnetic energy product number are undertaken by the IEC404-5 standard.Specimen size is the right cylinder of r=5mm * 10mm.
The following table 1 that the results are shown in the polyphenyl thioether composite material indices performance test that makes among above-described embodiment 1 to embodiment 4 and the comparative example 1.
Table 1
Can find out from embodiment 1 to embodiment 4, increase along with ferromagnetic oxide powder, the flexural strength of polyphenyl thioether composite material and modulus in flexure be corresponding increase also, melting index descends a little, wherein the magnetic property increase is especially obvious, illustrates that the content that increases ferromagnetic oxide powder is the effective ways that improve the magnetic property of matrix material.
Embodiment 3 compared with comparative example 1 learn, under the condition of identical ferrite magnetic powder content, the adding of cyclic polyester and coupling agent has obviously improved physical and mechanical properties, melting index and the magnetic property of polyphenyl thioether composite material.
In sum, the polyphenyl thioether composite material that the present invention is prepared is compared with conventional ferrite injecting magnetic polyphenyl thioether material, has good flowability, and excellent physical and mechanical properties and magnetic property.Can satisfy household electrical appliances, computer, communication equipment, automobile, and the user demand in the high-end field such as national defense industry, the design that is particularly suitable for some large complicated injecting magnetic accessories is used.Embodiment of the invention preparation method, simple to operate, with low cost, low for equipment requirements, be very suitable for suitability for industrialized production, have broad application prospects.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. polyphenyl thioether composite material comprises the recipe ingredient of following parts by weight:
Described ferromagnetic oxide powder is that density is 3.0 ~ 6.0g/cm
3In the same way or/and incorgruous ferromagnetic oxide powder;
Cyclic polyester is that molecular weight is 1000 ~ 100000 ring-type polybutylene terephthalate compound.
2. polyphenyl thioether composite material according to claim 1, it is characterized in that: described polyphenylene sulfide is that molecular weight is 1000 ~ 10000 PPS resin.
3. polyphenyl thioether composite material according to claim 1, it is characterized in that: described coupling agent is silane coupling agent.
4. polyphenyl thioether composite material according to claim 3, it is characterized in that: described coupling agent is γ-methacryloxypropyl trimethoxy silane.
5. polyphenyl thioether composite material preparation method may further comprise the steps:
Prescription according to the arbitrary described polyphenyl thioether composite material of claim 1 ~ 4 takes by weighing respectively each component;
With the mixing polyphenyl thioether composite material precursor that obtains of described each component;
Described polyphenyl thioether composite material precursor is extruded processing, obtain described polyphenyl thioether composite material.
6. polyphenyl thioether composite material preparation method according to claim 5, it is characterized in that: the described mixing time is 5 ~ 20 minutes, temperature is 260 ~ 330 ℃.
7. polyphenyl thioether composite material preparation method according to claim 5, it is characterized in that: described extruding is to adopt twin screw extruder to extrude, the temperature of described polyphenyl thioether composite material precursor each section in described twin screw extruder is respectively: 260 ~ 290 ℃ in a district, 270 ~ 300 ℃ in two districts, 280 ~ 320 ℃ in three districts, 285 ~ 325 ℃ in four districts, head is 290 ~ 330 ℃; Extruding the treatment time is 0.5 ~ 2 minute, and pressure is 20 ~ 50MPa.
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