CN102634124A - Fiber reinforced thermoplastic polymer matrix composite material and preparation method thereof - Google Patents
Fiber reinforced thermoplastic polymer matrix composite material and preparation method thereof Download PDFInfo
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- CN102634124A CN102634124A CN2012101242028A CN201210124202A CN102634124A CN 102634124 A CN102634124 A CN 102634124A CN 2012101242028 A CN2012101242028 A CN 2012101242028A CN 201210124202 A CN201210124202 A CN 201210124202A CN 102634124 A CN102634124 A CN 102634124A
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- thermoplastic polymer
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- composite material
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- 239000000835 fiber Substances 0.000 title claims abstract description 68
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 12
- 239000011160 polymer matrix composite Substances 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000007822 coupling agent Substances 0.000 claims abstract description 27
- 239000004793 Polystyrene Substances 0.000 claims abstract description 18
- 229910052582 BN Inorganic materials 0.000 claims abstract description 14
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010453 quartz Substances 0.000 claims abstract description 13
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 12
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 3
- 239000012783 reinforcing fiber Substances 0.000 claims abstract 13
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 229920010524 Syndiotactic polystyrene Polymers 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000001746 injection moulding Methods 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 239000008188 pellet Substances 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229920001955 polyphenylene ether Polymers 0.000 claims 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- 238000002844 melting Methods 0.000 claims 2
- 230000008018 melting Effects 0.000 claims 2
- 229920005669 high impact polystyrene Polymers 0.000 claims 1
- 239000004797 high-impact polystyrene Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000004891 communication Methods 0.000 abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 2
- 229920006380 polyphenylene oxide Polymers 0.000 abstract 2
- 238000005452 bending Methods 0.000 abstract 1
- -1 ppe Substances 0.000 description 13
- 238000012545 processing Methods 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 7
- 229920013657 polymer matrix composite Polymers 0.000 description 7
- 238000007654 immersion Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000004727 Noryl Substances 0.000 description 1
- 229920001207 Noryl Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种纤维增强热塑性聚合物基复合材料，由热塑性聚合物、增强纤维和占增强纤维重量比为0.2％～1％的偶联剂制成，所述热塑性聚合物和增强纤维的重量比为1∶1～9∶1，其中热塑性聚合物为聚苯乙烯(PS)、聚苯醚(PPO)、聚苯硫醚(PPS)中的任一种或其中任意两种或三种聚合物的混合物，增强纤维为石英纤维或氮化硼纤维或两种纤维的混合物，偶联剂为硅烷偶联剂或钛酸酯偶联剂；该材料具有绝缘强度高、介电常数小、拉伸强度和弯曲强度高等特点，可用于高压绝缘器件、卫星通讯窗口、雷达罩等功能结构件；本发明还提供了这类复合材料的制备方法。
The invention discloses a fiber-reinforced thermoplastic polymer-based composite material, which is made of a thermoplastic polymer, a reinforcing fiber and a coupling agent accounting for 0.2% to 1% by weight of the reinforcing fiber, the thermoplastic polymer and the reinforcing fiber The weight ratio is 1:1 to 9:1, wherein the thermoplastic polymer is any one of polystyrene (PS), polyphenylene oxide (PPO), polyphenylene sulfide (PPS) or any two or three of them A mixture of polymers, the reinforcing fiber is quartz fiber or boron nitride fiber or a mixture of the two fibers, and the coupling agent is a silane coupling agent or a titanate coupling agent; the material has high dielectric strength, low dielectric constant, It has the characteristics of high tensile strength and bending strength, and can be used for functional structural parts such as high-voltage insulating devices, satellite communication windows, and radomes; the invention also provides a preparation method of this type of composite material.
Description
Technical field
The invention belongs to the thermoplastic polymer in the polymer composite, especially quartz/boron nitride fibre strengthens thermoplastic polymer based matrix material.
Background technology
PS, ppe, polyphenylene sulfide are the thermoplasticity engineering materialss of one type of high comprehensive performance; Its outstanding feature is that corrosion-resistant, radiation hardness, mechanical property and electrical property are excellent, is mainly used in automobile making, electronic apparatus, chemical industry instrument and space industry etc. at present.Because this type of material has insulation strength height, the low (ε of specific inductivity
r=2.5～3), little (the tangent of the dielectric loss angle value: PS, ppe≤0.0006 of dielectric loss; Polyphenylene sulfide ≈ 0.001) characteristics such as come into one's own day by day in all kinds of High-Voltage Insulation devices, hertzian wave transparent structure spare (like satellite communication window, radome etc.) and pay close attention to.(be about 35-50MPa like the general purpose polystyrene tensile strength, flexural strength is 60～70MPa), has restricted the application of this type of material but because this type of strength of materials is on the low side.
At present; It mainly is to be main with the simple glass fiber reinforcement that this type of thermoplastic, polymeric materials strengthens toughening modifying; Spun glass can significantly improve the mechanical property of material, but because simple glass fiber specific inductivity big (about 4.0～6.6), dielectric loss coefficient big (3～7 * 10
-3); Dielectric properties to polymer matrix composite produce detrimentally affect (after adding the spun glass of 30wt.% in the PS; 9.5GHz under the condition, relative permittivity from 2.5 bring up to＞3.0, the tangent of the dielectric loss angle value from 0.0006 bring up to＞0.001).
Summary of the invention
In order to overcome the shortcoming of PS/ppe/polyphenylene sulfide polymer and glass fibre reinforced composion thereof; The present invention adopts quartz/SP 1 as fortifying fibre; Obtained one type of excellent quartz/boron nitride fibre of mechanical property, insulating property and dielectric properties and strengthened thermoplastic polymer based matrix material, the present invention also provides the preparation method of this type matrix material.
Technical scheme provided by the invention is:
A kind of fiber reinforced thermolplastic polymer matrix composite; By thermoplastic polymer, fortifying fibre with to account for the fortifying fibre weight ratio be that 0.2%～1% coupling agent is processed; The weight ratio of said thermoplastic polymer and fortifying fibre is 1: 1～9: 1; Said thermoplastic polymer is any or wherein any two or three kinds of mixture of polymers of PS (PS), ppe (PPO) and polyphenylene sulfide (PPS); Said fortifying fibre is silica fiber and/or boron nitride fibre, and said coupling agent is silane coupling agent or titanate coupling agent.
The optimum weight ratio of above-mentioned thermoplastic polymer and fortifying fibre is 7: 3～9: 1.
Above-mentioned silica fiber is silicon-dioxide (SiO
2) content is greater than 99.9% quartz glass fibre.
Above-mentioned PS (PS) is any in general purpose polystyrene (GPPS), syndiotactic polystyrene (sPS), isotactic polyphenylacetylene (iPS) or the high impact resistance polystyrene (HIPS); Above-mentioned ppe (PPO) is Noryl (MPPO).
Above-mentioned fortifying fibre is a whisker.
First kind of method of making above-mentioned fiber reinforced thermolplastic polymer matrix composite may further comprise the steps:
1] with ethanol be solution, it is 1～3% treatment solution that coupling agent is made into weight ratio, and fortifying fibre carries out immersion treatment in treatment solution, oven dry;
2] with thermoplastic polymer with through step 1] fortifying fibre handled adds in the forcing machine, is T in temperature
m～T
mAdd under+50 ℃ of temperature hot-extrudable, and cooling back pelletizing; Said T
mFusing point for thermoplastic polymer;
3] pellet that makes is added injection moulding machine, in temperature T
m～T
mInjection moulding under+50 ℃, pressure 70～120MPa.
Second kind of method of making above-mentioned fiber reinforced thermolplastic polymer matrix composite may further comprise the steps:
1] with ethanol be solution, it is 1～3% treatment solution that coupling agent is made into weight ratio, and fortifying fibre carries out immersion treatment in treatment solution, oven dry;
2] with thermoplastic polymer with through step 1] fortifying fibre handled adds in the forcing machine, is T in temperature
m～T
mAdd hot-extrudable under+50 ℃ of temperature; Said T
mFusing point for thermoplastic polymer;
3] extruded stock is directly transferred in the hot pressing die of heating, in temperature T
m～T
mCompression molding under+50 ℃, pressure 10～50MPa.
The present invention has following beneficial effect:
1, quartz/boron nitride fibre of the present invention strengthens thermoplastic polymer based matrix material; Keeping the polymer materials insulation strength high; When specific inductivity is little, improve the mechanical property of material greatly, comprised tensile strength, flexural strength and impact toughness; In addition, further reduced the dielectric loss coefficient of material.
2, quartz/boron nitride fibre of the present invention strengthens thermoplastic polymer based matrix material, has that material source is extensive, manufacture craft is simple, can satisfy the processing requirement of plastic shapings processing such as injection moulding, extrusion molding, mold pressing.
3, quartz/boron nitride fibre of the present invention strengthens thermoplastic polymer based matrix material, can be widely used in functional partses such as High-Voltage Insulation device, satellite communication window, radome.
Description of drawings
Fig. 1 is first kind of manufacture craft flow process of fiber reinforced thermolplastic polymer matrix composite of the present invention: fiber pre-treatment-extrude-injection moulding;
Fig. 2 is first kind of manufacture craft flow process of fiber reinforced thermolplastic polymer matrix composite of the present invention: fiber pre-treatment-extrusion-die pressing.
Embodiment
In order to overcome polymkeric substance and the not good shortcoming of glass fibre reinforced composion mechanical property, insulating property and dielectric properties thereof; The present invention adopts quartz/SP 1 as fortifying fibre; This is because compare with the simple glass fiber, and silica fiber and boron nitride fibre have all that mechanical property is good, dielectric strength is high, dielectric loss coefficient is little by (＜1.0 * 10
-3), the little advantages such as (3～3.8) of specific inductivity, polymkeric substance matchings such as electrical property and PS are good, simultaneously the polymkeric substance mechanical property had more significant raising effect.
Embodiment 1:
Raw material is formed: syndiotactic polystyrene, silica fiber, siloxanes coupling agent;
Syndiotactic polystyrene wherein: silica fiber=9: 1 (weight ratio); Siloxanes coupling agent (KH-550) weight is 1% of silica fiber weight;
Implementing process:
(a) fortifying fibre surface coupling processing: siloxanes coupling agent and absolute ethyl alcohol are made into the mixing solutions of 2% (weight ratio), and fortifying fibre carries out immersion treatment through towing mechanism in treatment solution, the oven dry processing;
(b) extrude: the sPS polymer powders is added in the loading hopper of twin screw extruder; Fortifying fibre adds by extruding the pusher side spout, and control twin screw rotating speed is 90rpm, and the fusing point of syndiotactic polystyrene is 270 ℃; So the processing district medial temperature is 280 ℃; Residence time 2min, die orifice pressure are 5MPa, through fusion, cool off, be drawn to the dicing machine pelletizing;
(c) injection moulding: the pellet that above-mentioned steps is worth adds the injection moulding machine loading hopper, is 285 ℃ at injection temperature, and pressure is injection moulding under the 100MPa condition, makes the matrix material blank of desired shape.
Embodiment 2:
Raw material is formed: syndiotactic polystyrene, silica fiber, siloxanes coupling agent;
Syndiotactic polystyrene wherein: silica fiber=7: 3 (weight ratio); Siloxanes coupling agent (KH-550) weight is 0.2% of silica fiber weight;
Implementing process is with described in the embodiment 1.
Embodiment 3:
Raw material is formed: syndiotactic polystyrene, silica fiber, siloxanes coupling agent;
Syndiotactic polystyrene wherein: silica fiber=7: 3 (weight ratio); Siloxanes coupling agent (KH-550) weight is 0.2% of silica fiber weight;
Implementing process:
(a) fortifying fibre surface coupling processing: siloxanes coupling agent and absolute ethyl alcohol are made into the mixing solutions of 2% (weight ratio), and fortifying fibre carries out immersion treatment through towing mechanism in treatment solution, the oven dry processing;
(b) extrude: the sPS polymer powders is added in the loading hopper of twin screw extruder, fortifying fibre adds by extruding the pusher side spout, and control twin screw rotating speed is 90rpm, and the processing district medial temperature is 280 ℃, and residence time 2min, die orifice pressure are 5MPa;
(c) mold pressing: extruded stock is directly transferred in the heated die through shifting interface, is compression molding under the 30MPa condition at 280 ℃, pressure.
Embodiment 4:
Raw material is formed: ppe, silica fiber, siloxanes coupling agent;
Ppe wherein: silica fiber=7: 3 (weight ratio); Siloxanes coupling agent (KH-550) weight is 0.2% of silica fiber weight;
Except that technological temperature, implementing process is with described in the embodiment 1, about 300 ℃ of the fusing point of ppe, so the processing district medial temperature is 310 ℃ in the extrusion step, the injection step technological temperature is 320 ℃.
Embodiment 5:
Raw material is formed: polyphenylene sulfide, silica fiber, titanate coupling agent;
Polyphenylene sulfide wherein: silica fiber=7: 3 (weight ratio); Titanate coupling agent weight is 0.2% of silica fiber weight;
Except working temperature, implementing process is with described in the embodiment 1, and the fusing point of polyphenylene sulfide is 280 ℃, so the processing district medial temperature is 320 ℃ in the extrusion step; The injection step technological temperature is 330 ℃.
Embodiment 6:
Raw material is formed: syndiotactic polystyrene, boron nitride fibre, siloxanes coupling agent;
Syndiotactic polystyrene wherein: boron nitride fibre=7: 3 (weight ratio); Siloxanes coupling agent (KH-550) weight is 0.4% of boron nitride fibre weight;
Implementing process is with described in the embodiment 1.
Need to prove that the foregoing description is the technology of formulating to quartz/SP 1 macrofiber, fortifying fibre need be drawn to through towing mechanism and carry out immersion treatment in the treatment solution, then oven dry; If the quartz/boron nitride fibre that uses is staple fibre or whisker, then can staple fibre or whisker directly be added also oven dry after the immersion treatment in the treatment solution, remaining complete processing is constant.
Prepared quartz/boron nitride fibre is strengthened thermoplastic polymer (PS/ppe/polyphenylene sulfide) based composites carry out performance test; Tensile strength is tested according to GB GB/T 1040-1992; Flexural strength and modulus in flexure are tested by GB GB/T 9341-2000; Notched Izod impact strength is tested by GB GB/T 1043-1993, and volume specific resistance is tested by GB GB/T 1410-2006, and specific inductivity and dielectric loss are tested by GB/T 5597-1999; Dielectric strength is tested by GB GB/T1408.1-99, has obtained the result shown in the table 1.
Claims (7)
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| CN2012101242028A CN102634124A (en) | 2012-04-25 | 2012-04-25 | Fiber reinforced thermoplastic polymer matrix composite material and preparation method thereof |
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|---|---|---|---|
| CN2012101242028A CN102634124A (en) | 2012-04-25 | 2012-04-25 | Fiber reinforced thermoplastic polymer matrix composite material and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103660410A (en) * | 2012-09-19 | 2014-03-26 | 上海杰德惠化学科技有限公司 | Wave-transmitting core clamping material of antenna cover and manufacturing method and application thereof |
| CN105694421A (en) * | 2016-03-21 | 2016-06-22 | 中国科学院长春应用化学研究所 | Fiber-reinforced thermoplastic composite material and preparation method thereof |
| CN106674785A (en) * | 2017-01-05 | 2017-05-17 | 辽宁大学 | Preparation method of modified PS (polystyrene) plastic thin film |
| CN107459805A (en) * | 2016-06-06 | 2017-12-12 | 华为技术有限公司 | A kind of antenna for base station cover and its manufacture method |
| CN108437487A (en) * | 2018-04-08 | 2018-08-24 | 武汉纺织大学 | A kind of polyphenyl thioether composite material and preparation method thereof of high content of glass fiber |
| EP3464449B1 (en) | 2016-05-26 | 2019-08-21 | SABIC Global Technologies B.V. | Thermoplastic compositions for electronics or telecommunication applications and shaped article therefore |
| CN110183788A (en) * | 2019-06-26 | 2019-08-30 | 保定威尔达节能科技有限公司 | A kind of fire prevention styrofoam and its production technology |
| CN112251003A (en) * | 2020-09-28 | 2021-01-22 | 广州辰东新材料有限公司 | Low-dielectric nano injection-molded thermoplastic polyester composite material and preparation method and application thereof |
| CN114437496A (en) * | 2022-03-09 | 2022-05-06 | 苏州市安美材料科技有限公司 | Heat-resistant plastic and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103660410A (en) * | 2012-09-19 | 2014-03-26 | 上海杰德惠化学科技有限公司 | Wave-transmitting core clamping material of antenna cover and manufacturing method and application thereof |
| CN105694421A (en) * | 2016-03-21 | 2016-06-22 | 中国科学院长春应用化学研究所 | Fiber-reinforced thermoplastic composite material and preparation method thereof |
| CN105694421B (en) * | 2016-03-21 | 2019-04-26 | 中国科学院长春应用化学研究所 | A kind of fiber reinforced thermoplastic composite material and preparation method thereof |
| EP3464449B1 (en) | 2016-05-26 | 2019-08-21 | SABIC Global Technologies B.V. | Thermoplastic compositions for electronics or telecommunication applications and shaped article therefore |
| CN107459805A (en) * | 2016-06-06 | 2017-12-12 | 华为技术有限公司 | A kind of antenna for base station cover and its manufacture method |
| CN106674785A (en) * | 2017-01-05 | 2017-05-17 | 辽宁大学 | Preparation method of modified PS (polystyrene) plastic thin film |
| CN108437487A (en) * | 2018-04-08 | 2018-08-24 | 武汉纺织大学 | A kind of polyphenyl thioether composite material and preparation method thereof of high content of glass fiber |
| CN110183788A (en) * | 2019-06-26 | 2019-08-30 | 保定威尔达节能科技有限公司 | A kind of fire prevention styrofoam and its production technology |
| CN112251003A (en) * | 2020-09-28 | 2021-01-22 | 广州辰东新材料有限公司 | Low-dielectric nano injection-molded thermoplastic polyester composite material and preparation method and application thereof |
| CN114437496A (en) * | 2022-03-09 | 2022-05-06 | 苏州市安美材料科技有限公司 | Heat-resistant plastic and preparation method thereof |
| CN114437496B (en) * | 2022-03-09 | 2024-01-02 | 苏州市安美材料科技有限公司 | Heat-resistant plastic and preparation method thereof |
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Application publication date: 20120815 |