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
- coupling agent
- fortifying fibre
- fiber reinforced
- polymer matrix
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Abstract
The invention discloses a fiber reinforced thermoplastic polymer matrix composite material which is prepared by a thermoplastic polymer, reinforced fiber, and a coupling agent the weight ratio of which is 0.2%-1% that of the reinforced fiber, wherein the weight ratio of the thermoplastic polymer to the reinforced fiber is 1:1-9:1, the thermoplastic polymer is a mixture of any one, two or three of polystyrene (PS), polyphenyl oxide (PPO) and polyphenylene sulfide (PPS), the reinforced fiber is a mixture of quartz fiber or boron nitride fiber, and the coupling agent is silane coupling agent or ester titanate coupling agent; and the material has the advantages of high insulation strength, small dielectric constant, high tensile strength, high flexural strength and the like, and can be used for functional structure members such as a high-pressure insulating device, a satellite communication window, a radome and the like; and the invention further provides a preparation method for the 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)
1. fiber reinforced thermolplastic polymer matrix composite; It is characterized in that: 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, ppe and polyphenylene sulfide; Said fortifying fibre is silica fiber and/or boron nitride fibre, and said coupling agent is silane coupling agent or titanate coupling agent.
2. fiber reinforced thermolplastic polymer matrix composite according to claim 1 is characterized in that: the weight ratio of said thermoplastic polymer and fortifying fibre is 7: 3～9: 1.
3. fiber reinforced thermolplastic polymer matrix composite according to claim 1 and 2 is characterized in that: said silica fiber is silicon-dioxide (SiO
2) content is greater than 99.9% quartz glass fibre.
4. fiber reinforced thermolplastic polymer matrix composite according to claim 3 is characterized in that: said PS is any in general purpose polystyrene, syndiotactic polystyrene, isotactic polyphenylacetylene or the high impact resistance polystyrene; Said ppe is Noryl.
5. fiber reinforced thermolplastic polymer matrix composite according to claim 4 is characterized in that: said fortifying fibre is a whisker.
6. a method of making claim 1 or 2 said fiber reinforced thermolplastic polymer matrix composites is characterized in that, 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.
7. a method of making claim 1 or 2 said fiber reinforced thermolplastic polymer matrix composites is characterized in that, 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.
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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 thermolplastic 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 |