CN102732020A - Flame-retardant glass fiber reinforced polyamide (PA) 66/ poly-p-phenylene oxide (PPO) alloy composition and preparation method thereof - Google Patents
Flame-retardant glass fiber reinforced polyamide (PA) 66/ poly-p-phenylene oxide (PPO) alloy composition and preparation method thereof Download PDFInfo
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- CN102732020A CN102732020A CN2012102473354A CN201210247335A CN102732020A CN 102732020 A CN102732020 A CN 102732020A CN 2012102473354 A CN2012102473354 A CN 2012102473354A CN 201210247335 A CN201210247335 A CN 201210247335A CN 102732020 A CN102732020 A CN 102732020A
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- 239000000956 alloy Substances 0.000 title claims abstract description 26
- 239000003063 flame retardant Substances 0.000 title claims abstract description 26
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 25
- 239000003365 glass fiber Substances 0.000 title claims abstract description 25
- 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 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 title claims abstract 7
- 239000004952 Polyamide Substances 0.000 title abstract 4
- 229920002647 polyamide Polymers 0.000 title abstract 4
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 title abstract 2
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 4
- 239000002270 dispersing agent Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000005461 lubrication Methods 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000001050 lubricating effect Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000001012 protector Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 4
- 230000002950 deficient Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000004807 localization Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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Abstract
The invention relates to a flame-retardant glass fiber reinforced polyamide (PA) 66/ poly-p-phenylene oxide (PPO) alloy composition and a preparation method of the composition. The composition comprises the components by weight percent: 20-41% of PA66, 20-41% of PPO, 0-10% of compatilizer, 0-15% of compound flame retardant masterbatch, 20-40% of glass fiber, 0.1-1% of antioxidant and 0.1-1% of lubricating dispersing agent. The preparation method of the composition comprises the following steps of: weighing all the components according to the weight ratio, putting the components in a high mixing machine, mixing for 2-5min and discharging; and then extruding and pelleting by using a twin-screw extruder, wherein the processing temperature is 245-270 DEG C, and the screw revolution is 30-40Hz. Compared with the prior art, the composition has the advantages of being high in comparative tracking index (CTI), low in flame retardant precipitation, halogen-free, environment-friendly, balanced in comprehensive performance and the like, thus being widely applied to products in the field of electronic and electric appliances such as a contactor, a leakage protector, a shell of a circuit breaker and the like.
Description
Technical field
The present invention relates to a kind of flame-proof glass fibre and strengthen alloy material, be specifically related to a kind of flame-proof glass fibre and strengthen PA66/PPO alloy composite and preparation method thereof.
Background technology
In recent years; The electric industrial boom of China; Increasing demand to the fire-retardant enhancement engineering plastics of high electric insulation increases, all need be with the engineering plastic materials with good comprehensive mechanical properties, flame retardant properties and electrical insulation capability like low-voltage vacuum contactor, isolating switch, earth leakage protective device, connector, low-tension switch, the electric element of thin-walled etc.In this product scope, the consumption of nylon/PPO alloy is maximum.Yet because the relative industry of development of fire retardant lags behind concerning the requirement that material improves day by day, a variety of fire retardants join mechanical property, the electrical insulation capability that can greatly reduce material in the material.For example, phase ratio creepage tracking index (CTI) drops to 200V even lower from 600V, and in addition, along with the enforcement of RoHs of European Union and WEEE instruction, traditional bromine is that flame-retardant system can not satisfy this requirement, and the use of some fire retardant simultaneously also can be restricted.Along with development of technology engineering plastics process of localization is also being accelerated.Rizhisheng New Technology Development Co., Ltd., Shanghai strengthens the PA66/PPO product to high CTI value, the low fire retardant property separated out flame-proof glass fibre and has carried out deep research.The high CTI value of being developed, the low fire retardant property separated out, flame-proof glass fibre strengthen the PA66/PPO alloy product and have successfully substituted the like product that companies such as BASF produce; Realized the production domesticization of this series products; When being included in the localization of raw material plan by some foreign capital affiliates, this material also begins to export to the European and American areas.
Summary of the invention
The objective of the invention is to overcome the defective that above-mentioned prior art exists, provide a kind of flame-proof glass fibre to strengthen PA66/PPO alloy composite and preparation method thereof.Compsn of the present invention has high CTI value, the low fire retardant property separated out, halogen-free environmental, and advantages such as over-all properties equilibrium can be widely used in the product of field of electronics such as contactor, earth leakage protective device, case for circuit breaker.
The objective of the invention is to realize through following technical scheme:
The present invention relates to a kind of flame-proof glass fibre and strengthen the PA66/PPO alloy composite, comprise each component of following weight percent content:
Preferably, the limiting viscosity of described PA66 is 2.4dL/g.
Preferably, the limiting viscosity of described PPO is 0.3～0.6dL/g.
Preferably, described compositional flame-retardant master batch is composite voluntarily by my company, is mixed by three kinds of components, specifically comprises each component of following weight percent content: deironing red phosphorus master batch: 50%; Antimigration agent: 25%; High CTI auxiliary agent: 25%.
Preferably, said spun glass is the alkali free glass fibre that handle through silane coupling agent on the surface.
Preferably, said oxidation inhibitor is Hinered phenols antioxidant.
Preferably, described lubrication dispersing agent is a silicone.
The invention still further relates to a kind of preparation method of aforesaid flame-proof glass fibre enhancing PA66/PPO alloy composite, be specially: said each component is put into high-speed mixer and mixing by weight ratio, discharging, the twin screw extruder extruding pelletization gets final product.
Preferably, the said blended time is 2～5 minutes.
Preferably, the extrusion temperature of said twin screw extruder is 245～270 ℃, and the screw rod revolution is 30～40HZ.
Compared with prior art, the present invention has following beneficial effect:
1, adopt compositional flame-retardant master batch system, compare with traditional fire-retardant master granule, compositional flame-retardant master batch system has following characteristics: 1) comprehensive mechanical property is higher; 2) can CTI be brought up to 660V from 320V; 3) overcome the product surface that common red phosphorus moves under certain condition, under the effect of oxygen G&W, finally to form the mordant phosphorus of metallic article be the defective of acidic substance to red phosphorus then.
2, the oxidation inhibitor that adds is Hinered phenols antioxidant, can improve compsn in the antioxidant property of the course of processing and the ageing resistance in the use.
3, adopt silicone as lubricant, improve the materials processed flowability, reduce frictional coefficient; Improve smooth property, under specific processing conditions, adopt dispersiveness better, the residence time is short; Shear weak slightly combination, prevent that fire retardant from decomposing, thereby guaranteed the steady quality of material.
4, have high CTI value, the low fire retardant property separated out, halogen-free environmental, advantages such as over-all properties equilibrium can be widely used in the product of field of electronics such as contactor, earth leakage protective device, case for circuit breaker.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.Following examples will help those skilled in the art further to understand the present invention, but not limit the present invention in any form.Should be pointed out that to those skilled in the art, under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement.These all belong to protection scope of the present invention.
Comparative Examples 1～3
The PA66/PPO alloy composite comprises each component of the weight percent content shown in the table 1; Its preparation method is following:
(1) takes by weighing raw material by the weight percent content shown in the table 1, put into high-speed mixer and mixing 2～5 minutes, discharging;
(2) above-mentioned mixed raw materials is added twin screw extruder, extruding pelletization, both said PA66/PPO alloy composite; Parameters such as the extrusion temperature of said twin screw extruder, screw rod revolution are as shown in table 2.
Embodiment 1～8
Flame-proof glass fibre strengthens the PA66/PPO alloy composite, comprises each component of the weight percent content shown in the table 1; Its preparation method is following:
(1) takes by weighing raw material by the weight percent content shown in the table 1, put into high-speed mixer and mixing 2～5 minutes, discharging; Compositional flame-retardant master batch in the table 1 comprises each component of following mass percentage content: deironing red phosphorus master batch: 50%; Antimigration agent: 25%; High CTI auxiliary agent: 25%;
(2) above-mentioned mixed raw materials is added twin screw extruder, extruding pelletization, both said flame-proof glass fibre enhancing PA66/PPO alloy composite; Parameters such as the extrusion temperature of said twin screw extruder, screw rod revolution are as shown in table 2.
The formula for raw stock of table 1 Comparative Examples 1～3 and embodiment 1～8
| Material name | PA66 | PPO | Compatilizer | The compositional flame-retardant master batch | Spun glass | Oxidation inhibitor | Lubrication dispersing agent |
| Comparative Examples 1 | 37.3 | 27 | 3 | 12 | 20 | 0.2 | 0.5 |
| Comparative Examples 2 | 33.3 | 27 | 3 | 11 | 25 | 0.2 | 0.5 |
| Comparative Examples 3 | 24.3 | 27 | 3 | 10 | 35 | 0.2 | 0.5 |
| Embodiment 1 | 27.3 | 30 | 9 | 0 | 33 | 0.4 | 0.3 |
| Embodiment 2 | 20 | 41 | 8 | 9.5 | 20 | 1 | 0.5 |
| Embodiment 3 | 25.3 | 27 | 3 | 9 | 35 | 0.1 | 0.6 |
| Embodiment 4 | 21.3 | 27 | 3 | 8 | 40 | 0.2 | 0.5 |
| Embodiment 5 | 22.3 | 27 | 3 | 7 | 40 | 0.2 | 0.5 |
| Embodiment 6 | 23.3 | 27 | 3 | 6 | 40 | 0.6 | 0.1 |
| Embodiment 7 | 41 | 20 | 10 | 5.8 | 22 | 0.2 | 1 |
| Embodiment 8 | 30 | 27 | 0 | 15 | 27 | 0.2 | 0.8 |
Table 2
Embodiment 9, performance test
Adopt the ASTM standard, the PA66/PPO alloy combination matter sample to embodiment 1～8 and Comparative Examples 1～3 make carries out the performance test contrast.The test performance contrast is as shown in table 3:
Table 3
Can know that by table 3 embodiment 1 compares with Comparative Examples 1,2,3, the high CTI, the low property the separated out flame-proof PA 6/PA12 alloy composite that adopt compositional flame-retardant master batch system of the present invention to make are described, have following some advantage:
(1) comprehensive mechanical property is higher: on mechanical performance indexs such as tensile strength, flexural strength, modulus in flexure, shock strength, all obtain bigger raising;
(2) the CTI value is higher: CTI is brought up to 660V from 320V;
(3) pH value that obtains of corrosion test becomes neutrality by acidity; Explain that the compositional flame-retardant master batch system that the present invention adopts has overcome the product surface that common red phosphorus moves in traditional fire-retardant master granule system under certain condition, under the effect of oxygen G&W, finally to form the mordant phosphorus of metallic article be the defective of acidic substance to red phosphorus then.
In sum, compsn of the present invention has high CTI value, the low fire retardant property separated out, halogen-free environmental, and advantages such as over-all properties equilibrium can be widely used in the product of field of electronics such as contactor, earth leakage protective device, case for circuit breaker.
Claims (10)
1. a flame-proof glass fibre strengthens the PA66/PPO alloy composite, it is characterized in that said composition comprises each component of following weight percent content:
2. flame-proof glass fibre according to claim 1 strengthens the PA66/PPO alloy composite, it is characterized in that the limiting viscosity of described PA66 is 2.4dL/g.
3. flame-proof glass fibre according to claim 1 strengthens the PA66/PPO alloy composite, it is characterized in that the limiting viscosity of described PPO is 0.3～0.6dL/g.
4. flame-proof glass fibre according to claim 1 strengthens the PA66/PPO alloy composite, it is characterized in that described compositional flame-retardant master batch comprises each component of following weight percent content: deironing red phosphorus master batch: 50%; Antimigration agent: 25%; High CTI auxiliary agent: 25%.
5. flame-proof glass fibre according to claim 1 strengthens the PA66/PPO alloy composite, it is characterized in that, described spun glass is the alkali free glass fibre that handle through silane coupling agent on the surface.
6. flame-proof glass fibre according to claim 1 strengthens the PA66/PPO alloy composite, it is characterized in that described oxidation inhibitor is Hinered phenols antioxidant.
7. flame-proof glass fibre according to claim 1 strengthens the PA66/PPO alloy composite, it is characterized in that described lubrication dispersing agent is a silicone.
8. a flame-proof glass fibre as claimed in claim 1 strengthens the preparation method of PA66/PPO alloy composite; It is characterized in that said preparation method is specially: said each component is put into high-speed mixer and mixing, discharging by weight ratio; The twin screw extruder extruding pelletization gets final product.
9. flame-proof glass fibre according to claim 8 strengthens the preparation method of PA66/PPO alloy composite, it is characterized in that the said blended time is 2～5 minutes.
10. flame-proof glass fibre according to claim 8 strengthens the preparation method of PA66/PPO alloy composite, it is characterized in that the extrusion temperature of said twin screw extruder is 245～270 ℃, and the screw rod revolution is 30～40Hz.
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| CN2012102473354A CN102732020A (en) | 2012-07-17 | 2012-07-17 | Flame-retardant glass fiber reinforced polyamide (PA) 66/ poly-p-phenylene oxide (PPO) alloy composition and preparation method thereof |
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| CN2012102473354A CN102732020A (en) | 2012-07-17 | 2012-07-17 | Flame-retardant glass fiber reinforced polyamide (PA) 66/ poly-p-phenylene oxide (PPO) alloy composition and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044896A (en) * | 2012-12-06 | 2013-04-17 | 上海日之升新技术发展有限公司 | High glow wire flame retarding reinforced PPO/PA alloy and preparation method thereof |
| CN106987120A (en) * | 2017-04-20 | 2017-07-28 | 广州市聚赛龙工程塑料股份有限公司 | A kind of oil resistant high CTI value halogen free flame-retardant polyphenylene oxide composite material and preparation method thereof |
| CN106987121A (en) * | 2017-05-02 | 2017-07-28 | 广州市聚赛龙工程塑料股份有限公司 | A kind of polyphenylene oxide composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382464A (en) * | 2011-09-07 | 2012-03-21 | 上海日之升新技术发展有限公司 | High-CTI (comparative tracking index) value and low-corrosivity red phosphorus flame-retarding glass fiber reinforced PA66 (polyamide 66) material and preparation method thereof |
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- 2012-07-17 CN CN2012102473354A patent/CN102732020A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382464A (en) * | 2011-09-07 | 2012-03-21 | 上海日之升新技术发展有限公司 | High-CTI (comparative tracking index) value and low-corrosivity red phosphorus flame-retarding glass fiber reinforced PA66 (polyamide 66) material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044896A (en) * | 2012-12-06 | 2013-04-17 | 上海日之升新技术发展有限公司 | High glow wire flame retarding reinforced PPO/PA alloy and preparation method thereof |
| CN106987120A (en) * | 2017-04-20 | 2017-07-28 | 广州市聚赛龙工程塑料股份有限公司 | A kind of oil resistant high CTI value halogen free flame-retardant polyphenylene oxide composite material and preparation method thereof |
| CN106987121A (en) * | 2017-05-02 | 2017-07-28 | 广州市聚赛龙工程塑料股份有限公司 | A kind of polyphenylene oxide composite material and preparation method thereof |
| CN106987121B (en) * | 2017-05-02 | 2020-05-19 | 广州市聚赛龙工程塑料股份有限公司 | Polyphenyl ether composite material and preparation method thereof |
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Application publication date: 20121017 |