CN101704993A - PET/LCP flame-retardant plastic and preparation method thereof - Google Patents
PET/LCP flame-retardant plastic and preparation method thereof Download PDFInfo
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- CN101704993A CN101704993A CN200910192886A CN200910192886A CN101704993A CN 101704993 A CN101704993 A CN 101704993A CN 200910192886 A CN200910192886 A CN 200910192886A CN 200910192886 A CN200910192886 A CN 200910192886A CN 101704993 A CN101704993 A CN 101704993A
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Abstract
The invention relates to the technical field of plastics, in particular to a PET/LCP flame-retardant plastic and a preparation method thereof. The invention includes the following materials by weight percentage: 42-69 percent of PET, 5-10 percent of LCP, 5-10 percent of compatilizer, 10-20 percent of glass fiber, 8-12 percent of flame retardant and 3-6 percent of antimony trioxide. The invention adopts the alloying of LCP and PET and fully uses the complementarity of two-phase crystallization to improve the processability of the PET and on the basis, realizes flame-retardant modification. The method can produce high-performance low-cost PET/LCP reinforcing flame-retardant engineering plastic without adding nucleating agent, excessive glass fiber and other modifiers. Proved by testing, the flame-retardant plastic can satisfy the requirement of fire prevention UL94-V0.
Description
Technical field
The present invention relates to the plastics technology field, relate in particular to a kind of PET/LCP flame retardant plastics and preparation method thereof.
Background technology
PET (polyethylene terephthalate) because it not only has good wear resistance, thermotolerance and chemical proofing, and is the most cheap engineering plastics, thereby is extensive use of by people; But defectives such as PET also exists, and some are slow as: crystallization velocity, crystallization imperfection, the bad grasp of degree of crystallinity and injection moulding difficulty make its application be subjected to certain restriction.In order to make full use of the premium properties of PET material, and satisfy its application requiring in all fields simultaneously, the main means that adopt of people are by add various auxiliary agents in PET, to satisfy the demand of people to PET low cost and premium properties thereof at present.Thereby, how to realize that the PET high performance is a new commanding elevation of modification industry contention, for this reason, people have done a large amount of research, as: U.S. Pat P4448913, announced a kind of phenylformic acid and polyolefinic PET mixture of having added; U.S. Pat P3435093 has announced a kind of PET an alkali metal salt that has added ethylene/methacrylic acid; But the two or melting index height, though or the melting index of PET has reduced significantly, and the Shooting Technique parameter is difficult to regulate when big product of moulding or thick article.
Along with development of science and technology, it is found that adding glass fibre not only can improve the intensity of PET system, and the dimensional stability of PET system and hardness are greatly improved; Yet, it only is the importing of glass fibre, its result of use is very limited also, as: when using the glass-fiber-reinforced polyester material to carry out moulding, just must use very high die temperature, reach such temperature, almost be irrealizable in the mouldability industry, so, the substance that the big again quantity research of people with it can fine compatibility.Chinese patent, publication number is that the application documents of CN101070421 discloses a kind of glass-fiber-reinforced polyester matrix material, mainly comprises PET60～66%, nylon-type nucleator 1～3.5%, Resins, epoxy chainextender 0.1～1.0%, oxidation inhibitor 0.05～0.2% and glass fibre 25～35%; Chinese patent, the patent No. is the matrix material that the document of ZL03142021.4 also discloses a kind of glass-fiber-reinforced polyester, having comprised: polyester 45～87%, nucleator are 1～3.5% toughness reinforcing, chainextender 1.5～20%, oxidation inhibitor 0.1～1% and glass fibre 10～37%.Though above dual mode has improved crystallization rate to a certain extent, all also need to improve crystallization rate by interpolation nucleator, crystallization promoter; Both having made and added nucleator and crystallization promoter, also only is suitably to improve, and can't accomplish from carrying out in essence perfectly, still has problems such as goods sticking to mould, size instability, warpage, the mouth of cutting off the water supply, the injection moulding difficulty; And additive dosage is bigger, and is big to performance impact, and cost is also higher.
Summary of the invention
One of purpose of the present invention is at the deficiencies in the prior art, and provide a kind of do not need to add nucleator just can be from having improved PET processibility and crystallization rate in essence, and cost is low and can realize the PET/LCP flame retardant plastics that enhancing is flame-retardant modified.
Two of purpose of the present invention is to provide the preparation method of described a kind of PET/LCP flame retardant plastics.
The present invention is achieved by following technology:
A kind of PET/LCP flame retardant plastics; The material that comprises following weight percent:
PET 42％～69％
LCP 5％～10％
Compatilizer 5%～10%
Glass fibre 10%～20%
Fire retardant 8%～12%
Antimonous oxide 3%～6%
Wherein, PET is a glass-fiber-reinforced polyester, and LCP is a liquid crystal high polymer material, and compatilizer is the olefin polymer that has added glycidyl methacrylate, and glycidyl methacrylate is called for short GMA, and this compatilizer can commercially obtain.
Described fire retardant is the one or more combination thing in decabromodiphynly oxide, eight bromo ether, hexabromocyclododecane, tetrabromo-bisphenol, the brominated epoxy resin.
Described glass fibre is an E type glass fibre.
Preparation method's preparation process of above-mentioned PET/LCP flame retardant plastics is as follows:
A, the PET with above-mentioned amount, LCP, compatilizer, fire retardant and antimonous oxide place stirrer to stir, and make mixture I;
B, the glass fibre of above-mentioned amount is joined among the mixture I, stir;
C, melt extrude, temperature is 250 ℃～280 ℃;
D, pelletizing packing.
Principle of the present invention is: adopt secondary board LCP of import polyester type and PET alloying, make full use of two-phase bonded superiority, produce high performance PET/LCP fire-resistant engineering plastics.LCP still keeps liquid crystal liquid crystal property in other macromolecular material, become the fiber phase, PET there is enhancement, also can meet or exceed physical strength after common engineering materials strengthens with tens percent glass fibre, show the characteristic of high strength and modulus even do not add strongthener.After joining the LCP of disperse phase in the another kind of polymer matrix as a component, under the effect of normal strain and shear strain, the mesomorphic phase generation melt-flow orientation in the compound system causes macromole to become fine, has improved the PET processibility.
Wherein, thermotropic liquid crystalline polymer material (TLCP) abbreviates liquid crystal high polymer material as, and English abbreviates LCP as.LCP is a kind of novel macromolecular material, and this material not only can bear high temperature, under molten state, presents liquid crystal liquid crystal property, and the orientation of height is arranged, so can play fibre-reinforced effect.LCP is excellent performance not only, has high strength, high rigidity, high temperature resistant, high electric insulation, strong flame retardant resistance, linear expansivity is little, molding shrinkage is low and very outstanding advantages such as Young's modulus, and heatproof reaches as high as 350 degree.LCP also has chemical-resistant resistance, acidproof, solvent and stem class etc., and intermolecular winding is considerably less, especially only needs a shear-stress seldom just can make its orientation.
LCP and PET, compatilizer, when fire retardant and antimonous oxide thorough mixing, the design structure that the LCP main chain is cut out by so-called molecule by rigidity or semirigid rod-shaped units segment and flexible unit segment forms. under molten state, this chain structure is bordering in order, form thermodynamically stable liquid crystal, can form height-oriented crystal condensed state structure under external force, be the orderly microcell of liquid crystal. crossing under the cool condition, the relaxation time of LCP molecule is very long, thereby the alignment state in the microcell can remain. this character of liquid crystal polymer condensed state, give the ability of material with self-enhancement. after joining the LCP of disperse phase in the PET matrix as a component, under the effect of normal strain and shear strain, mesomorphic phase generation melt-flow orientation in the compound system, cause macromole to become fine. the microcell particle of orientation is drawn as ellipticity, linear even acicular fiber reinforcement phase. especially under deformation speed, stiff molecule is orientated longshore current to consistent, form big L/D ratio, the fento of dense arrangement, so claim LCP fento REINFORCED PET polymer matrix composites again, the PET/LCP alloy of producing like this need not strengthen and just has very high rigidity and modulus, utilize two advantages that combine simultaneously, the crystallization rate of having improved PET again is slow, the shortcoming of injection moulding difficulty, made full use of the PET low price, the advantage that thermotolerance is high, do not need to add nucleator, do not need to add too much glass and other properties-correcting agent yet and just can produce the PET high performance engineering plastics.
Beneficial effect of the present invention is: the present invention utilizes LCP and PET alloying, does compatilizer by adding band glycidyl methacrylate (GMA) olefin polymer, improves the biphase consistency, realizes the alloying of LCP and PET; By adding a small amount of E type glass fibre, improve the second-order transition temperature of alloy, improve rigidity and modulus.By bromine class fireproofing agent and the modification of antimonous oxide cooperative flame retardant, make material reach the UL94V-0 requirement, the present invention utilizes two advantages that combine simultaneously, the crystallization rate of fundamentally improving PET reaches the shortcoming of injection moulding difficulty slowly, and makes full use of PET low price, advantage that thermotolerance is high, does not need to add nucleator, do not need to add too much glass fibre and other properties-correcting agent yet, just can produce the low PET high-performance refractory engineering plastics of cost, after tested, reach the requirement of fire prevention UL94-V0.
The present invention adopts LCP and PET alloying, make full use of two-phase crystalline complementarity, improve the PET processibility, and realize strengthening flame-retardant modified on this basis, the PET/LCP that produces high performance strengthens fire-resistant engineering plastics, makes full use of the LCP of the secondary board polyester type in market, reduces production costs, also do not have at present PET/LCP to strengthen the research and the patent report of fire-resistant engineering plastics, belong to initiative.
Description of drawings
Fig. 1 is preparation technology's schema of PET/LCP flame retardant plastics of the present invention.
Embodiment
Understand the present invention for the ease of those skilled in the art, enumerate several specific embodiments below the present invention is described further:
Embodiment 1
A kind of PET/LCP flame retardant plastics; PET 42% by weight percentage, LCP 10%, compatilizer 10%, decabromodiphynly oxide 12%, antimonous oxide 6% have been comprised.
The preparation method of above-mentioned PET/LCP flame retardant plastics, preparation process is as follows:
A, the PET with above-mentioned amount, LCP, compatilizer, decabromodiphynly oxide and antimonous oxide place stirrer to stir, and make mixture I;
B, 20% glass fibre is joined among the mixture I, stir;
C, melt extrude, temperature is 250 ℃;
D, pelletizing packing.
Embodiment 2
A kind of PET/LCP flame retardant plastics; PET 50% by weight percentage, LCP 6%, compatilizer 6%, eight bromo ether 12%, antimonous oxide 6% have been comprised.
The preparation method of above-mentioned PET/LCP flame retardant plastics, preparation process is as follows:
A, the PET with above-mentioned amount, LCP, compatilizer, eight bromo ether and antimonous oxide place stirrer to stir, and make mixture I;
B, 20% glass fibre is joined among the mixture I, stir;
C, melt extrude, temperature is 260 ℃;
D, pelletizing packing.
Embodiment 3
A kind of PET/LCP flame retardant plastics; PET 54% by weight percentage, LCP 10%, compatilizer 8%, hexabromocyclododecane 10%, antimonous oxide 3%. have been comprised
The preparation method of above-mentioned PET/LCP flame retardant plastics, preparation process is as follows:
A, the PET with above-mentioned amount, LCP, compatilizer, hexabromocyclododecane and antimonous oxide place stirrer to stir, and make mixture I;
B, 15% glass fibre is joined among the mixture I, stir;
C, melt extrude, temperature is 270 ℃;
D, pelletizing packing.
Embodiment 4
A kind of PET/LCP flame retardant plastics; PET 64%, LCP% by weight percentage, compatilizer 8%, brominated epoxy resin 8%, antimonous oxide 3% have been comprised.
The preparation method of above-mentioned PET/LCP flame retardant plastics, preparation process is as follows:
A, the PET with above-mentioned amount, LCP, compatilizer, brominated epoxy resin and antimonous oxide place stirrer to stir, and make mixture I;
B, 12% glass fibre is joined among the mixture I, stir;
C, melt extrude, temperature is 280 ℃;
D, pelletizing packing.
Embodiment 5
A kind of PET/LCP flame retardant plastics; PET69% by weight percentage, LCP 5%, compatilizer 5%, fire retardant (forming), antimonous oxide 3% have been comprised by what 6% eight bromo ether of 2% decabromodiphynly oxide.
The preparation method of above-mentioned PET/LCP flame retardant plastics, preparation process is as follows:
A, the PET with above-mentioned amount, LCP, compatilizer, fire retardant and antimonous oxide place stirrer to stir, and make mixture I;
B, 10% glass fibre is joined among the mixture I, stir;
C, melt extrude, temperature is 260 ℃;
D, pelletizing packing.
Embodiment 6
A kind of PET/LCP flame retardant plastics; PET 59% by weight percentage, LCP 5%, compatilizer 5%, fire retardant (forming), antimonous oxide 3% have been comprised by 2% decabromodiphynly oxide, 2% hexabromocyclododecane, 2% tetrabromo-bisphenol and 2% brominated epoxy resin.
The preparation method of above-mentioned PET/LCP flame retardant plastics, preparation process is as follows:
A, the PET with above-mentioned amount, LCP, compatilizer, fire retardant and antimonous oxide place stirrer to stir, and make mixture I;
B, 20% glass fibre is joined among the mixture I, stir;
C, melt extrude, temperature is 280 ℃;
D, pelletizing packing.
The present invention is through detecting, and its physical data sees the following form:
As can be seen from the above table, do not adding nucleator, only adding under the situation of a small amount of glass fibre and other properties-correcting agent, the performance of the plastics each side of producing can both reach high standard, but also has flame retardant effect simultaneously, the fire-retardant requirement that reaches fire prevention UL94-V0.
The above embodiment is a preferred embodiments of the present invention, is not to limit the scope of the present invention, so all equivalences of doing according to the described structure of claim of the present invention, feature and principle change or modify, all should be included in the claim scope of the present invention.
Claims (4)
1. a PET/LCP flame retardant plastics is characterized in that, comprises the material of following weight percent:
PET 42％～69％
LCP 5％～10％
Compatilizer 5%～10%
Glass fibre 10%～20%
Fire retardant 8%～12%
Antimonous oxide 3%～6%
Wherein, PET is a polyethylene terephthalate, and LCP is a liquid crystal high polymer material, and compatilizer is the olefin polymer that has added glycidyl methacrylate.
2. PET/LCP flame retardant plastics according to claim 1 is characterized in that, described fire retardant is the one or more combination thing in decabromodiphynly oxide, eight bromo ether, hexabromocyclododecane, tetrabromo-bisphenol, the brominated epoxy resin.
3. PET/LCP flame retardant plastics according to claim 1 is characterized in that, described glass fibre is an E type glass fibre.
4. the preparation method of the described PET/LCP flame retardant plastics of claim 1-3 is characterized in that preparation process is as follows:
A, the PET with above-mentioned amount, LCP, compatilizer, fire retardant and antimonous oxide place stirrer to stir, and make mixture I;
B, the glass fibre of above-mentioned amount is joined among the mixture I, stir;
C, melt extrude, temperature is 250 ℃～280 ℃;
D, pelletizing packing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910192886A CN101704993A (en) | 2009-09-30 | 2009-09-30 | PET/LCP flame-retardant plastic and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910192886A CN101704993A (en) | 2009-09-30 | 2009-09-30 | PET/LCP flame-retardant plastic and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040812A (en) * | 2010-12-30 | 2011-05-04 | 深圳市科聚新材料有限公司 | Polyethylene terephthalate (PET)/liquid crystal polymer (LCP) engineering plastics as well as preparation method and application thereof |
| CN102070888A (en) * | 2010-12-30 | 2011-05-25 | 金发科技股份有限公司 | High-strength polyarylether ester composite and preparation method thereof |
| CN102477215A (en) * | 2010-11-25 | 2012-05-30 | 合肥杰事杰新材料股份有限公司 | Heat-conducting flame-retardant polyethylene terephthalate composite and preparation method thereof |
| CN103275508A (en) * | 2013-06-21 | 2013-09-04 | 苏州新区特氟龙塑料制品厂 | Flame-retarding plastics |
| CN107383807A (en) * | 2017-08-25 | 2017-11-24 | 广东壹豪新材料科技股份有限公司 | A kind of LCP/PBT/PET ternary-alloy materials and preparation method thereof |
| CN107459807A (en) * | 2017-08-25 | 2017-12-12 | 广东壹豪新材料科技股份有限公司 | A kind of PPO/LCP/PET ternary-alloy materials and preparation method thereof |
| CN109385113A (en) * | 2018-10-30 | 2019-02-26 | 佛山市合宏泰业科技有限公司 | A kind of impact resistance PET/LCP composite material |
| CN109880310A (en) * | 2019-01-24 | 2019-06-14 | 广东壹豪新材料科技股份有限公司 | A kind of POK, TLCP, PET trielement composite material and its preparation process |
| CN110041665A (en) * | 2019-03-29 | 2019-07-23 | 苏州威瑞成新材料有限公司 | Heat-resisting highly crystalline REINFORCED PET/LCP alloy material of one kind and preparation method thereof |
| CN113492563A (en) * | 2021-07-09 | 2021-10-12 | 宁夏清研高分子新材料有限公司 | Flame-retardant LCP plastic |
-
2009
- 2009-09-30 CN CN200910192886A patent/CN101704993A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477215A (en) * | 2010-11-25 | 2012-05-30 | 合肥杰事杰新材料股份有限公司 | Heat-conducting flame-retardant polyethylene terephthalate composite and preparation method thereof |
| CN102477215B (en) * | 2010-11-25 | 2015-03-25 | 合肥杰事杰新材料股份有限公司 | Heat-conducting flame-retardant polyethylene terephthalate composite and preparation method thereof |
| CN102040812B (en) * | 2010-12-30 | 2012-08-22 | 深圳市科聚新材料有限公司 | Polyethylene terephthalate (PET)/liquid crystal polymer (LCP) engineering plastics as well as preparation method and application thereof |
| CN102040812A (en) * | 2010-12-30 | 2011-05-04 | 深圳市科聚新材料有限公司 | Polyethylene terephthalate (PET)/liquid crystal polymer (LCP) engineering plastics as well as preparation method and application thereof |
| CN102070888B (en) * | 2010-12-30 | 2013-06-12 | 金发科技股份有限公司 | High-strength polyarylether ester composite and preparation method thereof |
| CN102070888A (en) * | 2010-12-30 | 2011-05-25 | 金发科技股份有限公司 | High-strength polyarylether ester composite and preparation method thereof |
| CN103275508A (en) * | 2013-06-21 | 2013-09-04 | 苏州新区特氟龙塑料制品厂 | Flame-retarding plastics |
| CN107383807A (en) * | 2017-08-25 | 2017-11-24 | 广东壹豪新材料科技股份有限公司 | A kind of LCP/PBT/PET ternary-alloy materials and preparation method thereof |
| CN107459807A (en) * | 2017-08-25 | 2017-12-12 | 广东壹豪新材料科技股份有限公司 | A kind of PPO/LCP/PET ternary-alloy materials and preparation method thereof |
| CN109385113A (en) * | 2018-10-30 | 2019-02-26 | 佛山市合宏泰业科技有限公司 | A kind of impact resistance PET/LCP composite material |
| CN109880310A (en) * | 2019-01-24 | 2019-06-14 | 广东壹豪新材料科技股份有限公司 | A kind of POK, TLCP, PET trielement composite material and its preparation process |
| CN110041665A (en) * | 2019-03-29 | 2019-07-23 | 苏州威瑞成新材料有限公司 | Heat-resisting highly crystalline REINFORCED PET/LCP alloy material of one kind and preparation method thereof |
| CN113492563A (en) * | 2021-07-09 | 2021-10-12 | 宁夏清研高分子新材料有限公司 | Flame-retardant LCP plastic |
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Open date: 20100512 |