CN104004326A - Polyester composite material and preparation method thereof - Google Patents
Polyester composite material and preparation method thereof Download PDFInfo
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- CN104004326A CN104004326A CN201310060148.XA CN201310060148A CN104004326A CN 104004326 A CN104004326 A CN 104004326A CN 201310060148 A CN201310060148 A CN 201310060148A CN 104004326 A CN104004326 A CN 104004326A
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Abstract
The invention discloses a thermoplastic polyester resin composition with a low molding shrinkage, and a preparation method thereof. The thermoplastic polyester resin composition comprises, by weight, 100 parts of thermoplastic polyester resin, 10-45 parts of a styrene-acrylonitrile copolymer, 5-50 parts of an inorganic powdery filler and 5-50 parts of glass flake. The method is simple to operate, and the prepared composition is environmentally-friendly, has excellent molding machinability, and can be widely applied in the fields of electrical and electronic equipment, household equipment, office automation equipment, automobiles and the like.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of low molding shrinkage polymer blend and preparation method thereof.
Background technology
Thermoplastic polyester, as polybutylene terephthalate (PBT), Poly(Trimethylene Terephthalate) (PPT) and polyethylene terephthalate (PET) have excellent mechanical property and electric property, especially the very excellent shaping processability of polybutylene terephthalate, is extremely widely used in the fields such as electronic electric equipment, housed device, business automation equipment, automobile and mechanical means.
But it is low that vibrin exists second-order transition temperature simultaneously, product molding shrinking percentage is larger, the shortcoming such as rigidity deficiency under high temperature.Large quantity research attempts to improve above defect by blending and modifying, realizes constituent materials and has complementary advantages.Particularly, about the shrinking percentage aspect of vibrin, the natural characteristics of the molecular structure of vibrin own, removes molecular interlocking legibility, the features such as slippage is easy relatively, the easy orientation of crystallization, cause material in polyester resin anisotropy, the horizontal and vertical shrinking percentage of product differs larger, and warpage easily occurs.In recent years, due to the increase in demand of large-scale thin wall parts, the dimensional stability of vibrin and anti-warpage become a major issue.
Improve the publication of vibrin shrinking percentage, mainly with vibrin and amorphous polymer blending and modifying, as add PC, Chinese patent 1789333(publication number) < < environmental-friendly fire-retardant PC/PBT polyblend > >, Chinese patent 101914271A(publication number) < < environment-friendly flame retardant PBT/PC matrix material and preparation method thereof > > etc.; Or adding ABS, Chinese patent 102617997A(publication number) < < glass fibre strengthens PBT/PET matrix material and preparation method thereof > >; Again or adopt nucleator to improve, as Chinese patent 102040808A(publication number) the low warp glass fiber REINFORCED PET/PBT of < < high gloss Alloy And Preparation Method > >, Chinese patent 102070884A(publication number) < < flame-proof glass fibre REINFORCED PET/PBT Alloy And Preparation Method > > etc.These methods lay particular emphasis on from the viewpoint of improving vibrin crystallization, on the one hand, molding shrinkage to improve effect limited, too much the membership that adds of amorphous polymer reduces Some Mechanical Properties on the other hand.
Summary of the invention
In order to solve above-mentioned defect of the prior art, the present invention is combined with by foliated glass scale and fleut, effectively improves the molding shrinkage situation of polyester material.
In order to realize the molding shrinkage situation of improving polyester composite, the present invention has adopted following technical scheme.A polyester composite for low molding shrinkage, the main proportioning of said composition is as follows:
(a) thermoplastic polyester: 100 weight parts;
(b) styrene-acrylonitrile copolymer: 10-45 weight part;
(c) inorganic fleut: 5-50 weight part;
(d) glass flake: 5-50 weight part.
The natural characteristics of the molecular structure of thermoplastic polyester own, molecular interlocking legibility is removed, slippage is easy relatively, the features such as the easy orientation of crystallization, cause thermoplastic polyester material anisotropy, and the stress relaxation in moulding thermal history later stage and secondary crystal etc. cause product molding shrinking percentage large, and its horizontal and vertical shrinking percentage of product differs also larger.The polyester material that particularly glass fibre strengthens, its Injection Molding direction and moving phase vertical direction difference are larger.In the present invention, contriver find due to one-dimensional square to the anisotropy that causes of orientation (resin flows orientation or glass fibre orientation), can pass through two-dimensional shapes material (flaky material, as glass flake) interpolation, or with powdery (or claim three dimensional particles shape) thus the synergy of filler effectively improved.Therefore used (c) inorganic fleut and (d) glass flake in the present invention, the shrinking percentage of polyester composite reduced greatly.
The present invention is for described component (a) thermoplastic polyester, there is no special requirement, consider the popularity of current application, can be preferably any one or a few in polybutylene terephthalate (PBT), Poly(Trimethylene Terephthalate) (PTT) or polyethylene terephthalate (PET).
The present invention is for described component (b) styrene-acrylonitrile copolymer, there is no special requirement, consider with polyester material interface compatibility and improve, styrene-acrylonitrile copolymer is preferably acrylonitrile-styrene-glycidyl methacrylate copolymer, wherein, acrylonitrile content is the 10-40wt% of styrene-acrylonitrile copolymer, the 0.1-10wt% that glycidyl methacrylate content is styrene-acrylonitrile copolymer.
Described component (c) inorganics fleut is selected from one or more in aluminum oxide, zinc oxide, calcium oxide, zinc sulphide, Iron sulfuret, barium sulfate, zinc sulfate, Tai-Ace S 150, calcium sulfate, calcium carbonate, zinc carbonate or aluminium carbonate.More preferably barium sulfate, calcium sulfate or calcium carbonate.Calcium carbonate most preferably.Above-mentioned filler also can be processed with one or more surface treatment agent of coupling agent, organism or inorganics etc., preferably with coupling agent, carries out surface treatment as silane coupling agent, titanate coupling agent or aluminate coupling agent by known method.
Described component (d) glass flake is preferably non-alkali glass scale, and its thickness is 2-10 μ m, and sheet footpath is 10-300 order.
Said composition can also contain:
(e) fire retardant: 10-30 weight part;
(f) auxiliary flame retardant: 1-10 weight part;
(g) fortifying fibre: 20-70 weight part;
Described component (e) fire retardant is selected from one or more in tetrabromo-bisphenol, decabromodiphynly oxide, pentabromotoluene, hexabromocyclododecane, TDE, three-(tribromophenoxy)-triazine, brominated Polystyrene or brominated epoxy resin;
Described component (f) auxiliary flame retardant is selected from one or several in antimony type oxide or metaantimmonic acid salt;
Described component (g) fortifying fibre is one or several in glass fibre, carbon fiber, basalt fibre or aromatic polyamide fibre, and preferably fortifying fibre is special crosssection glass fibre, and aspect ratio is between 2-6.
The present invention provides a kind of preparation method of polyester composite of above-mentioned low molding shrinkage in addition.
By carry out melt blending after raw material pre-mixing at 200-270 ℃, obtain polyester composite;
The main proportioning of raw material is as follows:
(a) thermoplastic polyester: 100 weight parts;
(b) styrene-acrylonitrile copolymer: 10-45 weight part;
(c) inorganic fleut: 5-50 weight part;
(d) glass flake: 5-50 weight part.
The kind of main ingredient and proportioning are as described above.
In material, can also comprise:
(e) fire retardant: 10-30 weight part;
(f) auxiliary flame retardant: 1-10 weight part;
(g) fortifying fibre: 20-70 weight part;
Their kind and component are as described above.
In addition, can be as required, not damage the present invention, be limited to add conventionally use the known material adding, such as anti-dripping agent, hydrolysis-resisting agent, antioxidant, the reagent of avoiding light or ultraviolet light degradation, lubricant, releasing agent, tinting material, nucleator or softening agent etc. in thermoplastic resin.It is functional that the use of these auxiliary agents can improve some of composition, but its basic flame retardant properties and its mechanical properties are not had to what impact, can select general these commercially available auxiliary agents, and they are not necessary for the present invention.The consumption of other auxiliary agents can be according to the object consumption interpolation routinely of adding auxiliary agent.
By the design of above formula and complete processing, the shrinking percentage of resulting polyester reduces greatly.Due to its good thermotolerance, mechanical property and excellent flame retardant properties itself, the fields such as widespread use automobile, electronic apparatus component.
Embodiment
Adopt melt blending extrusion mechanism standby, the length-to-diameter ratio of twin screw extruder is 45, has 13 heating zone; The feeding device that has two cuff measuring instruments; With vacuum-pumping equipment.
Raw material explanation:
Polybutylene terephthalate PBT, 1050M, toray Co., Ltd.;
Polyethylene terephtalate, U46, toray Co., Ltd.;
Acrylonitrile-styrene-glycidyl methacrylate copolymer: AS3G, toray Co., Ltd.;
Polycarbonate, L-1225 Japan Di Ren KCC;
Acrylonitrile-butadiene-styrene (ABS) ABS, 2600P, toray Co., Ltd.;
Non-alkali glass scale: REFG-101 Nippon Sheet Glass Co Ltd;
There is alkali glass scale: the Sheng Heng of CV28 Xiangfan City chemical materials company limited;
Graphite: sheet, 200 orders, crystalline flake graphite, Qingdao City Tian He graphite company limited;
Mica: sheet, 500 orders, newly can be global mica material company limited;
Calcium carbonate: spherical, 500 orders, Haicheng Jinghua Minerals Co., Ltd;
Barium sulfate: Haicheng Jinghua Minerals Co., Ltd;
Short glass fiber: ECS303H, Chongqing Polycomp International Co., Ltd;
Basalt chopped fiber: CBF13-6, Shanghai Erjin Basalt Fiber Co., Ltd., Hengdian Group;
Fire retardant: FG-8500 Japan Di Ren KCC;
Auxiliary flame retardant: Sb2O3 Japan Di Ren KCC;
Anti-dripping agent A3800: polytetrafluoroethylene powder, Mitsubishi Li Yang Co., Ltd.;
Oxidation inhibitor IR1010: Ciba (China) company limited.
Performance test:
1) shrinking percentage test
Adopt 80*80*3mmt sample, utilize vernier callipers, measure respectively the shrinking percentage of Injection Molding direction and perpendicular flow direction.
2) mechanical property
Tensile strength: measure by standard ISO 527 with the standard batten that injection moulding is good, rate of extension 5mm/min, averages for 6 every group;
Flexural strength: measure by standard ISO 178 with the standard batten that injection moulding is good, crooked speed 2mm/min, averages for 6 every group;
Shock strength: measure by standard ISO 179 with the standard batten that injection moulding is good, average for 6 every group.
3) flame retardant resistance (vertical combustion method)
With the standard batten that injection moulding is good, by standard UL94, test.Concrete, Bunsen burner is placed in to the batten lower end of vertical placement, igniting 10S, then removes burning things which may cause a fire disaster, records the sample flaming combustion time; As sample certainly puts out in 30S after removing flame, again Bunsen burner is placed in to batten lower end igniting 10S, record burning things which may cause a fire disaster and remove rear sample flaming combustion time and flameless combustion time, observe simultaneously and whether produce molten drop and molten drop and whether ignite and be put in the absorbent cotton of batten below, each sample is got 5 battens and is one group and tests, as first group of test, do not pass through, can get again one group and test.
Comparative example 1
In ratio shown in table 1, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, graphite and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 1.
Comparative example 2
In ratio shown in table 1, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, mica and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 1.
Embodiment 1
In ratio shown in table 1, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, with glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 1.
Embodiment 2
In ratio shown in table 1, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, barium sulfate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 1.
Embodiment 3
In ratio shown in table 1, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 1.
Embodiment 4
In ratio shown in table 1, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 1.
Table 1 component proportion and performance table
As seen from Table 1, comparative example 1 and 2 explanations are with respect to glass flake, other class laminal fillers as graphite, that mica improves effect to the shrinking percentage of polyester composite is limited, and mechanical property also reduces relatively.Embodiment 1-4 explanation non-alkali glass scale than non-alkali glass scale, calcium carbonate than barium sulfate, glass fibre than basalt chopped fiber to composition shrinking percentage to improve effect better.
Comparative example 3
In ratio shown in table 2, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 2.
Comparative example 4
In ratio shown in table 2, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 2.
Comparative example 5
In ratio shown in table 2, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 2.
Comparative example 6
In ratio shown in table 2, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 2.
Embodiment 5
In ratio shown in table 2, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 2.
Embodiment 6
In ratio shown in table 2, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 2.
Embodiment 7
In ratio shown in table 2, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 2.
Embodiment 8
In ratio shown in table 2, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 2.
Table 2 component proportion and performance table
As seen from Table 2, comparative example 3-6 and embodiment 5-8 are glass flake and the impact of the different proportion of composing of calcium carbonate on result, and wherein comparative example 3 calcium carbonate contents are that 0(is containing calcium carbonate), comparative example 4 glass flake content are that 0(is containing glass flake).From the presentation of results of comparative example 3 and 4, the synergistic effect while simultaneously adding due to glass flake and calcium carbonate, that the shrinking percentage of polyester composite is improved to effect is unsatisfactory for above component separately; Meanwhile, from the presentation of results of comparative example 5 and 6, in both, one content is too low, can not be effective.
Comparative example 7
In ratio shown in table 3, take respectively thermoplastic polyester PBT and PET, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 3.
Comparative example 8
In ratio shown in table 3, take respectively thermoplastic polyester PBT and PET, polycarbonate, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 3.
Comparative example 9
In ratio shown in table 3, take respectively thermoplastic polyester PBT and PET, styrol copolymer ABS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 3.
Embodiment 9
In ratio shown in table 3, take respectively thermoplastic polyester PBT and PET, polycarbonate, styrol copolymer AS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 3.
Embodiment 10
In ratio shown in table 3, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS and ABS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 3.
Embodiment 11
In ratio shown in table 3, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 3.
Embodiment 12
In ratio shown in table 3, take respectively thermoplastic polyester PBT and PET, styrol copolymer AS, calcium carbonate, glass flake and fire retardant, use at normal temperatures the pre-mixing of high-speed mixing whipping appts even, compound is from main hopper, fortifying fibre is transported to quantitatively in parallel dual-screw extruding machine (Japan's steel processed) and is melt extruded by side feeding unit, 250 ℃ of extrusion temperatures, rotating speed 200rpm, through melting, extrude, cooling, pelletizing obtains granulated pellet, this pellet is through 120 ℃ of forced air dryings after 4 hours, with NEX1000 injection moulding machine (Japanese Jing company produce), be injection molded into standard batten, by above-mentioned testing method, carry out performance test.Results of property is shown in table 3.
Table 3 component proportion and performance table
As seen from Table 3, comparative example 7-9 and embodiment 9-10 are used separately ABS or PC, with ABS or PC and the shared Performance Ratio of AS, the necessity of AS component interpolation to improved performance be described.Embodiment 11 and 12 is the ratio adjustment of PBT and PET in the polyester impact on result, and user can decide final ratio according to the difference of each focus such as cost factor, mechanical property, flame retardant properties and molding shrinkage.
Claims (10)
1. a polyester composite for low molding shrinkage, is characterized in that, the main proportioning of said composition is as follows:
(a) thermoplastic polyester: 100 weight parts;
(b) styrene-acrylonitrile copolymer: 10-45 weight part;
(c) inorganic fleut: 5-50 weight part;
(d) glass flake: 5-50 weight part.
2. polyester composite according to claim 1, is characterized in that: described component (a) thermoplastic polyester is selected from one or more in polybutylene terephthalate, Poly(Trimethylene Terephthalate) or polyethylene terephthalate.
3. polyester composite according to claim 1, it is characterized in that: described component (b) styrene-acrylonitrile copolymer is acrylonitrile-styrene-glycidyl methacrylate copolymer, wherein, acrylonitrile content is the 10-40wt% of styrene-acrylonitrile copolymer, the 0.1-10wt% that glycidyl methacrylate content is styrene-acrylonitrile copolymer.
4. polyester composite according to claim 1, is characterized in that: described component (c) inorganics fleut is selected from one or more in aluminum oxide, zinc oxide, calcium oxide, zinc sulphide, Iron sulfuret, barium sulfate, zinc sulfate, Tai-Ace S 150, calcium sulfate, calcium carbonate, zinc carbonate or aluminium carbonate; Described component (d) glass flake is non-alkali glass scale, and its thickness is 2-10 μ m, and sheet footpath is 10-300 order.
5. polyester composite according to claim 1, is characterized in that: said composition also contains:
(e) fire retardant: 10-30 weight part;
(f) auxiliary flame retardant: 1-10 weight part;
(g) fortifying fibre: 20-70 weight part;
Wherein, described component (e) fire retardant is one or more in tetrabromo-bisphenol, decabromodiphynly oxide, pentabromotoluene, hexabromocyclododecane, TDE, three-(tribromophenoxy)-triazine, brominated Polystyrene or brominated epoxy resin; Described component (f) auxiliary flame retardant is one or several in antimony type oxide or metaantimmonic acid salt; Described component (g) fortifying fibre is one or several in glass fibre, carbon fiber, basalt fibre or aromatic polyamide fibre; Described fortifying fibre is special crosssection glass fibre, and aspect ratio is between 2-6.
6. a preparation method for polyester composite claimed in claim 1, is characterized in that: by carry out melt blending after raw material pre-mixing at 200-270 ℃, obtain polyester composite;
The main proportioning of raw material is as follows:
(a) thermoplastic polyester: 100 weight parts;
(b) styrene-acrylonitrile copolymer: 10-45 weight part;
(c) inorganic fleut: 5-50 weight part;
(d) glass flake: 5-50 weight part.
7. preparation method according to claim 6, is characterized in that: described component (a) thermoplastic polyester is selected from one or more in polybutylene terephthalate, Poly(Trimethylene Terephthalate) or polyethylene terephthalate.
8. preparation method according to claim 6, it is characterized in that: described component (b) styrene-acrylonitrile copolymer is acrylonitrile-styrene-glycidyl methacrylate copolymer, wherein, acrylonitrile content is the 10-40wt% of styrene-acrylonitrile copolymer, the 0.1-10wt% that glycidyl methacrylate content is styrene-acrylonitrile copolymer.
9. preparation method according to claim 6, is characterized in that: described component (c) inorganics fleut is selected from one or more in aluminum oxide, zinc oxide, calcium oxide, zinc sulphide, Iron sulfuret, barium sulfate, zinc sulfate, Tai-Ace S 150, calcium sulfate, calcium carbonate, zinc carbonate or aluminium carbonate; Described component (d) glass flake is non-alkali glass scale, and its thickness is 2-10 μ m, and sheet footpath is 10-300 order.
10. preparation method according to claim 6, is characterized in that: in material, also comprise:
(e) fire retardant: 10-30 weight part;
(f) auxiliary flame retardant: 1-10 weight part;
(g) fortifying fibre: 20-70 weight part;
Wherein, described component (e) fire retardant is one or more in tetrabromo-bisphenol, decabromodiphynly oxide, pentabromotoluene, hexabromocyclododecane, TDE, three-(tribromophenoxy)-triazine, brominated Polystyrene or brominated epoxy resin; Described component (f) auxiliary flame retardant is one or several in antimony type oxide or metaantimmonic acid salt; Described component (g) fortifying fibre is one or several in glass fibre, carbon fiber, basalt fibre or aromatic polyamide fibre; Described fortifying fibre is special crosssection glass fibre, and aspect ratio is between 2-6.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385121A (en) * | 2015-12-21 | 2016-03-09 | 上海锦湖日丽塑料有限公司 | Polyester composition used for nanometer injection molding and preparing method thereof |
| CN106147515A (en) * | 2016-06-22 | 2016-11-23 | 林金溪 | A kind of solventless epoxy coating and preparation method thereof |
| CN106280320A (en) * | 2016-08-31 | 2017-01-04 | 广东顺德顺炎新材料股份有限公司 | A kind of low warpage highlight antiflaming polybutylene terephthalate (PBT) and preparation method thereof |
| CN107266879A (en) * | 2017-07-21 | 2017-10-20 | 安徽江淮汽车集团股份有限公司 | A kind of uniform PET composite material of high-performance shrinkage factor and preparation method thereof |
| CN107325467A (en) * | 2017-07-12 | 2017-11-07 | 安徽凯密克企业管理咨询有限公司 | A kind of composite material and preparation method thereof for being used to prepare auto parts and components |
| CN108310455A (en) * | 2018-03-20 | 2018-07-24 | 嘉兴尔云信息科技有限公司 | Nanometer hydroxyapatite, phosphorylation polyester composite bone repairing material and preparation method thereof |
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| US4966935A (en) * | 1984-09-10 | 1990-10-30 | Polyplastics Co., Ltd. | Non-flammable polybutylene therephthalate composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4966935A (en) * | 1984-09-10 | 1990-10-30 | Polyplastics Co., Ltd. | Non-flammable polybutylene therephthalate composition |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385121A (en) * | 2015-12-21 | 2016-03-09 | 上海锦湖日丽塑料有限公司 | Polyester composition used for nanometer injection molding and preparing method thereof |
| CN106147515A (en) * | 2016-06-22 | 2016-11-23 | 林金溪 | A kind of solventless epoxy coating and preparation method thereof |
| CN106280320A (en) * | 2016-08-31 | 2017-01-04 | 广东顺德顺炎新材料股份有限公司 | A kind of low warpage highlight antiflaming polybutylene terephthalate (PBT) and preparation method thereof |
| CN107325467A (en) * | 2017-07-12 | 2017-11-07 | 安徽凯密克企业管理咨询有限公司 | A kind of composite material and preparation method thereof for being used to prepare auto parts and components |
| CN107266879A (en) * | 2017-07-21 | 2017-10-20 | 安徽江淮汽车集团股份有限公司 | A kind of uniform PET composite material of high-performance shrinkage factor and preparation method thereof |
| CN108310455A (en) * | 2018-03-20 | 2018-07-24 | 嘉兴尔云信息科技有限公司 | Nanometer hydroxyapatite, phosphorylation polyester composite bone repairing material and preparation method thereof |
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| CN104004326B (en) | 2017-05-17 |
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