CN104004326B - Polyester composite material and preparation method thereof - Google Patents
Polyester composite material and preparation method thereof Download PDFInfo
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- CN104004326B CN104004326B CN201310060148.XA CN201310060148A CN104004326B CN 104004326 B CN104004326 B CN 104004326B CN 201310060148 A CN201310060148 A CN 201310060148A CN 104004326 B CN104004326 B CN 104004326B
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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, and in particular to a kind of low molding shrinkage polymer blend and its preparation side
Method.
Background technology
Thermoplastic polyester, such as polybutylene terephthalate (PBT)（PBT）, PTT（PPT）
And polyethylene terephthalate（PET）There is excellent mechanical property and electric property, especially poly terephthalic acid fourth
The extremely excellent shaping processability of diol ester, by quite varied electronic electric equipment, housed device, office automation are applied to
In the fields such as equipment, automobile and plant equipment.
But polyester resin has that vitrification point is low simultaneously, product molding shrinkage factor is larger, rigid deficiency etc. under high temperature
Shortcoming.Numerous studies attempt to improve disadvantages described above to realize that component material has complementary advantages by blending and modifying.Especially with regard to poly-
The shrinkage factor aspect of ester resin, the inherent character of polyester resin itself molecular structure so that molecular entanglement legibility is removed, Relative sliding
Easily, the features such as crystallizing easily orientation, causes material in polyester resin anisotropy, and the horizontal and vertical shrinkage factor difference of product is larger,
Easily there is warpage.In recent years, due to the increase in demand of large-scale thin wall parts, the dimensional stability and warpage preventing of polyester resin become
One major issue.
Improve the publication of polyester resin shrinkage factor, mainly with polyester resin and amorphous polymer blending and modifying, such as
Addition PC, Chinese patent 1789333（Publication number）《Environmental-friendly fire-retardant PC/PBT plastic alloy》, Chinese patent 101914271A（It is public
The number of opening）《Environment-friendly flame retardant PBT/PC composites and preparation method thereof》Etc.；Or addition ABS, Chinese patent 102617997A（It is public
The number of opening）《A kind of glass fiber reinforcement PBT/PET composites and preparation method thereof》；Improve again or using nucleator, such as China
Patent 102040808A（Publication number）《Low warp glass fiber REINFORCED PET/PBT alloy of high glaze and preparation method thereof》, Chinese patent
102070884A（Publication number）《A kind of flame-proof glass fibre REINFORCED PET/PBT alloy and preparation method thereof》Etc..These methods stress
On the other hand in from improving from the aspect of polyester resin crystallization, on the one hand, the improvement of molding shrinkage is limited, excessive amorphous
The membership that adds of polymer reduces Some Mechanical Properties.
The content of the invention
In order to solve drawbacks described above of the prior art, the present invention is made by the combination of foliated glass scale and fleut
With being effectively improved the molding shrinkage situation of polyester material.
In order to realize improving the molding shrinkage situation of polyester composite, following technical scheme is present invention employs.It is a kind of
The polyester composite of low molding shrinkage, the main proportioning of said composition is as follows：
（a）Thermoplastic polyester：100 weight portions；
（b）SAN：10-45 weight portions；
（c）Inorganic powdered filler：5-50 weight portions；
（d）Glass flake：5-50 weight portions.
The inherent character of thermoplastic polyester molecular structure so that molecular entanglement legibility is removed, Relative sliding itself is easy,
Crystallization easily orientation the features such as, cause thermoplastic polyester material anisotropy, and the stress relaxation in molding thermal history later stage and
Secondary crystallization etc. causes product molding shrinkage factor big, and its horizontal and vertical shrinkage factor difference of product is also larger.Particularly glass
The fibre-reinforced polyester material of glass, its Injection Molding direction and mobile phase vertical direction difference it is larger.In the present invention, invention Crinis Carbonisatus
Now due to the orientation of one-dimensional square（Resin flow orientation or glass fibre are orientated）The anisotropy for causing, can be by two-dimentional shape
Shape material（Flaky material, such as glass flake）Addition, or and powdery（Or title three dimensional particles shape）The synergism of filler so as to
It is effectively improved.Therefore be employed herein（c）Inorganic powdered filler with（d）Glass flake so that polyester composite
Shrinkage factor is substantially reduced.
The present invention is for described component（a）Thermoplastic polyester, without special requirement, it is contemplated that at present application is wide
General property, it may be preferred to for polybutylene terephthalate (PBT)（PBT）, PTT（PTT）Or it is poly- to benzene two
Formic acid glycol ester（PET）In any one or a few.
The present invention is for described component（b）SAN, without special requirement, it is contemplated that with polyester
Material interface Compatibility improvement, SAN is preferably acrylonitrile-styrene-methyl propenoic acid glycidyl
Ester copolymer, wherein, acrylonitrile content for SAN 10-40wt%, glycidyl methacrylate
Content is the 0.1-10wt% of SAN.
Described component（c）Inorganic matters fleut selected from aluminium oxide, Zinc Oxide, calcium oxide, zinc sulfide, Iron sulfuret.,
One or more in barium sulfate, zinc sulfate, aluminum sulfate, calcium sulfate, Calcium Carbonate, zinc carbonate or aluminium carbonate.More preferably
Barium sulfate, calcium sulfate or Calcium Carbonate.Most preferably Calcium Carbonate.Above-mentioned filler can also be with coupling agent, Organic substance or inorganic matters etc.
One or more of surface conditioning agent is processed, preferably with coupling agent such as silane coupler, titanate coupling agent or Aluminate
Coupling agent is surface-treated with known method.
Described component（d）Glass flake is preferably alkali-free glass scale, and its thickness is 2-10 μm, and piece footpath is 10-300
Mesh.
Said composition can also contain：
（e）Fire retardant：10-30 weight portions；
（f）Auxiliary flame retardant：1-10 weight portions；
（g）Reinforcing fiber：20-70 weight portions；
Described component（e）Fire retardant selected from tetrabromobisphenol A, deca-BDE, pentabromotoluene, HBCD,
TDE, three-(tribromophenoxy）One or more in-triazine, brominated Polystyrene or brominated epoxy resin；
Described component（f）Auxiliary flame retardant selected from antimony type oxide or stibate apoplexy due to endogenous wind one or several；
Described component（g）Reinforcing fiber is in glass fibre, carbon fiber, basalt fibre or aromatic polyamide fibre
One or several, preferred reinforcing fiber be odd-shaped cross section glass fibre, aspect ratio is between 2 and 6.
The present invention is also provided with a kind of preparation method of the polyester composite of above-mentioned low molding shrinkage.
Raw material premix are closed carries out melt blending at 200-270 DEG C, obtains polyester composite；
The main proportioning of raw material is as follows：
（a）Thermoplastic polyester：100 weight portions；
（b）SAN：10-45 weight portions；
（c）Inorganic powdered filler：5-50 weight portions；
（d）Glass flake：5-50 weight portions.
The species and proportioning of key component is as described above.
Can also include in material：
（e）Fire retardant：10-30 weight portions；
（f）Auxiliary flame retardant：1-10 weight portions；
（g）Reinforcing fiber：20-70 weight portions；
Their species and component is as described above.
In addition, as needed the public affairs added in thermoplastic resin can be generally used in not damage the addition that is limited of the invention
Know material, for example anti-dripping agent, hydrolysis-resisting agent, antioxidant, the reagent for avoiding light or ultraviolet light degradation, lubricant, releasing agent,
Coloring agent, nucleator or plasticizer etc..The use of these auxiliary agents can improve some features of compositionss, but the resistance basic to its
Combustion performance and mechanical property do not have anything to affect substantially, can select general these commercially available auxiliary agents, and they are for the present invention
It is not necessary.The consumption of other auxiliary agents can be according to the routinely consumption addition of the purpose of addition auxiliary agent.
By the design of above formula and processing technique, the shrinkage factor of resulting polyester is substantially reduced.It is good due to its
Thermostability, mechanical performance and excellent fire resistance itself, extensively using fields such as automobile, electronic apparatus parts.
Specific embodiment
Standby using melt blending extrusion mechanism, the draw ratio of double screw extruder is 45, there is 13 thermals treatment zone；There are two cuffs
The feeding device of metrical instrument；With vacuum-pumping equipment.
Raw material explanation：
Polybutylene terephthalate (PBT) PBT, 1050M, toray Co., Ltd.；
Polyethylene terephtalate, U46, toray Co., Ltd.；
Acrylonitrile-styrene-glycidyl methacrylate copolymer：AS3G, toray Co., Ltd.；
Polycarbonate, Di Ren KCCs of L-1225 Japan；
Acrylonitrile-butadiene-styrene (ABS) ABS, 2600P, toray Co., Ltd.；
Alkali-free glass scale：REFG-101 Nippon Sheet Glass Co Ltd；
There is alkali glass scale：CV28 Xiangfan City Sheng Heng chemical materialss company limited；
Graphite：Lamellar, 200 mesh, crystalline flake graphite, Qingdao City day and graphite company limited；
Muscovitum：Lamellar, 500 mesh newly can global mica material company limited；
Calcium Carbonate：It is spherical, 500 mesh, 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：Di Ren KCCs of FG-8500 Japan；
Auxiliary flame retardant：Di Ren KCCs of Sb2O3 Japan；
Anti-dripping agent A3800：Polytetrafluoroethylene powder, Mitsubishi Li Yang Co., Ltd.；
Antioxidant IR1010：Ciba（China）Company limited.
Performance test：
1）Shrinkage factor is tested
Using 80*80*3mmt samples, using slide gauge, Injection Molding direction and perpendicular flow direction are determined respectively
Shrinkage factor.
2）Mechanical property
Tensile strength：Determined by standard ISO527 with the good standard batten of injection mo(u)lding, rate of extension 5mm/min, per group 6
Root is averaged；
Bending strength：Determined by standard ISO178 with the good standard batten of injection mo(u)lding, bending speed 2mm/min, per group 6
Root is averaged；
Impact strength：Determined by standard ISO179 with the good standard batten of injection mo(u)lding, 6 per group are averaged.
3）Anti-flammability（Vertical combustion）
Tested by standard UL94 with the good standard batten of injection mo(u)lding.Particularly, Bunsen burner is placed in and is vertically put
The batten lower end put, light a fire 10S, then removes burning things which may cause a fire disaster, records sample flaming combustion time；The 30S after flame is removed as samples
Interior self-extinguishment, then again by Bunsen burner be placed in batten lower end igniting 10S, record burning things which may cause a fire disaster remove rear sample flaming combustion time and nonflame
Burning time, whether while see whether to produce molten drop and molten drop igniting the absorbent cotton being put in below batten, each sample takes 5
Batten is tested for one group, and such as first group of test does not pass through, and can again take one group and be tested.
Comparative example 1
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate, stone are weighed respectively in ratio shown in table 1
Ink and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound passes through side from main hopper, reinforcing fiber
Feed arrangement is quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, 250 DEG C of extrusion temperature,
Rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, and the pellet is used Jing after 120 DEG C of forced air dryings 4 hours
NEX1000 injection machines（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.Performance is tied
Fruit is shown in table 1.
Comparative example 2
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate, cloud are weighed respectively in ratio shown in table 1
Female and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound passes through side from main hopper, reinforcing fiber
Feed arrangement is quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, 250 DEG C of extrusion temperature,
Rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, and the pellet is used Jing after 120 DEG C of forced air dryings 4 hours
NEX1000 injection machines（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.Performance is tied
Fruit is shown in table 1.
Embodiment 1
In ratio shown in table 1 weigh respectively thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate and
Glass flake and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound is from main hopper, reinforcing fiber
Parallel dual-screw extruding machine is quantitatively transported to by side feed arrangement（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 1.
Embodiment 2
Thermoplastic polyester PBT and PET, styrol copolymer AS, barium sulfate, glass are weighed respectively in ratio shown in table 1
Glass scale and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound leads to from main hopper, reinforcing fiber
Cross side feed arrangement and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 1.
Embodiment 3
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate, glass are weighed respectively in ratio shown in table 1
Glass scale and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound leads to from main hopper, reinforcing fiber
Cross side feed arrangement and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 1.
Embodiment 4
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate, glass are weighed respectively in ratio shown in table 1
Glass scale and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound leads to from main hopper, reinforcing fiber
Cross side feed arrangement and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 1.
The component proportion of table 1 and performance table
As seen from Table 1, comparative example 1 and 2 illustrates that relative to glass flake other class laminal filters such as graphite, Muscovitum are to poly-
The shrinkage factor improvement of ester composite is limited, and mechanical property also relative reduction.Embodiment 1-4 illustrates alkali-free glass squama
Improvement of the piece than alkali-free glass scale, Calcium Carbonate than barium sulfate, glass fibre than basalt chopped fiber to compositionss shrinkage factor
It is better.
Comparative example 3
In ratio shown in table 2 weigh respectively thermoplastic polyester PBT and PET, styrol copolymer AS, glass flake and
Fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound is fed from main hopper, reinforcing fiber by side
Device is quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, 250 DEG C of extrusion temperature, rotating speed
200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, and the pellet is used Jing after 120 DEG C of forced air dryings 4 hours
NEX1000 injection machines（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.Performance is tied
Fruit is shown in table 2.
Comparative example 4
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate and resistance are weighed respectively in ratio shown in table 2
Combustion agent, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound is filled from main hopper, reinforcing fiber by side charging
Put and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, 250 DEG C of extrusion temperature, rotating speed
200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, and the pellet is used Jing after 120 DEG C of forced air dryings 4 hours
NEX1000 injection machines（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.Performance is tied
Fruit is shown in table 2.
Comparative example 5
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate, glass are weighed respectively in ratio shown in table 2
Glass scale and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound leads to from main hopper, reinforcing fiber
Cross side feed arrangement and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 2.
Comparative example 6
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate, glass are weighed respectively in ratio shown in table 2
Glass scale and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound leads to from main hopper, reinforcing fiber
Cross side feed arrangement and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 2.
Embodiment 5
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate, glass are weighed respectively in ratio shown in table 2
Glass scale and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound leads to from main hopper, reinforcing fiber
Cross side feed arrangement and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 2.
Embodiment 6
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate, glass are weighed respectively in ratio shown in table 2
Glass scale and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound leads to from main hopper, reinforcing fiber
Cross side feed arrangement and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 2.
Embodiment 7
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate, glass are weighed respectively in ratio shown in table 2
Glass scale and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound leads to from main hopper, reinforcing fiber
Cross side feed arrangement and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 2.
Embodiment 8
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate, glass are weighed respectively in ratio shown in table 2
Glass scale and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound leads to from main hopper, reinforcing fiber
Cross side feed arrangement and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 2.
The component proportion of table 2 and performance table
As seen from Table 2, comparative example 3-6 and embodiment 5-8 are glass flake from the different proportion of composing of Calcium Carbonate to result
Impact, wherein the calcium carbonate content of comparative example 3 be 0（That is not calcium carbonate）, the glass flake content of comparative example 4 is 0（Glass is not contained
Glass scale）.Illustrate from the result of comparative example 3 and 4, cooperative effect when being added due to glass flake and Calcium Carbonate simultaneously, individually
Above component is unsatisfactory to the shrinkage factor improvement of polyester composite；Meanwhile, illustrate from the result of comparative example 5 and 6, two
One content is too low in person, can not reach effect.
Comparative example 7
Thermoplastic polyester PBT and PET, Calcium Carbonate, glass flake and fire retardant are weighed respectively in ratio shown in table 3,
Uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound is from main hopper, and reinforcing fiber is fixed by side feed arrangement
It is transported to parallel dual-screw extruding machine to amount（Japan's steel processed）In carry out melting extrusion, 250 DEG C of extrusion temperature, rotating speed
200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, and the pellet is used Jing after 120 DEG C of forced air dryings 4 hours
NEX1000 injection machines（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.Performance is tied
Fruit is shown in table 3.
Comparative example 8
Thermoplastic polyester PBT and PET, Merlon, Calcium Carbonate, glass flake are weighed respectively in ratio shown in table 3
And fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound is entered from main hopper, reinforcing fiber by side
Material device is quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, 250 DEG C of extrusion temperature turns
Fast 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, and the pellet is used Jing after 120 DEG C of forced air dryings 4 hours
NEX1000 injection machines（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.Performance is tied
Fruit is shown in table 3.
Comparative example 9
Thermoplastic polyester PBT and PET, styrol copolymer ABS, Calcium Carbonate, glass are weighed respectively in ratio shown in table 3
Glass scale and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound leads to from main hopper, reinforcing fiber
Cross side feed arrangement and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 3.
Embodiment 9
In ratio shown in table 3 weigh respectively thermoplastic polyester PBT and PET, Merlon, styrol copolymer AS,
Calcium Carbonate, glass flake and fire retardant, it is uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound from main hopper,
Reinforcing fiber is quantitatively transported to parallel dual-screw extruding machine by side feed arrangement（Japan's steel processed）In carry out melting extrusion,
250 DEG C of extrusion temperature, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of air blast of pellet Jing
After being dried 4 hours, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, is carried out by above-mentioned method of testing
Performance test.Results of property is shown in table 3.
Embodiment 10
Thermoplastic polyester PBT and PET, styrol copolymer AS and ABS, carbonic acid are weighed respectively in ratio shown in table 3
Calcium, glass flake and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound strengthens from main hopper
Fiber is quantitatively transported to parallel dual-screw extruding machine by side feed arrangement（Japan's steel processed）In carry out melting extrusion, extrude
250 DEG C of temperature, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of forced air dryings 4 of pellet Jing
After hour, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance survey is carried out
Examination.Results of property is shown in table 3.
Embodiment 11
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate, glass are weighed respectively in ratio shown in table 3
Glass scale and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound leads to from main hopper, reinforcing fiber
Cross side feed arrangement and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 3.
Embodiment 12
Thermoplastic polyester PBT and PET, styrol copolymer AS, Calcium Carbonate, glass are weighed respectively in ratio shown in table 3
Glass scale and fire retardant, uniform with the premixing of mixed at high speed agitating device at normal temperatures, compound leads to from main hopper, reinforcing fiber
Cross side feed arrangement and be quantitatively transported to parallel dual-screw extruding machine（Japan's steel processed）In carry out melting extrusion, extrusion temperature
250 DEG C, rotating speed 200rpm, Jing melting, extrusion, cooling, pelletizing obtain granulated pellet, 120 DEG C of pellet Jing forced air dryings 4 hours
Afterwards, NEX1000 injection machines are used（Japanese Jing companies produce）Standard batten is molded into, by above-mentioned method of testing performance test is carried out.
Results of property is shown in table 3.
The component proportion of table 3 and performance table
As seen from Table 3, comparative example 7-9 and embodiment 9-10 are exclusive use ABS or PC, shared with ABS or PC and AS
Performance comparision, illustrates necessity of the AS components addition to performance improvement.Embodiment 11 and 12 is the ratio of PBT and PET in polyester
Impact of the adjustment to result, user can be according to each focus such as cost factor, mechanical property, fire resistance and molding shrinkage
Difference determining final ratio.
Claims (10)
1. a kind of polyester composite of low molding shrinkage, it is characterised in that the main proportioning of said composition is as follows：
(a) thermoplastic polyester：100 weight portions；
(b) SAN：10-45 weight portions；
(c) Calcium Carbonate：5-50 weight portions；
(d) alkali-free glass scale：5-50 weight portions；
(g) glass fibre：20-70 weight portions.
2. polyester composite according to claim 1, it is characterised in that：Described component (a) thermoplastic polyester
One kind in polybutylene terephthalate (PBT), PTT or polyethylene terephthalate or
It is several.
3. polyester composite according to claim 1, it is characterised in that：Described component (b) styrene-acrylonitrile is common
Polymers is acrylonitrile-styrene-glycidyl methacrylate copolymer, wherein, acrylonitrile content is styrene-acrylonitrile
The 10-40wt% of copolymer, glycidyl methacrylate content is the 0.1-10wt% of SAN.
4. polyester composite according to claim 1, it is characterised in that：Described component (d) alkali-free glass scale, its
Thickness is 2-10 μm, and piece footpath is 10-300 mesh.
5. polyester composite according to claim 1, it is characterised in that：Said composition also contains：
(e) fire retardant：10-30 weight portions；
(f) auxiliary flame retardant：1-10 weight portions；
Wherein, described component (e) fire retardant is tetrabromobisphenol A, deca-BDE, pentabromotoluene, HBCD, ten bromines
Diphenylethane, three-(tribromophenoxy)-triazine, brominated Polystyrene or brominated epoxy resin in one or more；It is described
Component (f) auxiliary flame retardant be antimony type oxide or stibate apoplexy due to endogenous wind one or several；Described component (g) glass fibers
Tie up as odd-shaped cross section glass fibre, aspect ratio is between 2 and 6.
6. the preparation method of the polyester composite described in a kind of claim 1, it is characterised in that：By raw material premix close after
Melt blending is carried out at 200-270 DEG C, polyester composite is obtained；
The main proportioning of raw material is as follows：
(a) thermoplastic polyester：100 weight portions；
(b) SAN：10-45 weight portions；
(c) Calcium Carbonate：5-50 weight portions；
(d) alkali-free glass scale：5-50 weight portions；
(g) glass fibre：20-70 weight portions.
7. preparation method according to claim 6, it is characterised in that：Described component (a) thermoplastic polyester is selected from
One kind or several in polybutylene terephthalate (PBT), PTT or polyethylene terephthalate
Kind.
8. preparation method according to claim 6, it is characterised in that：Described component (b) SAN
For acrylonitrile-styrene-glycidyl methacrylate copolymer, wherein, acrylonitrile content is styrene-acrylonitrile copolymerization
The 10-40wt% of thing, glycidyl methacrylate content is the 0.1-10wt% of SAN.
9. polyester composite according to claim 1, it is characterised in that：Described component (d) alkali-free glass scale, its
Thickness is 2-10 μm, and piece footpath is 10-300 mesh.
10. preparation method according to claim 6, it is characterised in that：Also include in material：
(e) fire retardant：10-30 weight portions；
(f) auxiliary flame retardant：1-10 weight portions；
Wherein, described component (e) fire retardant is tetrabromobisphenol A, deca-BDE, pentabromotoluene, HBCD, ten bromines
Diphenylethane, three-(tribromophenoxy)-triazine, brominated Polystyrene or brominated epoxy resin in one or more；It is described
Component (f) auxiliary flame retardant be antimony type oxide or stibate apoplexy due to endogenous wind one or several；Described component (g) glass fibers
Tie up as odd-shaped cross section glass fibre, aspect ratio is between 2 and 6.
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| CN201310060148.XA CN104004326B (en) | 2013-02-26 | 2013-02-26 | Polyester composite material and preparation method thereof |
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| CN104004326B true CN104004326B (en) | 2017-05-17 |
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| 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 |
| CN106280320B (en) * | 2016-08-31 | 2020-11-06 | 广东顺德顺炎新材料股份有限公司 | Low-warpage high-gloss flame-retardant polybutylene terephthalate 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 |
| CN107266879B (en) * | 2017-07-21 | 2019-04-16 | 安徽江淮汽车集团股份有限公司 | A kind of uniform PET composite material of high-performance shrinking percentage and preparation method thereof |
| CN108310455B (en) * | 2018-03-20 | 2021-07-30 | 嘉兴尔云信息科技有限公司 | Nano hydroxyapatite and PGS-M composite bone repair material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4966935A (en) * | 1984-09-10 | 1990-10-30 | Polyplastics Co., Ltd. | Non-flammable polybutylene therephthalate composition |
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2013
- 2013-02-26 CN CN201310060148.XA patent/CN104004326B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4966935A (en) * | 1984-09-10 | 1990-10-30 | Polyplastics Co., Ltd. | Non-flammable polybutylene therephthalate composition |
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