CN106633681A - High-toughness polyester resin alloy composition and preparation method thereof - Google Patents
High-toughness polyester resin alloy composition and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a high-toughness polyester alloy composition and a preparation method thereof, wherein the composition mainly comprises the following raw materials by weight: (A) polybutylene terephthalate, (B) polyethylene terephthalate, and (C) an ionomer compound using an ethylene octene copolymer as a matrix. The preparation method comprises: adding (A) polybutylene terephthalate, (B) polyethylene terephthalate, (C) an ionomer compound using an ethylene octene copolymer as a matrix and other additives to a high speed material mixer, adding to a twin-screw extruder after the mixing, and carrying out melt extrusion granulation. According to the present invention, the polyester resin alloy reinforcing material composition has good impact resistance and good fluidity, and the product prepared by using the high-toughness polyester resin alloy reinforcing material composition has characteristics of low warping, high strength and high toughness, and is suitable for vehicles, mobile phones, and notebook computer products.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of high-tenacity polyester resin alloy composition and preparation method thereof.
Background technology
Thermoplastic polyester, as polybutylene terephthalate (PBT) (PBT), PTT (PTT) and polyethylene terephthalate (PET) have excellent mechanical property and electric property, especially PBT and PET has an extremely excellent molding processibility, and mechanical performance and electric property are applied in the middle of the fields such as electronic electric equipment, housed device, business automation equipment, automobile and plant equipment by quite varied.
PET glass transition temperatures are high, and crystallization rate is slow, and molding cycle is long, and fracture impact strength is low so that its application on engineering plastics is restricted.Using PET and other materials copolymerization, the comprehensive each of which performance of method energy of blending, learn from other's strong points to offset one's weaknesses, make up the defect in one-component performance, and improve the crystal property of PET.Generally, obtain the ideal blend of combination property, PET contents are relatively low, the alloy of high PET contents can not be leaned on only improves crystal property with other materials combined polymerization blending, typically also need to add nucleator, the crystallization nucleating agent of conventional polyester resin such as patent document 1 or patent document 2 are recorded, including graphite, carbon black, the oxide of second round metallic element, sulfate such as calcium sulfate, barium sulfate, phosphate such as calcium phosphate, silicate such as calcium silicates, magnesium silicate, oxalates such as calcium oxalate, stearate such as magnesium stearate, benzoate such as Sodium Benzoate, salicylate such as bigcatkin willow is misery and the inorganic nucleator such as talcum powder；Or, such as Du Pont90209120 or HoneywellDeng the organic nucleating agent that its structure is shown below.
But for the above polyester resin inorganic nucleator, when addition is fewer, raising nucleation rate is limited in one's ability, and addition increases can reduce matrix material performance, and dispersiveness is poor again.For the organic nucleating agent, although have preferably dispersiveness and nucleation capability, but also need larger addition, matrix material degraded can be caused to cause material property to decline, while also needing to add toughener just to play preferable toughening effect together.The toughener generally includes styrene block copolymer, ethylene/octene, polyacrylic core/shell particle or ethene/acrylic ester copolymer etc.; such as E.I.du Pont de Nemours and Company of Wilmington; Del. AC and PTW; the AX8900 of French A Kema; BF series of products or eastern beautiful TPEE series of products of SUMITOMO CHEMICAL chemistry etc.; but for reach significant improvement and needed for impact modifying agent amount scope, the toughener must account for 20-30 weight % of polymer substrate.And the toughener for adding high-load can disturb into nuclearity, crystal property, degree of crystallinity is so as to declining.
So, for PET/PBT alloy composites, more suitably nucleator and toughener are found also just into the task of top priority.
The US3368995 of patent document 1
The CN201210507239.9 of patent document 2.
The content of the invention
The problems of toughness and crystalline rate of polyester alloy composition are improved in order to solve above-mentioned prior art, the present invention by add component (C) ethylene copolymer octene based on from dimmer compound, its crystalline rate is improved while the toughness for improving polyester alloy composition, so as to realize the present invention.I.e. technical solution of the present invention is：
1. a kind of high-tenacity polyester resin alloy composition, wherein, the high-tenacity polyester resin alloy composition is included：(A) based on polybutylene terephthalate (PBT), (B) polyethylene terephthalate and (C) ethylene copolymer octene from dimmer compound.
2. a kind of high-tenacity polyester resin alloy composition according to above-mentioned 1, wherein, in the high-tenacity polyester resin alloy composition, (A) polybutylene terephthalate (PBT) is 20-40 weight portions；(B) polyethylene terephthalate is 40-70 weight portions；(C) based on ethylene copolymer octene from dimmer compound be 1-12 weight portions.
3. a kind of high-tenacity polyester resin alloy composition according to above-mentioned 1, wherein, include following formula I structure from dimmer compound based on component (C) the ethylene copolymer octene, wherein x, y be 1 to 10 positive integer and x：Y=9：1～5：1.
4. a kind of high-tenacity polyester resin alloy composition according to above-mentioned 1, wherein, the structure of following formula II or III is included from dimmer compound based on component (C) the ethylene copolymer octene, wherein, a, b are 1 to 10 positive integer, and a：B=9：1～3：2, wherein M are a kind of metal cation or ammonium ion.
5. a kind of high-tenacity polyester resin alloy composition according to above-mentioned 4, wherein, mass percent from dimmer compound in of the structure of the formula II or III based on component (C) the ethylene copolymer octene is 1-5%.
6. a kind of high-tenacity polyester resin alloy composition according to above-mentioned 1, wherein, based on its component (C) ethylene copolymer octene from dimmer compound be through such as following formula IV or formula V grafting compounds it is modified from dimmer compound, its weight/mass percentage composition in dimmer compound based on (C) ethylene copolymer octene is 1-5%.
7. a kind of high-tenacity polyester resin alloy composition according to above-mentioned 1, wherein, the high-tenacity polyester resin alloy composition is also comprising at least one in glass fibre, talcum powder, mica, calcium carbonate, calcium sulfate, magnesium sulfate, silica whisker or potassium titanate crystal whisker.
8. a kind of high-tenacity polyester resin alloy composition according to above-mentioned 1, wherein, also include antioxidant in the high-tenacity polyester resin alloy composition, the antioxidant is at least one in suffocated amine antioxidant, Hinered phenols antioxidant or phosphite ester kind antioxidant.
9. a kind of preparation method of high-tenacity polyester resin alloy composition as described in above-mentioned 1, by A) polybutylene terephthalate (PBT), (B) polyethylene terephthalate, add high speed mixers from dimmer compound and other additives based on (C) ethylene copolymer octene, mix 5-10 minutes；Blending material is added into double screw extruder melting extrusion granulation, processing temperature is 220 DEG C -290 DEG C, and engine speed is 100-300rpm.
According to property polyester resin alloy reinforcing material composition of the present invention, with good impact resistance and good mobility, its preparation method flow process is simple, continuous, production efficiency is high, obtained product surface is smooth, there is no fault of construction.Using in the product such as product, low warpage, high-intensity high-tenacity, it is adaptable to automobile, mobile phone, notebook computer obtained in high-tenacity polyester resin alloy reinforcing material composition of the present invention.
Specific embodiment
The specific embodiment of the present invention is illustrated below：
A kind of high-tenacity polyester resin alloy composition, wherein, the high-tenacity polyester resin alloy composition is included：
(A) based on polybutylene terephthalate (PBT), (B) polyethylene terephthalate and (C) ethylene copolymer octene from dimmer compound.
In order to obtain more excellent performance, preferred (A) polybutylene terephthalate (PBT) 20-40 weight portions in the present invention, (B) polyethylene terephthalate ratio be 40-70 weight portions, (C) based on ethylene copolymer octene from dimmer compound 1-12 weight portions.
(A) polybutylene terephthalate (PBT) (PBT)
In the present invention, PBT can be PBT homopolymers, PBT copolymer or its any blend, preferably PBT homopolymers.PBT copolymer preferably comprises at least 70mol%, or at least 80mol%, or at least 90mol%, or at least copolymerization units of the terephthalic acid (TPA) of 95mol% and butanediol ester.
(B) polyethylene terephthalate (PET)
In the present invention, PET its inherent viscosity is for about 0.4dL/g- about 2.0dL/g, and PET can be PET homopolymers, PET copolymer or its any blend.Preferably PET homopolymers.PET copolymer preferably comprises at least 70mol%, or at least 80mol%, or at least 90mol%, or at least ethylene glycol terephthalate of 95mol% as main copolymerization units.
(C) based on ethylene copolymer octene from dimmer compound.
In the present invention, (C) play a part of toughener and nucleator simultaneously from dimmer compound based on ethylene copolymer octene.
Based on (C) ethylene copolymer octene that the present invention is used from dimmer compound refer to main body be ethylene octene for copolymer through acid compound and active function groups graft modification again in inorganic base and formed containing metal cation or ammonium ion from dimmer compound.
Ethylene copolymer octene polymer its structure such as following formula 1 that the present invention is used, wherein x, y is 1 to 10 positive integer.
In the present invention, the mol ratio of ethene and octene has an impact to its performance in the ethylene copolymer octene polymer, and the content and distribution density of octene is closely related with toughening efficiency, while octene content increases corresponding mobility can reduce, therefore x：Y is preferably 9：1～5：1.
Consider from distribution performance of the polymer in resin body is improved, the chemical constitution of the grafting acid compound used by the present invention is preferably the compound such as following formula 2 or formula 3：
Consider from dispersiveness and raising ageing resistance, based on component (C) ethylene copolymer octene from dimmer compound preferably through such as following formula 4 or formula 5 grafting compounds it is modified from dimmer compound, because initiator graft modification percent grafting is relatively low, general its weight/mass percentage composition in dimmer compound based on (C) ethylene copolymer octene is 1-5%.
In the present invention, the structure of following formula 6 or 7 is preferably comprised from dimmer compound based on component (C) the ethylene copolymer octene, wherein, a, b are 1 to 10 positive integer, and a：B=9：1～3：2, wherein M are a kind of metal cation or ammonium ion, and metal cation can be specifically unit price or bivalent cation, including lithium, sodium, potassium, magnesium, calcium, barium, copper or zinc ion.Weight/mass percentage composition from dimmer compound in of the structure of the formula 6 or 7 based on component (C) the ethylene copolymer octene is preferably 1-5%
Additionally, not damaging in the range of effect of the present invention, silane compound can be added in the high-tenacity polyester resin alloy reinforcing material composition of the present invention.
Silane compound for example has epoxy radicals silicone hydride compound, amino silane compounds, ureido silane compound or isocynate silane compound, in addition to this it is possible to using other silane compounds.The specific example of the silane compound has：γ-glycidoxypropyltrimethoxy silane、γ-epoxypropoxy triethoxysilane、Or β-(3,4- expoxycyclohexyls) alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy radicals such as ethyl trimethoxy silane，γ mercaptopropyitrimethoxy silane、The alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl such as γ-mercaptopropyi methyl dimethoxysilane，γ-ureidopropyltriethoxysilane、γ-ureido-propyl trimethoxy silane、Or the alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups such as γ-(2- urea groups ethyls) TSL 8330，γ-NCO propyl-triethoxysilicane、γ-NCO propyl trimethoxy silicane、γ-NCO hydroxypropyl methyl dimethoxysilane、γ-NCO hydroxypropyl methyl diethoxy silane、γ-NCO ethyl dimethoxysilane、γ-NCO ethyl diethoxy silane、Or the alkoxysilane compound containing trialkylsilyl group in molecular structure containing NCO such as γ-NCO propyltrichlorosilan，γ-(2- amino-ethyls) amino propyl methyl dimethoxysilane、γ-(2- amino-ethyls) amino propyl methyl trimethoxy silane、The alkoxysilane compound containing trialkylsilyl group in molecular structure containing amino such as gamma-amino propyl trimethoxy silicane，And γ-hydroxypropyl trimethoxy silane、Or the alkoxysilane compound containing trialkylsilyl group in molecular structure of hydroxyl such as γ-hydroxypropyl triethoxysilane etc..
High-tenacity polyester alloy composite of the weight portion of silane compound relative to 100 weight portions, it is preferred that 0.05-2 weight portions, more preferably 0.1-1 weight portions, by the such silane compound of addition, can well improve the mechanical strength and toughening effect of polyester resin alloy composite.The weight portion of weight part ratio 0.05 of silane compound is few, then possibly cannot play a part of compatilizer.
Additionally, not damaging in the range of effect of the present invention, in the high-tenacity polyester resin alloy composition of the present invention antioxidant can be added, can further improve the heat resistance and heat endurance of resin combination.Antioxidant is preferably comprised chooses at least one from phenol antioxidant and phosphorus antioxidants.And during with phenol antioxidant and phosphorus antioxidants, can particularly efficiently keep heat resistance and heat endurance, therefore preferably.
As phenol antioxidant, hindered phenol compound is preferably used.Specific example has：Triethylene glycol is double (the 3- tert-butyl groups-(5- methyl -4- hydroxybenzyls) propionic ester)、N,N '-hexamethylene bis (3,5- di-t-butyl -4- hydroxy-hydrocineamides)、Four (methylene -3- (3 ',5 '-di-t-butyl -4 '-hydroxybenzyl) propionic ester) methane、(the 3- (3 ' of pentaerythrite four,5 '-di-t-butyl) -4 '-hydroxybenzyl) propionic ester)、1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls)-s- triazines -2，4，6-(1H,3H,5H)-triketone、1，1，3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane、4，4 '-butylidene is double (3- methyl-6-tert butyl phenyl)、N-octadecane base -3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester、3，(the 2- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy) -1 of 9- bis-,1- dimethyl ethyls) -2,4,8,The oxaspiros (5 of 10- tetra-,5) hendecane、Or 1,3,5- trimethyls -2,4,6- tri--(3,5- di-tert-butyl-4-hydroxyl benzyls) benzene etc..Wherein preferred ester type macromolecule hindered phenol type, specifically preferably use four (methylene -3- (3 ', 5 '-di-t-butyl -4 '-hydroxybenzyl) propionic ester) methane, (the 3- (3 ' of pentaerythrite four, 5 '-di-t-butyl) -4 '-hydroxybenzyl) propionic ester) or 3, (the 2- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy) -1 of 9- bis-, 1- dimethyl ethyls) -2,4,8, the oxaspiros of 10- tetra- (5,5) hendecane etc..
As phosphorus antioxidants; double (2 can be included; 6- di-t-butyl -4- aminomethyl phenyls) pentaerythrite-diphosphites, double (2; 4- di-tert-butyl-phenyls) pentaerythrite-diphosphites, double (2; 4- dicumylphenyls) pentaerythrite-diphosphites, three (2; 4- di-tert-butyl-phenyls) phosphite ester, four (2; 4- di-tert-butyl-phenyls) -4; 4 '-bis- phenylene phosphite esters, distearyl acyl group pentaerythrite-diphosphites, triphenyl phosphite or 3,5- dibutyl -4- hydroxybenzyl phosphate ester diethylesters etc..
Wherein, in the high-tenacity polyester resin alloy composition of the present invention, in order that antioxidant less volatilizees and decomposes, the high antioxidant of preferably fusing point, specifically preferably use double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythrite-diphosphites, double (2,4- di-tert-butyl-phenyl) pentaerythrite-diphosphites or double (2,4- dicumylphenyl) pentaerythrite-diphosphites etc..
The preferred 0.05-2 weight portions of antioxidant, more preferably 0.1-1 weight portions.
In the present invention, because inorganic filler can improve a part for crystallization property, arc resistance, anisotropy, mechanical strength, anti-flammability or the heat distortion temperature of the present composition etc., addition inorganic filler, the inorganic filler can be further coordinated to include fibre reinforced materials and the inorganic filler beyond fibre reinforced materials.Wherein, fibre reinforced materials includes glass fibre, carbon fiber, or the fibrous reinforcements such as Kafra fiber, as the inorganic filler beyond described fibre reinforced materials, it is not particularly limited, such as needle-like, it is granular, the inorganic filler of powder and stratiform, as concrete example, bead can be enumerated as, glass sheet stock, potassium titanate crystal whisker, calcium sulfate crystal whiskers, wollastonite, silica, kaolin, talcum, terre verte system clay mineral (montmorillonite, hectorite), vermiculite, mica, fluorine taincolite, basic zirconium phosphate, titanium phosphate, or dolomite etc., preferably use at least one.Alternatively, it is also possible to carry out the surface treatment of coupling agent treatment, epoxy compound finishing or ionization process etc. to the inorganic filler beyond above-mentioned fibre reinforced materials.In addition, the average grain diameter of the inorganic filler of granular, powder and stratiform, from from the aspect of impact strength, preferably 0.1-20 μm, particularly preferably 0.2-13 μm.In addition, the consumption of inorganic filler, mobility when shaping and from the aspect of the durability of forming machine or metal pattern, the preferably no more than amount of 1-45 weight % of composition total weight.Do not damaging in the range of effect of the present invention, in order to obtain more preferable mechanical property, the preferably at least one in glass fibre, talcum powder, mica, calcium carbonate, calcium sulfate, magnesium sulfate, silica whisker or potassium titanate crystal whisker.
In addition，Do not damaging in the range of effect of the present invention，Can add releasing agent (montanic acid and its slaine in the high-tenacity polyester resin alloy composition of the present invention、Its ester、Its half ester、Hard ester alcohol、Stearmide、It is polyamide-based、Biruea or Tissuemat E etc.，Wherein from generation gas when reducing shaping，Preferred polyamide class)、Pigment (cadmium sulfide、Phthalocyanine、Or color black masterbatch etc.)、Dyestuff (nigrosine etc.)、Crystal seed agent (talcum powder、Titanium dioxide、Kaolin、Clay、Or polyether-ether-ketone etc.)、Plasticizer (P-hydroxybenzoic acid monooctyl ester、Or N-butylbenzenesulfonamide etc.)、Antistatic additive (alkyl sulphate type anion system antistatic additive、Quaternary ammonium salt cationic system antistatic additive、The nonionic system such as polyoxyethylene sorbitol acid anhydride single-hard ester acid ester antistatic additive、Or glycine betaine system both sexes antistatic additive etc.)、Fire retardant (such as red phosphorus、Phosphate、Melamine hydrogen urea hydrochlorate、Magnesium hydroxide、The hydroxide such as aluminium hydroxide、Ammonium polyphosphate、Brominated Polystyrene、Brominated polyphenylether、Brominated polycarbonate、Combination of brominated epoxy resin or these bromide fire retardants and antimony oxide etc.)、Or other polymer.
A kind of preparation method of the high-tenacity polyester resin alloy composition of the present invention, first by A) polybutylene terephthalate (PBT), (B) polyethylene terephthalate, add high speed mixers from dimmer compound and other additives based on (C) ethylene copolymer octene, mix 5-10 minutes；Blending material is added into double screw extruder melting extrusion granulation, processing temperature is 220 DEG C -290 DEG C, and engine speed is 100-300rpm.
A kind of preparation method of the high-tenacity polyester resin alloy composition of the present invention, can be with from extruder side spout addition reinforcing material (glass fibre, potassium titanate crystal whisker etc.), when adding two kinds of reinforcing materials simultaneously, to make two kinds of reinforcing materials just add fashionable input amount more accurate simultaneously, using two batch chargers.
Further illustrate the present invention below by specific embodiment, following examples premised on technical solution of the present invention under implemented, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.
Embodiment
1. raw material explanation
(A) the beautiful 1100M in polybutylene terephthalate (PBT) east；
(B) the beautiful U46 in polyethylene terephthalate east；
(C) making by oneself from this society of dimmer compound based on ethylene copolymer octene, preparation method is as follows：
By POE product and the initiator azo-bis-isobutyl cyanide (AIBN) of the DOW companies of buying, methacrylic acid and methacrylate ethylene oxidic ester compare 80 according to mass fraction：10：10 are added to double-screw extruding pelletizing, and then 150 degree of melt temperature dries on particle.The particle of drying is filtered through chemical pure toluene or xylene soluble, then Jing alkaline matter 5%NaOH solution by titration, precipitation again, is dried, then the low temperature drying after 200 mesh sieve.It is obtained through as above step, following four kinds can be determined from aggressiveness, the Na ion concentrations from aggressiveness by chemical titration：
Assay method：A certain amount of dry copolymer about 0.1g of precise is dissolved in during the tetrahydrochysene of 20ml barks and mutter, with phenolphthalein as indicator, with the NaOH/CH of 0.1mol/L3OH solution is titrated, and then can try to achieve methacrylic acid molar content in the copolymer, while can be determined that Na ion concentrations.
Based on ethylene copolymer octene from dimmer compound (1)：Reactive terminal base is GMA, and ethene and octene ratio are 6：1, a:B is 9：1；
Based on ethylene copolymer octene from dimmer compound (2)：Reactive terminal base is GMA, and ethene and octene ratio are 9：1, a:B is 9：1；
Based on ethylene copolymer octene from dimmer compound (3)：Reactive terminal and for maleic anhydride, ethene and octene ratio are 6：1, a:B is 9：1；
Based on ethylene copolymer octene from dimmer compound (4)：Reactive terminal base is GMA, and ethene and octene ratio are 6：1, a：B=3：2；
Glass fibre is manufactured by NEC glass society, 10.5 μm of its single fiber diameter；
Potassium titanate crystal whisker：Shanghai allusion quotation is raised；
Antioxidant：Pentaerythrite four (3- (3 ', 5 '-di-t-butyl) -4 '-hydroxybenzyls) propionic ester), traditional Chinese medicines chemistry；
Silane compound：β-(3,4- expoxycyclohexyls) ethyl trimethoxy silane：Japanese SHIN-ETSU HANTOTAI；
Oxidic polyethylene cured (1160H), Mitsui Chemicals；
Black masterbatch (flame retardant grade), Puri Dehua work.
2. rigidity and toughness properties test：
Bending modulus and bending moment (breakaway poing displacement), are determined with the good standard batten of injection mo(u)lding by standard ISO178, bend speed 2mm/min, and 5 per group are averaged；
Charpy notch impact strengths, are determined with the good standard batten of injection mo(u)lding by standard ISO179, and 5 per group are averaged.
Bending modulus reflects the rigidity of material, and modulus is big, and rigidity is big, otherwise rigidity is little.
Charpy notch impact strengths reflect material by toughness during temporary impact, and intensity is bigger, illustrate that material impact resistance is strong, and bending moment is the deformation quantity produced when external force is slowly acted on material, and it more reflects the ductility of material.If notch impact strength and bending moment increase, it is believed that toughness of material is improved simultaneously.
3. the measure of crystalline rate
It is 2-5mg to take sample size, and all tests are carried out under the protection of nitrogen.Liquid nitrogen quenching is used after pellet sample is melted into 5min at 300 DEG C to eliminate thermal history, then quenching sample DSC is put into into, 300 DEG C is warming up to from 25 DEG C with 10 DEG C/min, from the glass transition temperature Tg of derived sample in the curve and cold crystallization peak Tcc temperature.
Embodiment 1-10, comparative example 1-3：
Raw material is as shown in Table 1-2.In addition to the reinforcing material such as glass fibre and potassium titanate crystal whisker, after other raw materials mix 5 minutes in high-speed mixer, granulated using society of JSW TEX30 α type biaxial extruders (L/D=45.5), add from extruder main spout, glass fibre and potassium titanate crystal whisker are added from extruder side spout, extruder temperature is set as 200 DEG C -290 DEG C, and screw speed is that 200 turns/min Jing are melted, extruded, cooling down, pelletizing obtains granular polyester alloy composite；After this shot-like particle is dried into 3h in 130 DEG C of baking oven, standard batten (batten die size is wide 10mm × thickness 4mm) is molded into, is tested by above-mentioned method of testing, gained test result is recorded in table 3, in 4.
Table 1
Table 2
Table 3
Table 4
The impact strength that the polymer blend from dimmer compound based on addition (C) ethylene copolymer octene is found by the Performance comparision of above-described embodiment and comparative example is significantly improved, for example embodiment 1 is compared with comparative example 1, impact strength has brought up to 10.5 from 6.4, improve about 60%, such as the embodiment 1 while crystallizing power of polyester alloy also increases, 2 can be seen that the Tcc of embodiment has significantly reduction with comparative example 3,4, it was demonstrated that the crystallizing power of polymer is improved.Simultaneously the crystallizing power of polymer is relevant with Na ion concentrations, such as embodiment 1 and embodiment 6, when Na ion concentrations are improved, Tcc cold crystallization temperatures substantially reduce illustrating that crystallizing power is improved, nucleus is promoted to grow up because improving sodium ions content post-consumer polymer and can form ion cluster in the molten state, but ion concentration is too high to cause the decomposition of polymer, may affect the combination property of product.By embodiment 1,8 and 10 it can be found that the performance of the scale effect polyester alloy of PBT/PET, when PBT contents are very few in polyester alloy composition, combination property can be deteriorated, it is advantageous to adding proportion be PBT20-40 parts, PET40-70 parts.
Claims (9)
1. a kind of high-tenacity polyester resin alloy composition, it is characterised in that：The high-tenacity polyester resin alloy
Composition is included：(A) polybutylene terephthalate (PBT), (B) polyethylene terephthalate, with
And based on (C) ethylene copolymer octene from dimmer compound.
2. a kind of high-tenacity polyester resin alloy composition according to claim 1, it is characterised in that：It is described
In high-tenacity polyester resin alloy composition, (A) polybutylene terephthalate (PBT) is 20-40 weight portions；
(B) polyethylene terephthalate is 40-70 weight portions；(C) based on ethylene copolymer octene
It is 1-12 weight portions from dimmer compound.
3. a kind of high-tenacity polyester resin alloy composition according to claim 1, it is characterised in that：It is described
Following formula I structure, wherein x, y are included based on component (C) ethylene copolymer octene from dimmer compound
Positive integer and x for 1 to 10：Y=9：1～5：1.
4. a kind of high-tenacity polyester resin alloy composition according to claim 1, it is characterised in that：It is described
The structure of following formula II or III is included from dimmer compound based on component (C) ethylene copolymer octene, wherein,
A, b are 1 to 10 positive integer, and a：B=9：1～3：2, wherein M are a kind of metal cations
Or ammonium ion.
5. a kind of high-tenacity polyester resin alloy composition according to claim 4, it is characterised in that：It is described
Quality percentage from dimmer compound in of the structure of formula II or III based on component (C) the ethylene copolymer octene
Content is 1-5%.
6. a kind of high-tenacity polyester resin alloy composition according to claim 1, it is characterised in that：Its group
Based on part (C) ethylene copolymer octene from dimmer compound be compound through such as following formula IV or formula V
Graft modification from dimmer compound, its based on (C) ethylene copolymer octene in dimmer compound
Weight/mass percentage composition be 1-5%.
7. a kind of high-tenacity polyester resin alloy composition according to claim 1, it is characterised in that：It is described
High-tenacity polyester resin alloy composition also includes glass fibre, talcum powder, mica, calcium carbonate, sulfuric acid
At least one in calcium, magnesium sulfate, silica whisker or potassium titanate crystal whisker.
8. a kind of high-tenacity polyester resin alloy composition according to claim 1, it is characterised in that：It is described
In high-tenacity polyester resin alloy composition also include antioxidant, the antioxidant be suffocated amine antioxidant,
At least one in Hinered phenols antioxidant or phosphite ester kind antioxidant.
9. a kind of as claimed in claim 1 preparation method of high-tenacity polyester resin alloy composition, its feature exists
In：
By A) polybutylene terephthalate (PBT), (B) polyethylene terephthalate, (C) ethylene copolymer
High speed mixer, 5-10 point of mixing are added based on octene from dimmer compound and other additives
Clock；Blending material is added into double screw extruder melting extrusion granulation, processing temperature is 220 DEG C -290 DEG C,
Engine speed is 100-300rpm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109370175A (en) * | 2018-11-27 | 2019-02-22 | 江苏万纳普新材料科技有限公司 | A kind of PBT direct injection molding efficient enhanced halogen-free flameproof functional agglomerate and preparation method thereof |
| CN109486131A (en) * | 2018-11-27 | 2019-03-19 | 江苏万纳普新材料科技有限公司 | A kind of PBT direct injection molding efficient enhanced flame retarding function master batch and preparation method thereof |
| CN109486132A (en) * | 2018-11-27 | 2019-03-19 | 江苏万纳普新材料科技有限公司 | A kind of PBT direct injection molding efficient enhanced halogen-free flame-retarded heat-conducting shading multifunctional mother granules and preparation method thereof |
| CN110240787A (en) * | 2019-05-09 | 2019-09-17 | 南通开普乐工程塑料有限公司 | Low warpage PBT composite of a kind of dimensionally stable and preparation method thereof |
| CN112592565A (en) * | 2020-11-19 | 2021-04-02 | 江苏博云塑业股份有限公司 | Low-warpage glass fiber reinforced PBT (polybutylene terephthalate) material and preparation method thereof |
| CN113337087A (en) * | 2021-06-17 | 2021-09-03 | 贵州省材料产业技术研究院 | High-performance polyester alloy material and preparation method thereof |
-
2015
- 2015-08-04 CN CN201510469492.3A patent/CN106633681A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109370175A (en) * | 2018-11-27 | 2019-02-22 | 江苏万纳普新材料科技有限公司 | A kind of PBT direct injection molding efficient enhanced halogen-free flameproof functional agglomerate and preparation method thereof |
| CN109486131A (en) * | 2018-11-27 | 2019-03-19 | 江苏万纳普新材料科技有限公司 | A kind of PBT direct injection molding efficient enhanced flame retarding function master batch and preparation method thereof |
| CN109486132A (en) * | 2018-11-27 | 2019-03-19 | 江苏万纳普新材料科技有限公司 | A kind of PBT direct injection molding efficient enhanced halogen-free flame-retarded heat-conducting shading multifunctional mother granules and preparation method thereof |
| CN109370175B (en) * | 2018-11-27 | 2021-03-23 | 江苏万纳普新材料科技有限公司 | Efficient enhanced halogen-free flame-retardant functional master batch for direct injection molding of PBT (polybutylene terephthalate) and preparation method thereof |
| CN109486131B (en) * | 2018-11-27 | 2021-03-23 | 江苏万纳普新材料科技有限公司 | Efficient enhanced flame-retardant functional master batch for direct injection molding of PBT (polybutylene terephthalate) and preparation method thereof |
| CN109486132B (en) * | 2018-11-27 | 2021-03-23 | 江苏万纳普新材料科技有限公司 | Efficient enhanced halogen-free flame-retardant heat-conducting shading multifunctional master batch for direct injection molding of PBT (polybutylene terephthalate) and preparation method thereof |
| CN110240787A (en) * | 2019-05-09 | 2019-09-17 | 南通开普乐工程塑料有限公司 | Low warpage PBT composite of a kind of dimensionally stable and preparation method thereof |
| CN112592565A (en) * | 2020-11-19 | 2021-04-02 | 江苏博云塑业股份有限公司 | Low-warpage glass fiber reinforced PBT (polybutylene terephthalate) material and preparation method thereof |
| CN113337087A (en) * | 2021-06-17 | 2021-09-03 | 贵州省材料产业技术研究院 | High-performance polyester alloy material and preparation method thereof |
| CN113337087B (en) * | 2021-06-17 | 2022-11-18 | 贵州省材料产业技术研究院 | High-performance polyester alloy material and preparation method thereof |
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Application publication date: 20170510 |