CN101787184A - Quickly crystallized polyester engineering plastic and preparation method thereof - Google Patents
Quickly crystallized polyester engineering plastic and preparation method thereof Download PDFInfo
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- CN101787184A CN101787184A CN200910312669A CN200910312669A CN101787184A CN 101787184 A CN101787184 A CN 101787184A CN 200910312669 A CN200910312669 A CN 200910312669A CN 200910312669 A CN200910312669 A CN 200910312669A CN 101787184 A CN101787184 A CN 101787184A
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Abstract
The invention relates to a quickly crystallized polyester engineering plastic and a preparation method thereof. The quickly crystallized polyester engineering plastic is prepared with the following components by way of extrusion in a double-screw extruder: 100 parts by weight of modified quickly crystallized polyester A, 0.05 to 5 parts by weight of nucleating agent B, 10 to 40 parts by weight of glass fibers C, 10 to 30 parts by weight of flame retardant D, 1 to 15 parts by weight of flexibilizer E and 0.01 to 3 parts by weight of antioxidant F. The engineering plastic has the advantages of high crystallization speed, high mechanical strength, quick injection moulding and low-temperature demoulding, the finished product cannot be deformed, and the engineering plastic prepared with the quickly crystallized polyester engineering plastic composition has the advantages of high crystallization speed, high mechanical strength, quick injection moulding and low-temperature demoulding.
Description
Technical field
The present invention relates to the quickly crystallized polyester engineering plastic made with modification fast crystallization polyester, crystallization nucleating agent, glass fibre, fire retardant and toughner.Say in more detail, relate to have rapid crystallization, the characteristic of polyester engineering plastic such as tensile strength, shock strength, flexural strength, heat resistance; Fast demoulding characteristic at low temperatures during with rapid crystallization performance and injection moulding.
Background technology
Polyethylene terephthalate (PET) extensively is applied to fields such as synthon, film and engineering plastics at present.Its outstanding feature is to have performances such as good thermotolerance, electrical insulating property, chemical proofing and asepsis environment-protecting; And have lower production cost and high cost performance.
Particularly in textile industry, PET is a kind of important synthetic fiber material.The output of the PET of China section at present is up to up to ten million ton/years, owing to reasons such as the industrial structure is unreasonable have caused China's fiber level PET excessive.The harmful competition of price and the decline of polyester corporate profit have been caused, problems such as production capacity surplus.
Except being used in the textile industry, PET can also be applied in film, on bottle blowing and the engineering plastics.Particularly be applied on the engineering plastics.PET engineering plastics and nylon, polypropylene, engineering plastics such as polycarbonate and PBT are compared, and have unique cost performance.PET engineering plastics good rigidly stretches mechanical property height such as bending; Heat resisting temperature height (can reach 220 ℃); Good electrical property (higher insulating property, high CTI value); Attracting especially is low price.Therefore to develop the PET engineering plastics be very promising and economic worth.Particularly can digest the at present excessive PET section of China.
But because the PET texture ratio is than rigidity, so it is a kind of superpolymer of hemicrystalline, and its crystallization rate is slower, and degree of crystallinity is incomplete, and speed was slow when this had directly caused its injection moulding, and molding cycle is long; Degree of crystallinity is low simultaneously makes that its heat-drawn wire is low, poor mechanical property.These have all limited its application in engineering plastics.People are devoted to improve the crystallization rate of PET always for many years, improve its processing characteristics.Mainly concentrate on the research of PET crystallization nucleating agent for the research of this respect, by adding nucleator and nucleation accelerating agent, improving PET crystallization rate and degree of crystallinity, and die temperature when reducing injection moulding, to reach the requirement that engineering plastics are used.
For example: patent, CN1775852A contains the preparation method of superfine oxide thermoplastic polyester engineering plastics, has described inorganic oxides such as silicon-dioxide, titanium dioxide, aluminium sesquioxide and has improved thermoplastic polyester engineering plastics crystalline method as nucleator.Obtained the reasonable thermoplastic polyester engineering plastics of mechanical property, heat resistance and frictional behaviour.
Patent CN1600812A polyester engineering plastic alloy and manufacture method have been described the polyester engineering plastic alloy that obtains high tenacity with polyurethane or polyester elastomer and polyester blend.
200710173612.0 a kind of polyester composite composition is provided, it comprises following composition and weight part content: polyester 100 weight parts, polyethylene naphthalate fiber 5-60 weight part, nucleator 0.8-1.8 weight part, and optional processing aid 0-1 weight part.Described polyester composite composition can make the polyester composite that crystallization is fast and intensity is high.
" improvement of PET engineering plastics crystal property " is (referring to " improvement of PET engineering plastics crystal property " of Wu Tong, Zheng Xiao seedling, Li Yanli, the 19th the 2nd phase of volume of Beijing Institute of Clothing Tech's journal) improvement of PET engineering plastics crystal property is studied, point out " improve the crystal property of PET; generally set about from two aspects: the one, adopt approach such as plasticising, copolymerization and blend (adding or do not add crystallization nucleating agent); reduce its second-order transition temperature, promote crystallization and crystal growing; The 2nd, add suitable crystallization nucleating agent or crystal and increase agent, improve the crystallization velocity of PET "; and consult on the basis of lot of documents; according to existence conditions; the utilization Orthogonal Method chooses suitable crystallization promoter and crystallization nucleating agent matches; and add certain interfacial compatibilizer, formulated 4 assembly sides.Test result shows, compares with blank PET, and the crystal property of PET blend has obtained very big improvement.
Above method can not solve that PET engineering plastics crystallization velocity is slow, and the moulding and the demoulding are slow, and problem such as injection moulding temperature height.
Summary of the invention
First purpose of the present invention is to overcome above-mentioned defective, provides that a kind of crystallization velocity is fast, mechanical strength is high, injection moulding is fast and demoulding and the indeformable quickly crystallized polyester engineering plastic of finished product at low temperatures.
Second purpose of the present invention is to provide a kind of preparation method of quickly crystallized polyester engineering plastic of the present invention, this method is simple to operate, advantage such as prepared fast crystallization engineering plastics crystallization velocity is fast, mechanical strength is high, injection moulding is fast and demoulding and finished product are indeformable at low temperatures.
For realizing first purpose of the present invention, the present invention adopts following technical scheme:
A kind of quickly crystallized polyester engineering plastic, wherein, described quickly crystallized polyester engineering plastic is made through extruding in twin screw extruder by following feed composition:
Modification fast crystallization polyester A 100 weight parts
Crystallization nucleating agent B 0.05～5 weight part
Glass fibre C 10～40 weight parts
Fire retardant D 10～30 weight parts
Toughner E 1～15 weight part
Oxidation inhibitor F 0.01～3 weight part;
Preferably in twin screw extruder, extrude and make by following feed composition:
Modification fast crystallization polyester A 100 weight parts
Crystallization nucleating agent B 0.15～3 weight part
Glass fibre C 20～30 weight parts
Fire retardant D 15～25 weight parts
Toughner E 2～10 weight parts
Oxidation inhibitor F 0.02～2 weight part.
According to aforesaid quickly crystallized polyester engineering plastic, wherein, described feed composition also comprises color master-batch, and described color master-batch is 0.5～10 weight part, preferred 1～6 weight part.
According to aforesaid quickly crystallized polyester engineering plastic, wherein, the limiting viscosity of described modification fast crystallization polyester A is 0.5～1.2dl/g, preferred 0.6～1.0dl/g;
The modification fast crystallization polyester A that described modification fast crystallization polyester A is made up of the copolymer composition of the polyalkylene terephthalates of 80～100 moles of % and 0～20 mole of %;
The polymkeric substance copolyreaction of preferred terephthalic acid or derivatives thereof of described polyalkylene terephthalates and aklylene glycol makes, and perhaps the mixture copolyreaction for terephthalic acid or derivatives thereof and aklylene glycol makes,
The more preferably mixture of one or more in polyethylene terephthalate, Poly(Trimethylene Terephthalate) or the polybutylene terephthalate, most preferably two or more mixtures.
According to aforesaid quickly crystallized polyester engineering plastic, wherein, described crystallization nucleating agent B is one or more the combination in inorganic particles, organic sodium salt class or the Ionomer;
Wherein, described inorganic particles is 0.1～8 weight part, preferred 0.2～6 weight part; Described organic sodium salt class is 0.05～5 weight part, preferred 0.1～3 weight part; Described Ionomer is 0.1～6 weight part, preferred 0.3～5 weight part;
The preferred titanium dioxide of described inorganic particles, silicon-dioxide, zinc oxide, aluminum oxide, talcum powder, kaolin, hydrotalcite, polynite or lime carbonate;
Described organic sodium salt class preferred sodium benzoate, Sodium P-Chlorobenzoate, sodium stearate, barium stearate or montanic acid sodium;
Described Ionomer optimal ethylene-sodium acrylate ionic polymer or ethylene-methyl methacrylate sodium ion polymkeric substance.
According to aforesaid quickly crystallized polyester engineering plastic, wherein, described glass fibre C is one or more the combination in alkali-free roving glass fiber or the alkali-free short glass fiber.
According to aforesaid quickly crystallized polyester engineering plastic, wherein, described fire retardant D is the combination of brominated flame retardant and antimony based flame retardant, perhaps is the combination of one or more halogen-free flame retardantss; The preferred decabromodiphenyl oxide of described brominated flame retardant, eight bromo ether, TDE, brominated oxidative ethane or bromination distyryl; Preferred antimonous oxide of described antimony based flame retardant or sodium antimonate; The preferred hypophosphite of described halogen-free flame retardants, phosphorus nitrogen is composite or the red phosphorus master batch.
According to aforesaid quickly crystallized polyester engineering plastic, wherein, described toughner E is polyester elastomer or rubber particles, and described polyester elastomer or rubber particles are the compound that contains 2 or above functional group;
Described toughner E optimal ethylene-ethyl propenoate-glycidyl methacrylate, ethylene-propylene acid butyl ester-glycidyl methacrylate, ethylene-methyl methacrylate butyl ester-glycidyl acrylate, ethylene-octene copolymer, ethylene-octene copolymer grafted maleic anhydride, ethene-vinyl acetate-copolymer-maleic anhydride, styrene-ethylene butylene-styrene multipolymer or styrene-ethylene butylene-styrene copolymer grafted maleic anhydride.
For realizing second purpose of the present invention, the present invention adopts following technical scheme:
A kind of preparation method of quickly crystallized polyester engineering plastic provided by the present invention, wherein, described preparation method comprises the steps:
1) with described feed composition drying;
2) it is even dried modification fast crystallization polyester A, crystallization nucleating agent B, fire retardant D, toughner E and oxidation inhibitor F to be put into the high-speed mixing stirrer for mixing, gets mixture;
3) place twin screw extruder to extrude in mixture and glass fibre C, after extruding, the water-cooled tie rod, granulated and dried, packing promptly gets described quickly crystallized polyester engineering plastic.
According to the preparation method of aforesaid quickly crystallized polyester engineering plastic, wherein, after the described modification fast crystallization polyester A drying, its water content is 30～200ppm, preferred 50～100ppm.
According to the preparation method of aforesaid quickly crystallized polyester engineering plastic, wherein, die head temperature is made as 240～310 ℃, preferred 250～300 ℃ when placing twin screw extruder to extrude the mixture in the step 3).
Below be detailed description of the present invention:
On the one hand, the invention provides a kind of quickly crystallized polyester engineering plastic, it is slow to have solved in the prior art polyester engineering plastic crystallization velocity, and moulding and demoulding are slow, and problem such as injection moulding temperature height.
Quickly crystallized polyester engineering plastic provided by the present invention is made through extruding in twin screw extruder by following composition:
Modification fast crystallization polyester A 100 weight parts
Crystallization nucleating agent B 0.05～5 weight part
Glass fibre C 10～40 weight parts
Fire retardant D 10～30 weight parts
Toughner E 1～15 weight part
Oxidation inhibitor F 0.01～3 weight part.
Crystallization velocity is to limit the major cause that PET uses in the engineering plastics field for a long time slowly.Prior art is improved the crystal property of PET, generally starts with from two aspects: the one, adopt approach such as plasticising, copolymerization and blend, and reduce its second-order transition temperature, promote crystallization and crystal growing; The 2nd, add suitable crystallization nucleating agent or crystal and increase agent, improve the crystallization velocity of PET.Though adopt its crystal property of aforesaid method to make moderate progress, effect is also not obvious.
The present invention adopts to be melt extruded at twin screw extruder together by modification fast crystallization polyester A, crystallization nucleating agent B, glass fibre C, fire retardant D, toughner E and oxidation inhibitor F and makes.Wherein modification fast crystallization polyester A is the polymeric modification fast crystallization polyester, has added flexible copolymerization component in polymerization process.After the flexible composition,, and make the easier slippage of polyester molecule chain in the copolymerization at the reactive force that has reduced on the molecular level between the polyester molecule chain; Make easier the folding of polyester molecule chain enter crystal.Because flexible composition is aggregated on the polyester macromolecule chain, therefore intensity and the performance for polyester material do not influence simultaneously.
Polyester material is easily degraded at high temperature, among the present invention, adds oxidation inhibitor and can prevent that polyester material from high temperature degrading.
In addition, the adding of crystallization nucleating agent provides ctystallizing point for the polyester macromolecule chain among the present invention, and promptly macromolecular chain is assembled around nucleator, the folding then crystalline region that enters.Therefore, the present invention adds crystallization nucleating agent and polymeric modification adds the crystallization velocity that crystallization promoter can be accelerated polyester greatly, improves degree of crystallinity.
The present invention is through further test, shows that the crystal property of the quickly crystallized polyester engineering plastic that makes when the following weight part composition of selection is better:
Modification fast crystallization polyester A 100 weight parts
Crystallization nucleating agent B 0.15～3 weight part
Glass fibre C 20～30 weight parts
Fire retardant D 15～25 weight parts
Toughner E 2～10 weight parts
Oxidation inhibitor F 0.02～2 weight part.
Among the present invention, described oxidation inhibitor F is 1010, triphenyl phosphite or trimethyl phosphite etc.
The usage quantity of oxidation inhibitor F does not have special requirement.Can require to add according to reality.With respect to A component 100 weight parts, preferred 0.01～3 weight part, preferred again 0.02～2 weight part.
Among the present invention, can further add color master-batch according to the whether painted needs of product, color master-batch can be carbonarius master batch, titanium white white master batch, the red master batch of ferrochrome, yellow masterbatch or brown master batch etc.
Among the present invention, the usage quantity of described color master-batch does not have special requirement.Can require to add according to reality.With respect to A component 100 weight parts, preferred 0.5～10 weight part, preferred again 1～6 weight part.
In the quickly crystallized polyester engineering plastic provided by the present invention, wherein, the modification fast crystallization polyester A that described modification fast crystallization polyester A is made up of the copolymer composition of 80%～100% polyalkylene terephthalates and 0～20%, described copolymer composition is a m-phthalic acid, phthalic acid, naphthalene dicarboxylic acids, to the penylene dicarboxylic acid, Pyromellitic Acid, succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, the Kui diacid, lactic acid, carbonic acid, the dicarboxylic acid derivatives that contains sulfonate, 1,2-ethylene glycol, 1, ammediol, 1, the 4-butyleneglycol, 1, the 6-hexylene glycol, neopentyl glycol, 1, the 4-cyclohexanedimethanol, Diethylene Glycol, polyoxyethylene glycol, polytetramethylene glycol, tetramethylolmethane, the 4-hydroxy-benzoic acid, 6-caprolactone, dihydroxyphenyl propane, Resorcinol or 1, the 4-terephthalyl alcohol;
Aforesaid copolymer composition can be in main chain or the side chain polycondensation with polyalkylene terephthalates, does not have special restriction for method of copolymerization etc.
Described crystallization nucleating agent B is one or more the combination in inorganic particles, organic salt or the Ionomer;
Described glass fibre C is one or more the combination in alkali-free roving glass fiber or the alkali-free short glass fiber;
Usage quantity for glass fibre C composition of the present invention does not have special requirement, but for respect to A composition 100 weight parts, preferred 10～40 weight parts, preferred again 20～30 weight parts.
Described fire retardant D is the combination or the halogen-free flame retardants of brominated flame retardant and antimony based flame retardant;
Described antimony based flame retardant is selected from the combination of antimony based flame retardants such as brominated flame retardants such as decabromodiphenyl oxide, eight bromo ether, TDE, brominated oxidative ethane, brominated Polystyrene and antimonous oxide, sodium antimonate; It can also be a kind of or combination more than 2 kinds of halogen-free flame retardantss such as, red phosphorus master batch composite as hypophosphite, phosphorus nitrogen.
Described toughner E is polyester elastomer or rubber particles, described polyester elastomer or rubber particles are the compound that contains 2 or above functional group, optimal ethylene-ethyl propenoate-glycidyl methacrylate, ethylene-propylene acid butyl ester-glycidyl methacrylate, ethylene-methyl methacrylate butyl ester-glycidyl acrylate, ethylene-octene copolymer, the ethylene-octene copolymer grafted maleic anhydride, ethene-vinyl acetate-copolymer-maleic anhydride, styrene-ethylene butylene-styrene multipolymer or styrene-ethylene butylene-styrene copolymer grafted maleic anhydride.
In the quickly crystallized polyester engineering plastic provided by the present invention, wherein, described polyalkylene terephthalates is that the polymkeric substance copolyreaction of terephthalic acid or derivatives thereof and aklylene glycol makes, and perhaps the mixture copolyreaction for terephthalic acid or derivatives thereof and aklylene glycol makes;
Described inorganic particles is titanium dioxide, silicon-dioxide, zinc oxide, aluminum oxide, talcum powder, kaolin, hydrotalcite, polynite or lime carbonate;
Described organic sodium salt class is Sodium Benzoate, Sodium P-Chlorobenzoate, sodium stearate, barium stearate or montanic acid sodium;
Described Ionomer is ethylene-acrylic acid sodium ion polymkeric substance or ethylene-methyl methacrylate sodium ion polymkeric substance.
In the quickly crystallized polyester engineering plastic provided by the present invention, wherein, described polyalkylene terephthalates is one or more the mixture in polyethylene terephthalate, Poly(Trimethylene Terephthalate) or the polybutylene terephthalate.In the quickly crystallized polyester engineering plastic provided by the present invention, wherein, the limiting viscosity of described modification fast crystallization polyester A is 0.5～1.2dl/g, preferred 0.6～1.0dl/g.
Among the present invention,, select 0.5～1.2dl/g, preferred 0.6～1.0dl/g for the limiting viscosity of modification fast crystallization polyester A composition.Because when limiting viscosity is lower than 0.5 dl/g, the intensity of quickly crystallized polyester engineering plastic is lower, and melt viscosity increases when surpassing 1.2dl/g, and screw rod adds become difficulty and crystal property of trade union and is affected.
In the quickly crystallized polyester engineering plastic provided by the present invention, wherein, described inorganic particles is 0.1～8 weight part, preferred 0.2～6 weight part.
Among the present invention, there is not special requirement for the inorganic particles particle diameter in the B composition, but preferred 0.01～5 μ m, preferred again 0.02～3 μ m.The inorganic particles that the present invention uses can use silane compound, titanate compound, isocyanate compound etc. to carry out surface treatment as required.Usage quantity for the inorganic particles in the B component does not have special requirement, but with respect to A composition 100 weight parts, preferred 0.1～8 weight part, preferred again 0.2～6 weight part.
In the quickly crystallized polyester engineering plastic provided by the present invention, wherein, described organic sodium salt class is 0.05～5 weight part, preferred 0.1～3 weight part.
Among the present invention, do not have special requirement, need not powder handling yet for the organic sodium salt class particle diameter in the B composition.The usage quantity of organic sodium salt class does not have special requirement, but with respect to A composition 100 weight parts, preferred 0.05～5 weight part, preferred again 0.1～3 weight part.
In the quickly crystallized polyester engineering plastic provided by the present invention, wherein, described Ionomer is 0.1～6 weight part, preferred 0.3～5 weight part.
Among the present invention, do not have special requirement, need not powder handling yet for the particle diameter of the Ionomer in the B composition.The usage quantity of Ionomer does not have special requirement, but with respect to A composition 100 weight parts, 0.1～6 weight part, preferred again 0.3～5 weight part.
The fusing point of quickly crystallized polyester engineering plastic of the present invention is 240～260 ℃; Preferred 245～255 ℃; Preferred again 248～255 ℃.
The fusion-crystallization peak temperature of quickly crystallized polyester engineering plastic of the present invention is 200～225 ℃; Preferred 205～220 ℃, preferred again 210～218 ℃.
The tensile strength of quickly crystallized polyester engineering plastic of the present invention is 110～140MPa, preferred 120～135MPa, preferred again 125～130MPa.
Quickly crystallized polyester engineering plastic flexural strength of the present invention is 170～220MPa, preferred 180～210MPa, preferred again 185～200MPa.
The simply supported beam notched Izod impact strength of quickly crystallized polyester engineering plastic of the present invention is 5～12KJ/m
2, preferred 7～10KJ/m
2, preferred again 9～10KJ/m
2
The heat-drawn wire of quickly crystallized polyester engineering plastic of the present invention is at 190～240 ℃, and preferred 200～230 ℃, preferred again 220～225 ℃.
The flame retardant resistance of quickly crystallized polyester engineering plastic of the present invention is V2～V0, preferred V0.
Advantages such as the crystallization velocity of quickly crystallized polyester engineering plastic of the present invention is fast, injection moulding fast, low temperature fast demoulding.
The demould time of quickly crystallized polyester engineering plastic of the present invention is 3～15 seconds/time; Preferred 5～10 seconds/time.
On the other hand, the invention provides a kind of preparation method of quickly crystallized polyester engineering plastic, this method is simple to operate, advantage such as prepared fast crystallization engineering plastics crystallization velocity is fast, mechanical strength is high, injection moulding is fast and demoulding and finished product are indeformable at low temperatures.
The preparation method of quickly crystallized polyester engineering plastic provided by the present invention comprises the steps:
1) with described feed composition drying;
2) it is even dried modification fast crystallization polyester A, crystallization nucleating agent B, fire retardant D, toughner E and oxidation inhibitor to be put into the high-speed mixing stirrer for mixing, gets mixture;
3) place twin screw extruder to extrude in mixture and glass fibre C, after extruding, the water-cooled tie rod, granulated and dried, packing promptly gets described quickly crystallized polyester engineering plastic.
Among the preparation method of quickly crystallized polyester engineering plastic provided by the present invention, wherein, after the described modification fast crystallization polyester A drying, its water content is 30～200ppm, preferred 50～100ppm.
Polyester can be degraded when high temperature process.Among the present invention, controlling moisture content can prevent that polyester A from degrading when high temperature process.
Among the preparation method of quickly crystallized polyester engineering plastic provided by the present invention, when in the step 3) mixture and glass fibre C being placed twin screw extruder, the main spout that mixture is extruded from twin screw adds, and glass fibre C adds inlet from glass and enters screw rod.
Among the preparation method of quickly crystallized polyester engineering plastic provided by the present invention, wherein, when placing twin screw extruder to extrude mixture and the glass fibre C in the step 3), each heating interval temperature is made as 240～310 ℃, preferred 250～300 ℃.Described heating interval is 7 districts altogether.
Compared with prior art, the present invention has following advantage:
(1) quickly crystallized polyester engineering plastic provided by the present invention is because polymeric modification fast crystallization polyester A in the feed composition has added flexible copolymerization component in polymerization process.After the flexible composition,, and make the easier slippage of polyester molecule chain in the copolymerization at the reactive force that has reduced on the molecular level between the polyester molecule chain; Make easier the folding of polyester molecule chain enter crystal.Simultaneously because flexible composition be aggregated on the polyester macromolecule chain therefore for the intensity and the not influence of performance of polyester material.
(2) quickly crystallized polyester engineering plastic provided by the present invention, because the adding of crystallization nucleating agent B provides ctystallizing point for the polyester macromolecule chain in its feed composition, promptly macromolecular chain is assembled around nucleator, the folding then crystalline region that enters.Therefore, we add crystallization nucleating agent and polymeric modification adds the crystallization velocity that crystallization promoter can be accelerated polyester greatly, improve degree of crystallinity.
(3) the hypocrystalline time t of quickly crystallized polyester engineering plastic provided by the present invention
1/2: 224 ℃ is 213s; And 224 ℃ of second crystallization times of general polyester engineering plastic are 676s.The crystallization velocity of quickly crystallized polyester engineering plastic of the present invention is 3 times of general polyester engineering plastic.
(4) demould time of quickly crystallized polyester engineering plastic provided by the present invention is 3～5 seconds/time, and general polyester engineering plastic is 5～8 seconds/time.
(5) the present invention has simple to operate, advantage such as crystallization velocity is fast, mechanical strength is high, injection moulding is fast and the demoulding and finished product are indeformable at low temperatures.
Embodiment
Below be the specific embodiment of the present invention, described embodiment is in order to further describe the present invention, rather than restriction the present invention.
Embodiment 1
With the fast crystallization polyethylene terephthalate of 100 parts of polymeric modifications that is dried to below the water content 100ppm, limiting viscosity 0.80dl/g (K100 of China Textile Academy), 6 parts ethylene-methyl methacrylate sodium ion polymkeric substance (Sulyn8920 of E.I.Du Pont Company), 30 parts alkali-free roving glass fiber (the prosperous glass E200 in Tongzhou, Beijing), the antimonous oxide of 10 parts decabromodiphynly oxide (102E of U.S. Albemarle Corporation) and 3 parts (flash star antimony industry company), 1010 of ethylene-methyl methacrylate butyl ester-glycidyl acrylate of 8 parts (PTW of E.I.Du Pont Company) and 0.5 part mixes.Twin screw extruder melt extrudes under 280 ℃.Water-cooled tie rod, pelletizing.Promptly get quickly crystallized polyester engineering plastic.
Embodiment 2
With the fast crystallization polyethylene terephthalate of 100 parts of polymeric modifications that is dried to below the water content 100ppm, 1010 of the antimonous oxide (flash star antimony is company already) of limiting viscosity 0.80dl/g (K100 of China Textile Academy), ethylene-propylene acetoacetic ester-glycidyl methacrylate (atropic luxuriant and rich with fragrance sodium the AX8900 of company) of 6 parts, 30 parts alkali-free roving glass fiber (the prosperous glass E200 in Tongzhou, Beijing), 0.5 part montanic acid sodium (NAV101 Clariant company), 15 parts brominated oxidative ethane (Israel Dead Sea bromine company 2100) and 3 parts and 0.5 part mixes.Twin screw extruder melt extrudes under 260～280 ℃.Water-cooled tie rod, pelletizing.Promptly get quickly crystallized polyester engineering plastic.
Embodiment 3
With the fast crystallization polyethylene terephthalate of 100 parts of polymeric modifications that is dried to below the water content 100ppm, 1010 of the sodium antimonate (flash star antimony industry company) of the talcum powder (Haicheng talcum company) of limiting viscosity 0.8dl/g (K100 of China Textile Academy), 2 parts ethylene-methyl methacrylate sodium ion polymkeric substance (Sulyn8920 of E.I.Du Pont Company) and 0.5 part, 14 parts brominated Polystyrene (U.S. Albemarle Corporation 7010) and 4 parts, ethylene-methyl methacrylate butyl ester-glycidyl acrylate (PTW of E.I.Du Pont Company) of 8 parts and 0.5 part mixes.Twin screw extruder melt extrudes under 260～280 ℃.Water-cooled tie rod, pelletizing.Promptly get quickly crystallized polyester engineering plastic.
Embodiment 4
With the fast crystallization polyethylene terephthalate of 100 parts of polymeric modifications that is dried to below the water content 100ppm, limiting viscosity 0.8dl/g (K100 of China Textile Academy), 10 parts of polybutylene terephthalates, 1010 of the sodium antimonate (flash star antimony industry company) of limiting viscosity 1.0 (Yizheng Fiber Optical plant company of China Petrochemical Industry), 0.5 part talcum powder (Haicheng talcum company), 14 parts brominated Polystyrene (U.S. Albemarle Corporation 7010) and 4 parts, ethylene-methyl methacrylate butyl ester-glycidyl acrylate (PTW of E.I.Du Pont Company) of 8 parts and 0.5 part mixes.Twin screw extruder melt extrudes under 260～280 ℃.Water-cooled tie rod, pelletizing.Promptly get quickly crystallized polyester engineering plastic.
Embodiment 5
With the fast crystallization polyethylene terephthalate of 80 parts of polymeric modifications that is dried to below the water content 100ppm, limiting viscosity 0.8dl/g (K100 of China Textile Academy), 20 parts polybutylene terephthalate, the polynite that limiting viscosity 1.0dl/g (Yizheng Fiber Optical plant company of China Petrochemical Industry) is 1 part (DK200 of Zhejiang Feng Hong clay company limited), the antimonous oxide of 14 parts brominated Polystyrene (U.S. Albemarle Corporation 7010) and 3 parts (flash star antimony industry company), 1010 of ethylene-methyl methacrylate butyl ester-glycidyl acrylate of 8 parts (PTW of E.I.Du Pont Company) and 0.5 part mixes.Twin screw extruder melt extrudes under 260～280 ℃.Water-cooled tie rod, pelletizing.Promptly get quickly crystallized polyester engineering plastic.
Embodiment 6
With the fast crystallization polyethylene terephthalate of 100 parts of polymeric modifications that is dried to below the water content 100ppm, 1010 of the sodium antimonate (flash star antimony industry company) of limiting viscosity 0.75dl/g (K100 of China Textile Academy), 0.5 part talcum powder (Haicheng talcum company), 14 parts brominated Polystyrene (U.S. Albemarle Corporation 7010) and 4 parts, ethylene-methyl methacrylate butyl ester-glycidyl acrylate (PTW of E.I.Du Pont Company) of 8 parts and 0.5 part mixes.Twin screw extruder melt extrudes under 260～280 ℃.Water-cooled tie rod, pelletizing.Promptly get quickly crystallized polyester engineering plastic.
Embodiment 7
1) be that 1010 of the fast crystallization polyethylene terephthalate of 100 parts of polymeric modifications of 0.5dl/g, 0.5 part talcum powder, 30 parts alkali-free roving glass fiber, 14 parts brominated Polystyrene, 4 parts sodium antimonate, ethylene-methyl methacrylate butyl ester-glycidyl acrylate of 8 parts and 0.5 part carries out drying with limiting viscosity, wherein the fast crystallization polyethylene terephthalate of polymeric modification is dried to below the water content 100ppm;
2) it is even dried other feed composition except that the alkali-free roving glass fiber to be put into the high-speed mixing stirrer for mixing, gets mixture;
3) with step 2) mixture of gained adds from the main spout of twin screw extruder, will add inlet from glass through the alkali-free roving glass fiber of step 1) drying treatment and enter screw rod, and each heating interval temperature of twin screw extruder is made as 300 ℃ and melt extrudes; After extruding, the water-cooled tie rod, granulated and dried, packing promptly gets quickly crystallized polyester engineering plastic.
The fusing point of the quickly crystallized polyester engineering plastic of gained is 240 ℃, and fusion-crystallization peak temperature is 200 ℃, and tensile strength is 110MPa, and flexural strength is 170MPa, and the simply supported beam notched Izod impact strength is 5KJ/m
2, heat-drawn wire is 190 ℃, and flame retardant resistance is V0, and the demoulding time is 15 seconds/time.
Embodiment 8
1) be that the fast crystallization Poly(Trimethylene Terephthalate) of 100 parts of polymeric modifications of 1.2 dl/g, 0.1 part titanium dioxide, 20 parts alkali-free short glass fiber, 15 parts TDE, 4 parts sodium antimonate, ethylene-propylene acetoacetic ester-glycidyl methacrylate of 10 parts and 0.01 part triphenyl phosphite carry out drying with limiting viscosity, wherein the fast crystallization Poly(Trimethylene Terephthalate) of polymeric modification is dried to water content 50ppm;
2) it is even dried other feed composition except that the alkali-free short glass fiber to be put into the high-speed mixing stirrer for mixing, gets mixture;
3) with step 2) mixture of gained adds from the main spout of twin screw extruder, will add inlet from glass through the alkali-free short glass fiber of step 1) drying treatment and enter screw rod, and each heating interval temperature of twin screw extruder is made as 250 ℃ and melt extrudes; After extruding, the water-cooled tie rod, granulated and dried, packing promptly gets quickly crystallized polyester engineering plastic.
The fusing point of the quickly crystallized polyester engineering plastic of gained is 260 ℃, and fusion-crystallization peak temperature is 225 ℃, and tensile strength is 140MPa, and flexural strength is 220MPa, and the simply supported beam notched Izod impact strength is 12KJ/m
2, heat-drawn wire is 240 ℃, and flame retardant resistance is V0, and the demoulding time is 3 seconds/time.
Embodiment 9
1) be that the fast crystallization polybutylene terephthalate of 100 parts of polymeric modifications of 0.6dl/g, 8 parts silicon-dioxide, 10 parts alkali-free roving glass fiber, 14 parts decabromodiphenyl oxide, 4 parts antimonous oxide, ethylene-propylene acid butyl ester-glycidyl methacrylate of 1 part and 3 parts trimethyl phosphite carry out drying with limiting viscosity, wherein the fast crystallization polybutylene terephthalate of polymeric modification is dried to water content 200ppm;
2) it is even dried other feed composition except that the alkali-free roving glass fiber to be put into the high-speed mixing stirrer for mixing, gets mixture;
3) with step 2) mixture of gained adds from the main spout of twin screw extruder, will add inlet from glass through the alkali-free roving glass fiber of step 1) drying treatment and enter screw rod, and each heating interval temperature of twin screw extruder is made as 310 ℃ and melt extrudes; After extruding, the water-cooled tie rod, granulated and dried, packing promptly gets quickly crystallized polyester engineering plastic.
The fusing point of the quickly crystallized polyester engineering plastic of gained is 245 ℃, and fusion-crystallization peak temperature is 205 ℃, and tensile strength is 120MPa, and flexural strength is 180MPa, and the simply supported beam notched Izod impact strength is 7KJ/m
2, heat-drawn wire is 200 ℃, and flame retardant resistance is V0, and the demoulding time is 5 seconds/time.
Embodiment 10
1) be that 1010 of the polymeric modification fast crystallization polyester formed of 50 parts of polyethylene terephthalates of 1.0dl/g and 50 parts of Poly(Trimethylene Terephthalate) that limiting viscosity is 1.0dl/g, 0.2 part talcum powder, 10 parts alkali-free roving glass fiber, 14 parts brominated oxidative ethane, 4 parts sodium antimonate, ethene-vinyl acetate-copolymer-maleic anhydride of 15 parts and 0.5 part carries out drying with limiting viscosity, wherein the polymeric modification fast crystallization polyester is dried to water content 30ppm;
2) it is even dried other feed composition except that the alkali-free roving glass fiber to be put into the high-speed mixing stirrer for mixing, gets mixture;
3) with step 2) mixture of gained adds from the main spout of twin screw extruder, will add inlet from glass through the alkali-free roving glass fiber of step 1) drying treatment and enter screw rod, and each heating interval temperature of twin screw extruder is made as 240 ℃ and melt extrudes; After extruding, the water-cooled tie rod, granulated and dried, packing promptly gets quickly crystallized polyester engineering plastic.
The fusing point of the quickly crystallized polyester engineering plastic of gained is 255 ℃, and fusion-crystallization peak temperature is 220 ℃, and tensile strength is 135MPa, and flexural strength is 210MPa, and the simply supported beam notched Izod impact strength is 10KJ/m
2, heat-drawn wire is 230 ℃, and flame retardant resistance is V0, and the demoulding time is 15 seconds/time.
Embodiment 11
1) be that 1010 of the polymeric modification fast crystallization polyester formed of 40 parts of polyethylene terephthalates of 1.0dl/g and 60 parts of polybutylene terephthalates that limiting viscosity is 1.0dl/g, 0.5 part kaolin, 30 parts alkali-free short glass fiber, 20 parts brominated Polystyrene, 5 parts sodium antimonate, 2 parts styrene-ethylene butylene-styrene copolymer grafted toxilic acid and 0.5 part carries out drying with limiting viscosity, wherein the polymeric modification fast crystallization polyester is dried to water content 150ppm;
2) it is even dried other feed composition except that the alkali-free short glass fiber to be put into the high-speed mixing stirrer for mixing, gets mixture;
3) with step 2) mixture of gained adds from the main spout of twin screw extruder, will add inlet from glass through the alkali-free short glass fiber of step 1) drying treatment and enter screw rod, and each heating interval temperature of twin screw extruder is made as 280 ℃ and melt extrudes; After extruding, the water-cooled tie rod, granulated and dried, packing promptly gets quickly crystallized polyester engineering plastic.
The fusing point of the quickly crystallized polyester engineering plastic of gained is 248 ℃, and fusion-crystallization peak temperature is 210 ℃, and tensile strength is 125MPa, and flexural strength is 185MPa, and the simply supported beam notched Izod impact strength is 9KJ/m
2, heat-drawn wire is 220 ℃, and flame retardant resistance is V0, and the demoulding time is 12 seconds/time.
Embodiment 12
1) be that 1010 of the fast crystallization polyethylene terephthalate of 100 parts of polymeric modifications of 0.58dl/g, 0.5 part hydrotalcite, 25 parts alkali-free roving glass fiber, 14 parts brominated Polystyrene, 4 parts sodium antimonate, ethylene-methyl methacrylate butyl ester-glycidyl acrylate of 8 parts, 0.5 part of carbonarius master batch and 0.5 part carries out drying with limiting viscosity, wherein the fast crystallization polyethylene terephthalate of polymeric modification is dried to below the water content 80ppm;
2) it is even dried other feed composition except that the alkali-free roving glass fiber to be put into the high-speed mixing stirrer for mixing, gets mixture;
3) with step 2) mixture of gained adds from the main spout of twin screw extruder, will add inlet from glass through the alkali-free roving glass fiber of step 1) drying treatment and enter screw rod, and each heating interval temperature of twin screw extruder is made as 290 ℃ and melt extrudes; After extruding, the water-cooled tie rod, granulated and dried, packing promptly gets quickly crystallized polyester engineering plastic.
The fusing point of the quickly crystallized polyester engineering plastic of gained is 255 ℃, and fusion-crystallization peak temperature is 218 ℃, and tensile strength is 130MPa, and flexural strength is 200MPa, and the simply supported beam notched Izod impact strength is 10KJ/m
2, heat-drawn wire is 225 ℃, and flame retardant resistance is V0, and the demoulding time is 15 seconds/time.
Claims (10)
1. a quickly crystallized polyester engineering plastic is characterized in that, described quickly crystallized polyester engineering plastic is extruded in twin screw extruder by following feed composition and made:
Modification fast crystallization polyester A 100 weight parts
Crystallization nucleating agent B 0.05～5 weight part
Glass fibre C 10～40 weight parts
Fire retardant D 10～30 weight parts
Toughner E 1～15 weight part
Oxidation inhibitor F 0.01～3 weight part;
Preferably in twin screw extruder, extrude and make by following feed composition:
Modification fast crystallization polyester A 100 weight parts
Crystallization nucleating agent B 0.15～3 weight part
Glass fibre C 20～30 weight parts
Fire retardant D 15～25 weight parts
Toughner E 2～10 weight parts
Oxidation inhibitor F 0.02～2 weight part.
2. quickly crystallized polyester engineering plastic according to claim 1 is characterized in that described feed composition also comprises color master-batch, and described color master-batch is 0.5～10 weight part, preferred 1～6 weight part.
3. quickly crystallized polyester engineering plastic according to claim 1 and 2 is characterized in that, the limiting viscosity of described modification fast crystallization polyester A is 0.5～1.2dl/g, preferred 0.6～1.0dl/g; The modification fast crystallization polyester A that described modification fast crystallization polyester A is made up of the copolymer composition of the polyalkylene terephthalates of 80～100 moles of % and 0～20 mole of %; The polymkeric substance copolyreaction of preferred terephthalic acid or derivatives thereof of described polyalkylene terephthalates and aklylene glycol makes, perhaps the mixture copolyreaction for terephthalic acid or derivatives thereof and aklylene glycol makes, the more preferably mixture of one or more in polyethylene terephthalate, Poly(Trimethylene Terephthalate) or the polybutylene terephthalate, most preferably two or more mixtures.
4. quickly crystallized polyester engineering plastic according to claim 1 and 2 is characterized in that, described crystallization nucleating agent B is one or more the combination in inorganic particles, organic sodium salt class or the Ionomer; Wherein, described inorganic particles is 0.1～8 weight part, preferred 0.2～6 weight part; Described organic sodium salt class is 0.05～5 weight part, preferred 0.1～3 weight part; Described Ionomer is 0.1～6 weight part, preferred 0.3～5 weight part; The preferred titanium dioxide of described inorganic particles, silicon-dioxide, zinc oxide, aluminum oxide, talcum powder, kaolin, hydrotalcite, polynite or lime carbonate; Described organic sodium salt class preferred sodium benzoate, Sodium P-Chlorobenzoate, sodium stearate, barium stearate or montanic acid sodium; Described Ionomer optimal ethylene-sodium acrylate ionic polymer or ethylene-methyl methacrylate sodium ion polymkeric substance.
5. quickly crystallized polyester engineering plastic according to claim 1 and 2 is characterized in that, described glass fibre C is one or more the combination in alkali-free roving glass fiber or the alkali-free short glass fiber.
6. quickly crystallized polyester engineering plastic according to claim 1 and 2 is characterized in that, described fire retardant D is the combination of brominated flame retardant and antimony based flame retardant, perhaps is the combination of one or more halogen-free flame retardantss; The preferred decabromodiphenyl oxide of described brominated flame retardant, eight bromo ether, TDE, brominated oxidative ethane or bromination distyryl; Preferred antimonous oxide of described antimony based flame retardant or sodium antimonate; The preferred hypophosphite of described halogen-free flame retardants, phosphorus nitrogen is composite or the red phosphorus master batch.
7. quickly crystallized polyester engineering plastic according to claim 1 and 2 is characterized in that, described toughner E is polyester elastomer or rubber particles, and described polyester elastomer or rubber particles are the compound that contains 2 or above functional group; Described toughner E optimal ethylene-ethyl propenoate-glycidyl methacrylate, ethylene-propylene acid butyl ester-glycidyl methacrylate, ethylene-methyl methacrylate butyl ester-glycidyl acrylate, ethylene-octene copolymer, ethylene-octene copolymer grafted maleic anhydride, ethene-vinyl acetate-copolymer-maleic anhydride, styrene-ethylene butylene-styrene multipolymer or styrene-ethylene butylene-styrene copolymer grafted maleic anhydride.
8. the preparation method of any described quickly crystallized polyester engineering plastic of claim 1-7 is characterized in that, described preparation method comprises the steps:
1) with described feed composition drying;
2) it is even dried modification fast crystallization polyester A, crystallization nucleating agent B, fire retardant D, toughner E and oxidation inhibitor F to be put into the high-speed mixing stirrer for mixing, gets mixture;
3) place twin screw extruder to extrude in mixture and glass fibre C, after extruding, the water-cooled tie rod, granulated and dried, packing promptly gets described quickly crystallized polyester engineering plastic.
9. the preparation method of quickly crystallized polyester engineering plastic according to claim 8 is characterized in that, after the described modification fast crystallization polyester A drying, its water content is 30～200ppm, preferred 50～100ppm.
10. according to Claim 8 or the preparation method of 9 described quickly crystallized polyester engineering plastics, it is characterized in that, when placing twin screw extruder to extrude mixture and the glass fibre C in the step 3), each heating interval temperature is made as 240～310 ℃, preferred 250～300 ℃.
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Application publication date: 20100728 |