CN101481494A - Thermoplastic polyester alloy nano composite material and preparation thereof - Google Patents
Thermoplastic polyester alloy nano composite material and preparation thereof Download PDFInfo
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- CN101481494A CN101481494A CNA2009100454588A CN200910045458A CN101481494A CN 101481494 A CN101481494 A CN 101481494A CN A2009100454588 A CNA2009100454588 A CN A2009100454588A CN 200910045458 A CN200910045458 A CN 200910045458A CN 101481494 A CN101481494 A CN 101481494A
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- thermoplastic polyester
- oxidation inhibitor
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- 229920000728 polyester Polymers 0.000 title claims abstract description 26
- 239000000956 alloy Substances 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims abstract description 23
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 22
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 19
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 18
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 10
- -1 polybutylene terephthalate Polymers 0.000 claims abstract description 38
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 32
- 239000007822 coupling agent Substances 0.000 claims abstract description 30
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 25
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000002086 nanomaterial Substances 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000003112 inhibitor Substances 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 239000005543 nano-size silicon particle Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- 239000008116 calcium stearate Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000012802 nanoclay Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012174 chinese wax Substances 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 239000011858 nanopowder Substances 0.000 claims description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims 2
- 239000002994 raw material Substances 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 238000005809 transesterification reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000037452 priming Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 229920004449 Halon® Polymers 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000001818 nuclear effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012899 standard injection Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention relates to a thermoplastic polyester alloy nano-composite material and a method for preparing the same, the composite material has ingredients and mass percents of: 50-95% of polybutylene terephthalate (PBT), 0-40% of polyethylene terephthalate (PET), 0.1-5% inorganic nano-materials subjected to surface treatment with a coupling agent and 0-5% of other auxiliary agents; the ingredients are molten and mixed together at the temperature ranging from 210-265 DEG C to obtain the thermoplastic polyester alloy nano-composite material. The polyester alloy nano-composite material prepared by the method results in high dispersion in the nanoparticles thereof, which effectually prohibits transesterification reaction between the polyester alloys and prominently enhances the heat resistance of the polyester substrate; the polyester alloy nano-composite material also has excellent surface finish, which lowers the costs while advancing tensile strength and flexural modulus thereof and can be applied to the manufacturing of parts in automobile industry and electronic industry extensively.
Description
Technical field
The present invention relates to a kind of polyester alloy material and preparation method thereof, particularly, is earlier to the nano inorganic material processing that organises, thus then with the compound high performance heat resistant macromolecular material that obtains such as thermoplastic polyester.
Background technology
Polybutylene terephthalate (PBT) is that oyster white is translucent to opaque, crystalline thermoplastic polyester.Have superior heat resistance, toughness, resistance to fatigue, self-lubricating, low-friction coefficient, weathering resistance, low water absorption characteristics such as (only being 0.1%), and in wet environment, still keep various rerum naturas (comprising electrical property), electrical insulating property is good, but volume resistance, dielectric loss are big.Heat-resisting water, bases, acids, oils but be subject to halon and corrode, hydrolytic resistance is poor, crystallization rapidly under the low temperature, good forming ability; Comparing that the Other Engineering plastics have excellent over-all propertieies such as the synthetic technology difficulty is lower and noticeable, is the good material of making electronics/electric parts and automobile component; Molecule chain rigidity and high crystallinity have all caused PBT crystallization shrinking percentage big, poor dimensional stability, and heat-drawn wire is low, and these two outstanding shortcomings become the obstacle that PBT applies.Generally improve its performance by the method for blending and modifying, mainly contain glass fibre filling-modified or with other polymer blending modifications, can access better heat-resisting and high intensity.But use glass modification desired content big (about 30%wt) merely, poor surface smoothness has influenced the attractive in appearance and lightweight of goods.The toughness reinforcing enhancing polybutylene terephthalate (CN1537891) of developments such as Qi Rongrong has added nano material and has promoted its performance, but its glass add-on is up to 60 parts, may be unfavorable to product surface, under some occasions, can not reach the effect of exempting from the priming paint spraying, increased treatment process, cost increases; Cross limit full (CN1519591) and adopted polybutylene terephthalate, polyethylene terephthalate (PET), and some non-fine fillers have been added, the result has obtained high glossiness, high smooth degree and has exempted from the optical transmitting set material of priming paint spraying, but because the transesterification reaction between the polyester alloy exists, possible deterioration its over-all properties.
The present invention utilizes PET to have higher thermostability than PBT, better mobile and lower shrinking percentage, and special surface effects and the small-size effect of nano particle, the one-tenth nuclear effect and the control of PBT/PET basal body structure of nano particle are combined effectively, by effective dispersion and the interface structure control of nano particle in the PBT/PET matrix, nanoparticle has obtained the dispersion of height, effectively suppressed the transesterification reaction between polyester alloy, prepared ternary nano composite material, improve the surface smoothness of its thermotolerance and goods greatly, also improved the intensity and the modulus of material simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of thermoplastic polyester alloy nano composite material, by mass percentage, by 50～98% polybutylene terephthalate (PBT), 0～40% polyethylene terephthalate (PET), 0.1～5% carry out auxiliary agents such as surface-treated inorganic nano material, 0～5% oxidation inhibitor and/or lubricant through coupling agent and form.
Another purpose of the present invention is to provide the preparation method of above-mentioned a kind of thermoplastic polyester alloy nano composite material, at first, above-mentioned each component is added homogenizer jointly mix, and rotating speed is 500～7500 rev/mins, mixing time 5～10 minutes; Extrude in twin screw extruder then, temperature range is 210～265 ℃, and the melt blending granulation makes.
Wherein, PBT recommends to use its homopolymer, and intrinsic viscosity [η] is 0.8～1.0 (Ubbelohde viscosimetry), and density is 1.20～1.34g/cm3; The adding of PET is to improve the surface flatness of goods and the basal component of smooth finish, it has the melt temperature higher than PBT, add-on can not obtain the goods of the surface smoothness of high glossiness and excellence very little, add-on too greatly then not only causes the transesterification reaction degree to increase, also deterioration the performance of goods, the gloss appearance degree reduces, and therefore preferred mass percent is 10～30%; The oxidation inhibitor of recommending to use is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010, Ciba (Ciba) company product), N, N-is two, and [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine (oxidation inhibitor 1098, Ciba (Ciba) company produces) and/or three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168, Ciba (Ciba) company produces); Lubricant of the present invention is silicone, silicone oil, Chinese wax oil, whiteruss, Zinic stearas or calcium stearate, or the mixture of being made up of them.Be preferably silicone or calcium stearate, adding the quality percentage composition is 0.1～2%.
Inorganic nano material of the present invention yardstick on the one dimension direction at least is a nano level, the disperse phase yardstick is 10～100nm, can be a kind of or two kinds compound in nanoclay, nano silicon, nano-calcium carbonate, nano titanium oxide, nano zine oxide or the nano-aluminium oxide.Be preferably nano silicon, nano-calcium carbonate and nanoclay.Coupling agent is a kind of in silane coupling agent (KH550, KH560, KH570), titanate coupling agent (JN114, JN198), the aluminate coupling agent (SG-Al 821), and consumption is 1～12% of an inorganic nano material quality.Preferred coupling agent is KH550, JN114, and recommending usage quantity is 3～8% of nano inorganic material.
The surface treatment method of inorganic nano is: coupling agent is dissolved in the dehydrated alcohol ultra-sonic dispersion and obtains coupling agent dispersed liquid after evenly; Inorganic nano material then is scattered in and obtains the inorganic nano material dispersion liquid in the deionized water, described coupling agent dropwise added in the described inorganic nano material dispersion liquid, and after adding in the 2h, under the condition of mechanical stirring and heating, reaction 2～4h; 65～105 ℃ of dryings behind the comminution by gas stream, obtain the nano-powder of handling well.
The thermoplastic polyester alloy nano composite material of the present invention's preparation, nanoparticle has obtained the dispersion of height, dispersion size can reach about 50～100nm, suppressed the transesterification reaction between alloy effectively, significantly improve the thermotolerance of polyester matrix, had surface of good smooth finish, reduced cost, simultaneously also improve its tensile strength and modulus in flexure, can be widely used in automobile and electronic industry component production.
Description of drawings
Fig. 1 is the field emission scan photo (FE-SEM) of the thermoplastic polyester alloy nano composite material of embodiment 1 preparation.
Embodiment
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this following examples only are used for that the invention will be further described; can not be interpreted as limiting the scope of the invention; some nonessential improvement and adjustment that the professional and technical personnel in this field content according to the present invention is made still belong to protection scope of the present invention.
Embodiment 1
Behind dry 2h under 120 ℃, ultra-sonic dispersion obtains aqueous dispersions in deionized water with nano silicon (CAB-O-SIL M-5); Taking by weighing and accounting for the nano silicon quality is that 3% KH550 is scattered in the dehydrated alcohol; Scattered coupling agent dropwise adds in the nano silicon aqueous dispersions, after adding in the 2h, and under the condition of mechanical stirring and heating, reaction 3h; 85 ℃ of vacuum-dryings, behind the comminution by gas stream, obtain the nano silicon of handling well.
Polybutylene terephthalate is dry 4h under 120 ℃; polyethylene terephthalate is dry 4h under 145 ℃; afterwards the polybutylene terephthalate of 80 mass parts, the polyethylene terephthalate of 20 mass parts, the nano silicon of handling well of 2 mass parts, the antioxidant 1010 of 0.15 mass parts, the oxidation inhibitor 168 of 0.15 mass parts are directly mixed; add in the twin screw extruder; the adjusting rotating speed is 300～600rmp; melt extrude under 210～265 ℃, granulation obtains target compound.Its FE-SEM figure sees Fig. 1.
Embodiment 2
With nano silicon (CAB-O-SIL M-5, particle diameter 20nm, surface-area 200m
2/ g) at 120 ℃ down behind the dry 2h, ultra-sonic dispersion obtains aqueous dispersions in deionized water; Taking by weighing and accounting for the nano silicon quality is that 3% KH550 is scattered in the dehydrated alcohol; Scattered coupling agent dropwise adds in the nano silicon aqueous dispersions, after adding in the 2h, and under the condition of mechanical stirring and heating, reaction 3h; 85 ℃ of vacuum-dryings, behind the comminution by gas stream, obtain the nano silicon of handling well.
Polybutylene terephthalate is dry 4h under 120 ℃; polyethylene terephthalate is dry 4h under 145 ℃; afterwards the polyethylene terephthalate of 90 mass parts, the nano silicon of handling well of 10 mass parts, the antioxidant 1010 of 0.15 mass parts, the oxidation inhibitor 168 of 0.15 mass parts are directly mixed; add in the twin screw extruder; the adjusting rotating speed is 300～600rmp; melt extrude under 235～275 ℃, granulation obtains master batch.
Then; the master batch of 20 mass parts, the polybutylene terephthalate of 80 mass parts, the antioxidant 1010 of 0.15 mass parts, the oxidation inhibitor 168 of 0.15 mass parts are directly mixed; add in the twin screw extruder; the adjusting rotating speed is 300～600rmp; melt extrude under 210～265 ℃, granulation obtains target compound.
Embodiment 3
The nano-calcium carbonate that with particle diameter is 20～50nm is at 120 ℃ down behind the dry 2h, and ultra-sonic dispersion obtains the nano-calcium carbonate aqueous dispersions in deionized water; Taking by weighing and accounting for the nano-calcium carbonate quality is that 5% coupling agent JN114 is scattered in the dehydrated alcohol; Scattered coupling agent is dropwise added in the nano-calcium carbonate aqueous dispersions, after adding in the 2h, under the condition of mechanical stirring and heating, reaction 3h; 85 ℃ of vacuum-dryings, behind the comminution by gas stream, obtain the nano-calcium carbonate of handling well.
Polybutylene terephthalate is dry 4h under 120 ℃; polyethylene terephthalate is dry 4h under 145 ℃; afterwards the polybutylene terephthalate of 80 mass parts, the polyethylene terephthalate of 20 mass parts, the nano-calcium carbonate of handling well of 3 mass parts, the calcium stearate of 1.2 mass parts, the antioxidant 1010 of 0.15 mass parts, the oxidation inhibitor 168 of 0.15 mass parts are directly mixed; add in the twin screw extruder; the adjusting rotating speed is 300～600rmp; melt extrude under 210～265 ℃, granulation obtains target compound.
Embodiment 4
Behind dry 2h under 120 ℃, ultra-sonic dispersion obtains aqueous dispersions in deionized water with nano imvite NA-MMT (90mmol/100g); Taking by weighing and accounting for the nano imvite quality is that 8% coupling agent KH550 is scattered in the dehydrated alcohol; Scattered coupling agent is dropwise added in the nano imvite aqueous dispersions, after adding in the 2h, under the condition of mechanical stirring and heating, reaction 3h; 85 ℃ of vacuum-dryings, behind the comminution by gas stream, obtain the nano imvite of handling well.
Polybutylene terephthalate is dry 4h under 120 ℃; polyethylene terephthalate is dry 4h under 145 ℃; afterwards the polybutylene terephthalate of 80 mass parts, the polyethylene terephthalate of 20 mass parts, the nano imvite of handling well of 2 mass parts, the antioxidant 1010 of 0.15 mass parts, the oxidation inhibitor 168 of 0.15 mass parts are directly mixed; add in the twin screw extruder; the adjusting rotating speed is 300～600rmp; melt extrude under 210～265 ℃, granulation obtains target compound.
Comparative Examples 1
Polybutylene terephthalate is dry 4h under 120 ℃, polyethylene terephthalate is dry 4h under 145 ℃, afterwards the polybutylene terephthalate of 80 mass parts, the polyethylene terephthalate of 20 mass parts, the antioxidant 1010 of 0.15 mass parts, the oxidation inhibitor 168 of 0.15 mass parts are directly mixed, add in the twin screw extruder, the adjusting rotating speed is 300～600rmp, under 210～265 ℃, melt extrude granulation.
Comparative Examples 2
Behind 120 ℃ of following dry 2h of nano silicon (CAB-O-SIL M-5), ultra-sonic dispersion obtains aqueous dispersions in deionized water; Taking by weighing and accounting for the nano silicon quality is that 3% coupling agent KH550 is scattered in the dehydrated alcohol; Scattered coupling agent is dropwise added in the nano silicon aqueous dispersions, after adding in the 2h, under the condition of mechanical stirring and heating, reaction 3h; 85 ℃ of vacuum-dryings, behind the comminution by gas stream, obtain the nano silicon of handling well.
Polybutylene terephthalate is dry 4h under 120 ℃, afterwards the polybutylene terephthalate of 98 mass parts, the nano silicon of handling well of 2 mass parts, the antioxidant 1010 of 0.15 mass parts, the oxidation inhibitor 168 of 0.15 mass parts are directly mixed, add in the twin screw extruder, the adjusting rotating speed is 300～600rmp, under 210～265 ℃, melt extrude granulation.
By the above-mentioned pellet of finishing, 130 ℃ of dry 4h press dried pellet the standard injection moulding sample preparation in the table 1 then, and test result is listed in the table 1 simultaneously.
Table 1
Found out that by table 1 and Fig. 1 the nano silicon of coupling agent treatment has been realized highly nano level dispersion in the PBT/PET matrix, disperseing yardstick is 50～100nm (see figure 1).Compare with Comparative Examples, form thermoplastic polyester alloy nano composite material by modified manometer silicon dioxide, PBT, PET and oxidation inhibitor, heat-drawn wire significantly improves, be up to 187.3 ℃, tensile strength and modulus in flexure also all are significantly improved, and can be widely used in the manufacturing of automobile and electronic industry component.
Claims (9)
1, a kind of thermoplastic polyester alloy nano composite material, it is characterized in that: represent that with mass percent described matrix material is that raw material is formed by 50～98% polybutylene terephthalate, 0～40% polyethylene terephthalate, 0.1～5% the inorganic nano material of crossing through coupling agent treatment, 0～5% auxiliary agent;
Described auxiliary agent is oxidation inhibitor and/or lubricant, and required ratio is 1:20～10:1;
The quality of described coupling agent is 1～12% of a described inorganic nano material quality.
2, thermoplastic polyester alloy nano composite material according to claim 1 is characterized in that, described polybutylene terephthalate is a homopolymer, and intrinsic viscosity [η] is 0.8～1.0, and density is 1.20～1.34g/cm
3, the quality percentage composition is 60～98%.
3, thermoplastic polyester alloy nano composite material according to claim 1 is characterized in that, the mass percent of described polyethylene terephthalate is 10～30%; The quality of described coupling agent is 3～8% of a described inorganic nano material quality.
4, thermoplastic polyester alloy nano composite material according to claim 1, it is characterized in that, the described inorganic nano material of crossing through the coupling agent treatment yardstick on the one dimension direction at least is a nano level, the yardstick of disperse phase is 10～100nm, and described disperse phase is the compound of a kind of in nanoclay, nano silicon, nano-calcium carbonate, nano titanium oxide, nano zine oxide and the nano-aluminium oxide or two kinds.
5, thermoplastic polyester alloy nano composite material according to claim 1, it is characterized in that, described lubricant is the mixture of one or more compositions in silicone, silicone oil, Chinese wax oil, whiteruss, Zinic stearas and the calcium stearate, and the quality percentage composition is 0.1～2%.
6, thermoplastic polyester alloy nano composite material according to claim 1, it is characterized in that, described oxidation inhibitor is the mixture of one or more compositions in antioxidant 1010, oxidation inhibitor 168, antioxidant 264, oxidation inhibitor 1098 and the triphenyl phosphite, and described oxidation inhibitor quality percentage composition is 0.1～1%.
7, the preparation method of the described thermoplastic polyester alloy nano composite material of claim 1, it is characterized in that, at first be that 40～98% polybutylene terephthalate, 0～40% polyethylene terephthalate, 0.1～5% the inorganic nano material of crossing through coupling agent treatment, 0～5% auxiliary agent add homogenizer jointly and mix with mass percent, rotating speed is 500～7500 rev/mins, mixing time 5～10 minutes; Melt blending granulation in twin screw extruder, temperature range are 210～265 ℃;
Described auxiliary agent is oxidation inhibitor and/or lubricant;
Described inorganic nano material after the coupling agent treatment yardstick on the one dimension direction at least is a nano level, the yardstick of disperse phase is 10～100nm, and described disperse phase is the compound of a kind of in nanoclay, nano silicon, nano-calcium carbonate, nano titanium oxide, nano zine oxide and the nano-aluminium oxide or two kinds.
8, preparation method according to claim 7, it is characterized in that described inorganic nano material is made by following method: will account for described inorganic nano material quality earlier and be 1～12% described coupling agent and be dissolved in and carry out ultra-sonic dispersion in the dehydrated alcohol and obtain coupling agent solution; Inorganic nano material then is dispersed in the dispersion liquid that obtains inorganic nano material in the deionized water; Then described coupling agent solution is dropwise added in the dispersion liquid of described inorganic nano material, after adding in the 2h, under the condition of mechanical stirring and heating, reaction 2～4h; 65～105 ℃ dry down, behind the comminution by gas stream, obtains the nano-powder of handling well;
Described coupling agent is a kind of in silane coupling agent, titanate coupling agent, the aluminate coupling agent.
According to claim 7 or 8 described preparation methods, it is characterized in that 9, described lubricant is the mixture of one or more compositions in silicone, silicone oil, Chinese wax oil, whiteruss, Zinic stearas and the calcium stearate;
Described oxidation inhibitor is the mixture of one or more compositions in antioxidant 1010, oxidation inhibitor 168, antioxidant 264, oxidation inhibitor 1098 and the triphenyl phosphite.
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