CN1216101C - Preparation method of toughness enhanced and reinforced polybutanediol terephthalate nanometer composition - Google Patents
Preparation method of toughness enhanced and reinforced polybutanediol terephthalate nanometer composition Download PDFInfo
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- CN1216101C CN1216101C CN 200310108106 CN200310108106A CN1216101C CN 1216101 C CN1216101 C CN 1216101C CN 200310108106 CN200310108106 CN 200310108106 CN 200310108106 A CN200310108106 A CN 200310108106A CN 1216101 C CN1216101 C CN 1216101C
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Abstract
The present invention provides a preparation method of toughened and strengthened polybutylene terephthalate nanometer composite materials. A mixture of polybutylene terephthalate, inorganic nanometer materials, a reaction compatibilizer, an antioxidant and a lubricating agent which are uniformly mixed in a high-speed agitator is added in a common double-screw extruder, and then the mixture is reactively blended with glass fiber at a certain temperature and rotary speed. The mixture is granulated by extrusion, and the toughened and strengthened polybutylene terephthalate nanometer composite materials are obtained. The method of the present invention is simple, and the obtained nanometer composite materials have superior combination properties, such as high heat resistance, high toughness, good surface smoothness, etc., and have wide industrial application prospects.
Description
Technical field:
The present invention relates to the preparation method of a kind of toughness reinforcing enhancing polybutylene terephthalate (PBT) nano composite material, relate in particular to and a kind ofly polybutylene terephthalate, inorganic nano material, reaction compatilizer, oxidation inhibitor, lubricant and glass fibre are carried out reactive blending, and obtain having the novel method of high performance toughness reinforcing enhancing PBT nano composite material with twin screw extruder.The invention belongs to technical field of polymer processing.
Background technology:
As everyone knows, polybutylene terephthalate is a kind of thermoplastic engineering plastic, has excellent size stability, thermotolerance, chemical resistance and excellent mechanical property etc., and is widely used in fields such as electronics, electric and automobile.Because shortcomings such as polybutylene terephthalate poor water resistance, the high temperature use properties is relatively poor and intensity is lower are often carried out modification with glass fibre or other polymer blendings, can access better heat-resisting and higher intensity.But then impelling strength is relatively poor to use the thermoplastic polyester of glass modification merely; surface smoothness is bad; regular meeting causes glass emergence on the surface when being injection molded into goods; influence product properties and outward appearance; in order to improve the surface smoothness of PBT/ glass fiber composite material, Ji Jiliang etc. have developed a kind of high gloss, rapid shaping strengthens polybutylene terephthalate (CN00124686.0).And in order to improve the toughness of PBT, people also do a lot (as patent CN00816306.5; US4,753,890; EP737,715; EP531,008 etc.) all used core-shell type multipolymer, ethylene copolymer or modified elastic body that PBT has been carried out modification, prepared material with better impelling strength, but may cause flowing property to descend, unfavorable to injection moulding massive article or meticulous goods, and tensile strength, flexural strength and thermotolerance etc. are also not ideal enough.
Summary of the invention:
The objective of the invention is to defective at present PBT modification aspect prior art, a kind of toughness reinforcing enhancing polybutylene terephthalate nano composite material preparation method is proposed, when the toughness of material and intensity were improved, performances such as surface smoothness and thermotolerance also were improved.
For realizing such purpose, in technical scheme of the present invention, adopt twin screw extruder that polybutylene terephthalate, inorganic nano material, reaction compatilizer, oxidation inhibitor, lubricant and glass fibre are carried out reactive blending, and obtain having high performance toughness reinforcing enhancing PBT nano composite material.In weight part is 100 parts polybutylene terephthalate; add 1-25 part inorganic nano material; 0.1-20 part reaction compatilizer; 0.1-10 part oxidation inhibitor; 0.1-20 part lubricant; on homogenizer, mix earlier; the rotating speed of homogenizer is 300-7500 rev/min; in common twin screw extruder, extrude then and make pellet with 10-60 part glass fibre; extruder temperature is 200-320 ℃; rotating speed is 50-600 rev/min; the residence time of material in screw rod is 1-15 minute; after the material of extruding cools off through the water-cooled cooling tank; through the dicing machine pelletizing; obtain pellet; in baking oven 80-200 ℃ dry 10-30 hour, promptly get toughness reinforcing enhanced polybutylene terephthalate nano composite material.
Polybutylene terephthalate of the present invention is the polycondensate of terephthalic acid and butyleneglycol.
Inorganic nano material of the present invention is for being of a size of nano level at least on the one dimension direction, the disperse phase yardstick is the 1-100 nanometer, is two or more compound in nano imvite, nano silicon, nano-aluminium oxide, nano titanium oxide, nano-zinc sulfide, nano-calcium carbonate or the nanometer moly-sulfide.
Reaction compatilizer of the present invention is that a class can be carried out transesterification reaction with polybutylene terephthalate and the material of better avidity can be arranged with inorganic nano material, be silane coupling agent, titanate coupling agent, vulcabond (TDI), p-Hydroxybenzoate, octadecylamine, hexadecylamine, 4,4 '-isopropylidene two (phenol salicylate), the salicylic acid phenyl ester, Resins, epoxy, the epoxidation vinyl benzene multipolymer, the epoxidized ethylene multipolymer, vinylbenzene-alkylmethacrylate polymer, styrene-maleic anhydride copolymer (SMA), PAUR, polyoxyethylene glycol (PEO), polythene-ethenol multipolymer (EVOH), ethylene-vinyl acetate copolymer (EVA), maleic anhydride grafted polyethylene multipolymer (PE-g-MAH), maleic anhydride inoculated polypropylene multipolymer (PP-g-MAH), polyethylene acrylic acid grafts (PE-g-AA), the polypropylene grafted thing of vinylformic acid (PP-g-AA), glycidyl methacrylate-polyethylene graft copolymer (GMA-g-PE), glycidyl methacrylate-polypropylene graft copolymer (GMA-g-PP), maleic anhydride graft styrene-butadiene-styrene multipolymer (MAH-g-SBS), maleic anhydride graft acrylonitrile-butadiene-styrene copolymer (MAH-g-ABS), or the mixture of forming by them.
Oxidation inhibitor of the present invention can be four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), N, [3-(3 for N '-two, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine (oxidation inhibitor 1098), three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168), 2,6-di-tert-butyl-4-methy phenol (antioxidant 264), Tyox B (anti-oxidant DLTP), 4,4 '-(β, β '-dihydroxyl dipropyl oxygen phenyl) 2,2-propane (dihydroxyphenyl propane) or triphenyl phosphite, or the mixture of forming by them.
Lubricant of the present invention can be the two fatty amides of estersil, silicone oil, silicone, organosilane, polymer organosilane, ethylene bis-fatty acid amine, ethylene, erucicamide, amine hydroxybenzene, whiteruss, Chinese wax oil, Zinic stearas, calcium stearate or barium stearate, or the mixture of being made up of them.
Glass fibre of the present invention is long glass fibres or short glass fiber.
The prepared PBT nano composite material of the present invention has not only improved original PBT toughness and intensity, and aspects such as surface smoothness and thermotolerance also are significantly improved, and wide application and industrial prospect are arranged.
Embodiment:
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Example formulations sees Table 1; in weight part is 100 parts polybutylene terephthalate; the inorganic nano material of the listed formula ratio of table 1; the reaction compatilizer; oxidation inhibitor and lubricant; on homogenizer, mix earlier; the rotating speed of homogenizer is 3000 rev/mins; in common twin screw extruder, extrude then and make pellet with the long glass fibres of the listed formula ratio of table 1; extruder temperature is 210 ℃ of feeding sections; 230 ℃ of compression sections; 240 ℃ of 250 ℃ of homogenizing zones and die temperatures; rotating speed is 320 rev/mins; the residence time of material in screw rod is 2 minutes; after the material of extruding cools off through the water-cooled cooling tank; through the dicing machine pelletizing; obtain pellet, 120 ℃ of dryings are 24 hours in baking oven, promptly get toughness reinforcing enhancing polybutylene terephthalate nano composite material.It is 2 listed that the performance of material sees Table.
From the result of embodiment as can be seen, the polybutylene terephthalate nano composite material that the present invention obtains has the good comprehensive performance, and thermotolerance, toughness, intensity etc. are far superior to pure PBT, and wide application and industrial prospect are arranged.
Table 1 Example formulations
| Pure PBT | 100 parts of polybutylene terephthalates | 0 part of inorganic nano material | 0 part of reaction compatilizer | Antioxidant 1010 is 0.2; Antioxidant 264 is 0.6 | 0 part of lubricant | 0 part in glass fibre |
| Embodiment 1 | 100 parts of polybutylene terephthalates | 0.5 part of 0.5 part of inorganic nano material-nano titanium oxide and nanometer moly-sulfide | 0.1 part of reaction compatilizer-metatitanic acid coupling agent | Oxidation inhibitor-oxidation inhibitor 1098 is 0.1 | 0.1 part of lubricant-silicone oil | 10 parts of glass fibre-roving glass fibers |
| Embodiment 2 | 100 parts of polybutylene terephthalates | 3 parts of 0.5 part of inorganic nano material-nano silicon and nano imvites | 0.3 part of 1 part of reaction compatilizer-GMA-g-PE and silane coupling agent | Oxidation inhibitor-antioxidant 1010 is 0.2; Antioxidant 264 is 0.6 | 1 part of lubricant-0.5 part of Chinese wax oil and calcium stearate | 15 parts of glass fibre-roving glass fibers |
| Embodiment 3 | 100 parts of polybutylene terephthalates | 2 parts of 5 parts of inorganic nano material-nano-aluminium oxides and nano imvites | 0.5 part of reaction compatilizer-EVA and SMA1 part | 168 0.3 parts in oxidation inhibitor-oxidation inhibitor and antioxidant 264 are 0.5 part | 2 parts of 0.3 part of lubricant-silicone oil and Zinic stearass | 25 parts of glass fibre-roving glass fibers |
| Embodiment 4 | 100 parts of polybutylene terephthalates | 3 parts of 8 parts of inorganic nano material-nano imvites and nano-calcium carbonates | Reaction compatilizer-EVA2 part and TDI3 part | 168 0.3 parts in oxidation inhibitor-oxidation inhibitor and antioxidant 1010 are 1 part | 1.5 parts of lubricant-1 part of Chinese wax oil and silicone oil | 45 parts of glass fibre-roving glass fibers |
| Embodiment 5 | 100 parts of polybutylene terephthalates | 2 parts of 3 parts of inorganic nano material-nano imvites, 1 part of nano-calcium carbonate and nano silicons | Reaction compatilizer-SMA2 part and TDI0.1 part | 1 part of 168 0.5 parts in oxidation inhibitor-oxidation inhibitor and dihydroxyphenyl propane | 3 parts of lubricant-erucicamides | 60 parts of glass fibre-roving glass fibers |
Table 2 embodiment performance of composites test result
| Project | Testing method | Performance index | |||||
| Pure PBT | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | ||
| Heat-drawn wire (℃) | GB1634 | 47 | 96 | 196 | 201 | 205 | 212 |
| Tensile strength (MPa) | GB1040 | 48 | 87 | 103 | 112 | 118 | 126 |
| Flexural strength (MPa) | GB9341 | 74 | 127 | 163 | 178 | 195 | 205 |
| Modulus in flexure (MPa) | GB9341 | 1988 | 4568 | 6365 | 7734 | 8840 | 15400 |
| Notched Izod impact strength (kJ/m 2) | GB1843 | 4.32 | 6.12 | 6.58 | 8.49 | 12.42 | 9.92 |
| Smooth finish | Observe | Good | Good | Good | Good | Good | Better |
| Glass emergence on the surface | Observe | / | Good | Good | Good | Better | |
Claims (6)
1, a kind of toughness reinforcing enhancing polybutylene terephthalate nano composite material preparation method, it is characterized in that: in weight part is 100 parts polybutylene terephthalate, add 1-25 part inorganic nano material, 0.1-20 part reaction compatilizer, 0.1-10 part oxidation inhibitor, 0.1-20 part lubricant, on homogenizer, mix earlier, the rotating speed of homogenizer is 300-7500 rev/min, in common twin screw extruder, extrude then and make pellet with 10-60 part glass fibre, extruder temperature is 200-320 ℃, rotating speed is 50-600 rev/min, the residence time of material in screw rod is 1-15 minute, the material of extruding is after cooling, pelletizing obtains pellet, in baking oven 80-200 ℃ dry 10-30 hour, obtain toughness reinforcing enhanced polybutylene terephthalate nano composite material.
2, toughness reinforcing enhancing polybutylene terephthalate nano composite material preparation method as claimed in claim 1 is characterized in that described polybutylene terephthalate is the polycondensate of terephthalic acid and butyleneglycol.
3, toughness reinforcing enhancing polybutylene terephthalate nano composite material preparation method as claimed in claim 1, it is characterized in that described inorganic nano material is to be of a size of nano level at least on the one dimension direction, the disperse phase yardstick is the 1-100 nanometer, is two or more compound in nano imvite, nano silicon, nano-aluminium oxide, nano titanium oxide, nano-zinc sulfide, nano-calcium carbonate or the nanometer moly-sulfide.
4, toughness reinforcing enhancing polybutylene terephthalate nano composite material preparation method as claimed in claim 1, it is characterized in that described reaction compatilizer is a silane coupling agent, titanate coupling agent, vulcabond, p-Hydroxybenzoate, octadecylamine, hexadecylamine, 4,4 '-isopropylidene is two, the salicylic acid phenyl ester, Resins, epoxy, vinylbenzene-alkylmethacrylate polymer, styrene-maleic anhydride copolymer, PAUR, polyoxyethylene glycol, the polythene-ethenol multipolymer, ethylene-vinyl acetate copolymer, the maleic anhydride grafted polyethylene multipolymer, the maleic anhydride inoculated polypropylene multipolymer, the polyethylene acrylic acid grafts, the polypropylene grafted thing of vinylformic acid, glycidyl methacrylate-polyethylene graft copolymer, glycidyl methacrylate-polypropylene graft copolymer, maleic anhydride graft styrene-butadiene-styrene multipolymer or maleic anhydride graft acrylonitrile-butadiene-styrene copolymer, or the mixture of forming by them.
5, toughness reinforcing enhancing polybutylene terephthalate nano composite material preparation method as claimed in claim 1, it is characterized in that described oxidation inhibitor is antioxidant 1010, oxidation inhibitor 1098, oxidation inhibitor 168, antioxidant 264, Tyox B, dihydroxyphenyl propane or triphenyl phosphite, or the mixture of forming by them.
6, toughness reinforcing enhancing polybutylene terephthalate nano composite material preparation method as claimed in claim 1, it is characterized in that described lubricant is the two fatty amides of estersil, silicone oil, silicone, organosilane, polymer organosilane, ethylene bis-fatty acid amine, ethylene, erucicamide, amine hydroxybenzene, whiteruss, Chinese wax oil, Zinic stearas, calcium stearate or barium stearate, or the mixture of forming by them.
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| CN 200310108106 CN1216101C (en) | 2003-10-23 | 2003-10-23 | Preparation method of toughness enhanced and reinforced polybutanediol terephthalate nanometer composition |
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