CN102532824B - Flame-retardant reinforced warping-resistance PBT/PTT (polybutylene terephthalate/polytrimethylene terephthalate) alloy material and preparation method thereof - Google Patents
Flame-retardant reinforced warping-resistance PBT/PTT (polybutylene terephthalate/polytrimethylene terephthalate) alloy material and preparation method thereof Download PDFInfo
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- CN102532824B CN102532824B CN201010619046.3A CN201010619046A CN102532824B CN 102532824 B CN102532824 B CN 102532824B CN 201010619046 A CN201010619046 A CN 201010619046A CN 102532824 B CN102532824 B CN 102532824B
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a flame-retardant reinforced warping-resistance PBT/PTT (polybutylene terephthalate/polytrimethylene terephthalate) alloy material, which comprises the following components in parts by weight: 30-40 parts of PBT, 10-30 parts of PTT, 0.3-1 part of lubricating agent, 0.1-0.8 part of ester exchange inhibitor, 0.3-0.8 part of antioxidant, 0.5-5 parts of nucleating agent, 5-10 parts of flame retardant, 1-5 parts of flame-retardant synergist, 2-10 parts of toughening agent, 0-30 parts of glass fiber and 10-30 parts of mineral powder. According to the invention, the PBT and the PTT are blended to be made into the alloy material, and the flame-retardant reinforced warping-resistance PBT/PTT alloy material has the advantage of low cost, solves the problem that high fire resistance and high CTI (comparative tracking index) value as well as high mechanical property of the PBT/PTT alloy material are difficult to coexist and has the characteristics of strong warping resistance and heat resistance. The flame-retardant reinforced warping-resistance PBT/PTT alloy material has good mechanical property, high flame retardance and high CTI value; and a product made of the flame-retardant reinforced warping-resistance PBT/PTT alloy material is smooth in smooth and free of warping.
Description
Technical field
The present invention relates to a kind of polymer composite, particularly relate to a kind of fire-retardant enhancing resistance to warpage PBT/PTT alloy material and preparation method thereof.
Background technology
Polyethylene terephthalate (PBT) is one of the most tough and tensile engineered thermoplastic materials, and it is those semi-crystalline materials, has extraordinary chemical stability, physical strength, electrical insulation characteristics and thermostability.Poly(Trimethylene Terephthalate) (PTT) is a kind of new polyester macromolecular material having development prospect of new research and development after polyethylene terephthalate the 1950's (PET) and the polybutylene terephthalate seventies (PBT), has the advantages such as good mechanical property, good elasticity, wear resistance, insulativity, water-absorbent are low.And because the industrial preparative method of the starting material 1,3-PD synthesizing PTT has in recent years had breakthrough, the scale operation of PTT is with low cost, has price advantage.PTT melt crystallization speed, higher than PET, adds PTT in PBT, and shaping efficiency has exceeded PBT/PET alloy, and has excellent combination property, the effect reduced costs.
The easy buckling deformation but PTT is heated, under low temperature mould, article surface is coarse and floating fibre is more, and it is lower to compare resistance to electric trace index (CTI), have impact on the use properties of PBT/PTT alloy material.
Summary of the invention
The present invention provides a kind of PBT/PTT alloy material and preparation method thereof with high CTI value, high flame retardant, enhancing, resistance to warpage to solve above-mentioned prior art Problems existing, alloy material good mechanical property, flame retardant resistance are high, electrical property is good, CTI value is high, and product surface is smooth without warpage.
Object of the present invention is achieved through the following technical solutions:
A kind of fire-retardant enhancing resistance to warpage PBT/PTT alloy material, comprises following component and parts by weight:
PBT 30-40，
PTT 10-30，
Lubricant 0.3-1,
Ester exchange inhibitor 0.1-0.8,
Oxidation inhibitor 0.3-0.8,
Nucleator 0.5-5,
Fire retardant 5-10,
Fire retarding synergist 1-5,
Toughner 2-10,
Glass fibre 0-30,
Mineral powder 10-30.
The limiting viscosity of described PBT is 0.7-1.3dL/g, and density is 1.30-1.35g/cm
3; The viscosity of described PTT is 0.7-1.0dL/g, and density is 1.33-1.37g/cm
3.
Described lubricant is one or both in silicone oil or Chinese wax oil.
Described ester exchange inhibitor is one or both in triphenyl phosphite, Sodium phosphate dibasic.
Described oxidation inhibitor is one or both in antioxidant 1010, irgasfos 168; Described nucleator is ionomer nucleator, as the surlyn 8920 of Du Pont, the Aclyn 285 of Honeywell.
Described fire retardant is one or both in decabromodiphenyl oxide or brominated epoxy resin; Described fire retarding synergist is one or both in sodium antimonate, weisspiessglanz.
Described toughner is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer AX8900.
Described glass fibre is the alkali free glass fibre of silicon-coating alkyl treating compound.
Described mineral powder is for carry out surface-treated mica powder through coupling agent, and granularity is not more than 800 orders; Described coupling agent is one or both in titanate coupling agent, silane coupling agent.
A preparation method for fire-retardant enhancing resistance to warpage PBT/PTT alloy material, comprises the following steps:
By polybutylene terephthalate PBT and Poly(Trimethylene Terephthalate) PTT respectively at forced air drying at 130 DEG C 3 hours; Take dried PBT, PTT by weight ratio, lubricant, ester exchange inhibitor, oxidation inhibitor, nucleator, fire retardant, fire retarding synergist, toughner, mineral powder mix in high-speed mixer; By the material that mixes in twin screw extruder with glass fibre blending, carry out extruding pelletization; The temperature of twin screw extruder is 190-245 DEG C.
Compared with prior art, the present invention has following beneficial effect:
At present, improving one of most effective means of plastic material flame retardant properties is add bromide fire retardant.But brominated flame-retardant easily generates carbon-coating under DC Electric Field, the generation of accelerated material creepage trace.The connection cutting off surperficial carbon granules improves material resistance to electric trace effective means.Mica powder can play dilution fire retardant, finely dispersed effect, and effectively can intercept the formation of carbon-coating under high electric field action.Mica, with the aspect ratio two-dimensional sheet structure of its uniqueness, can play plane enhancement in the plastic, modifiedly enhances product performance and evenly orientation not buckling deformation.
When adding PTT melt blending in PBT, easily transesterification reaction occurs, weaken material monolithic performance, the larger degradation of PTT consumption is more obvious.Add the generation that triphenyl phosphite or Sodium phosphate dibasic effectively can suppress transesterification reaction, avoid alloy material degradation, thus PTT can be made to add PBT with vast scale carry out blended.
The present invention makes alloy material by blended for PBT and PTT, has the advantage that cost is low, and solves the problem that PBT/PTT alloy material high flame retardant and high CTI value, high-mechanical property be difficult to coexist, and has resistance to warpage, feature that thermotolerance is strong concurrently simultaneously.Alloy material good mechanical property, flame retardant resistance are high, CTI value is high, and product surface is smooth without warpage.
Embodiment
The present invention is described in detail below in conjunction with each embodiment.
In embodiment 1-5, component and proportioning (parts by weight) are in table 1.PBT (solution solvent viscosity ratio 1.0dL/g), PTT (solution solvent viscosity ratio 0.92dL/g) are mixed 5 minutes with lubricant, ester exchange inhibitor, oxidation inhibitor, nucleator, fire retardant, fire retarding synergist, toughner, mineral powder after weighing by proportioning in high-speed mixer, mixture adds twin screw extruder by the first charging opening, glass fibre adds forcing machine by the second charging opening, carries out extruding pelletization.
Extruder temperature is set to: 190 DEG C, I district, 220 DEG C, II district, 240 DEG C, III district, 240 DEG C, IV district, 235 DEG C, V district, 235 DEG C, VI district, 240 DEG C, VII district, 240 DEG C, VIII district, head 245 DEG C, after material is extruded, through water-cooled, pelletizing, pellet forced air drying 3 hours at 130 DEG C, make batten by injection moulding machine, place under 23 DEG C of constant temperature after 16 hours and test, the performance test results is in table 2.
In comparative example 1-3, component and proportioning (parts by weight) are in table 1.Carry out processing, preparing test bars according to the technique of embodiment 1-5, the performance test results is in table 2.
Table 1
Table 2
Embodiment 6
A preparation method for fire-retardant enhancing resistance to warpage PBT/PTT alloy material, comprises the following steps:
By PBT and PTT respectively at forced air drying at 130 DEG C 3 hours, the limiting viscosity of PBT is 0.7dL/g, and density is 1.30g/cm
3, the viscosity of PTT is 0.7dL/g, and density is 1.33g/cm
3, take dried PBT30 weight part by weight ratio, PTT30 weight part, lubricant silicone oil 0.3 weight part, ester exchange inhibitor triphenyl phosphite 0.1 weight part, antioxidant 1010 0.3 weight part, nucleator surlyn 8,920 0.5 weight part, Decabromodiphenyl Ether 5 weight part, fire retarding synergist sodium antimonate 1 weight part, toughner AX89002 weight part, carry out surface-treated mica powder (granularity is 800 orders) 10 weight parts through titanate coupling agent to mix in high-speed mixer, by the material that mixes in twin screw extruder with the alkali free glass fibre 5 weight part blending of silicon-coating alkyl treating compound, carry out extruding pelletization, the temperature of twin screw extruder is 190-245 DEG C.
Embodiment 7
A preparation method for fire-retardant enhancing resistance to warpage PBT/PTT alloy material, comprises the following steps:
By PBT and PTT respectively at forced air drying at 130 DEG C 3 hours, the limiting viscosity of PBT is 1.3dL/g, and density is 1.35g/cm
3, the viscosity of PTT is 1.0dL/g, and density is 1.37g/cm
3, take dried PBT40 weight part by weight ratio, PTT10 weight part, lubricant Chinese wax oil 1 weight part, ester exchange inhibitor Sodium phosphate dibasic 0.8 weight part, irgasfos 168 0.8 weight part, nucleator Aclyn 2855 weight part, flame retardant brominated epoxy resin 10 weight part, fire retarding synergist weisspiessglanz 5 weight part, toughner AX8900 10 weight part, carry out surface-treated mica powder (granularity is 600 orders) 30 weight parts through silane coupling agent to mix in high-speed mixer, by the material that mixes in twin screw extruder with the alkali free glass fibre 30 weight part blending of silicon-coating alkyl treating compound, carry out extruding pelletization, the temperature of twin screw extruder is 190-245 DEG C.
Embodiment 8
A preparation method for fire-retardant enhancing resistance to warpage PBT/PTT alloy material, comprises the following steps:
By PBT and PTT respectively at forced air drying at 130 DEG C 3 hours, the limiting viscosity of PBT is 1.2dL/g, and density is 1.31g/cm
3, the viscosity of PTT is 0.8dL/g, and density is 1.36g/cm
3, take dried PBT32 weight part by weight ratio, PTT22 weight part, lubricant silicone oil 0.3 weight part, Chinese wax oil 0.2 weight part, ester exchange inhibitor triphenyl phosphite 0.2 weight part, Sodium phosphate dibasic 0.2 weight part, antioxidant 1010 0.2 weight part, irgasfos 168 0.3 weight part, ionomer nucleator 2.5 weight part, Decabromodiphenyl Ether 5 weight part, brominated epoxy resin 3 weight part, fire retarding synergist sodium antimonate 1 weight part, weisspiessglanz 1 weight part, toughner AX8900 7 weight part, carry out surface-treated mica powder (granularity is not more than 800 orders) 22 weight parts through silane coupling agent to mix in high-speed mixer, by the material that mixes in twin screw extruder with the alkali free glass fibre 18 weight part blending of silicon-coating alkyl treating compound, carry out extruding pelletization, the temperature of twin screw extruder is 190-245 DEG C.
Be only several specific embodiments of the application above, but the application is not limited thereto, the changes that any person skilled in the art can think of, all should drops in the protection domain of the application.
Claims (9)
1. a fire-retardant enhancing resistance to warpage PBT/PTT alloy material, is characterized in that, comprise following component and parts by weight:
Described glass fibre is the alkali free glass fibre of silicon-coating alkyl treating compound;
Described mineral powder is for carry out surface-treated mica powder through coupling agent, and granularity is not more than 800 orders.
2. a kind of fire-retardant enhancing resistance to warpage PBT/PTT alloy material as claimed in claim 1, it is characterized in that, the limiting viscosity of described PBT is 0.7-1.3dL/g, and density is 1.30-1.35g/cm
3; The viscosity of described PTT is 0.7-1.0dL/g, and density is 1.33-1.37g/cm
3.
3. a kind of fire-retardant enhancing resistance to warpage PBT/PTT alloy material as claimed in claim 1, is characterized in that, described lubricant is one or both in silicone oil or Chinese wax oil.
4. a kind of fire-retardant enhancing resistance to warpage PBT/PTT alloy material as claimed in claim 1, is characterized in that, described ester exchange inhibitor is one or both in triphenyl phosphite, Sodium phosphate dibasic.
5. a kind of fire-retardant enhancing resistance to warpage PBT/PTT alloy material as claimed in claim 1, is characterized in that, described oxidation inhibitor is one or both in antioxidant 1010, irgasfos 168; Described nucleator is ionomer nucleator.
6. a kind of fire-retardant enhancing resistance to warpage PBT/PTT alloy material as claimed in claim 1, is characterized in that, described fire retardant is one or both in decabromodiphenyl oxide or brominated epoxy resin; Described fire retarding synergist is one or both in sodium antimonate, weisspiessglanz.
7. a kind of fire-retardant enhancing resistance to warpage PBT/PTT alloy material as claimed in claim 1, it is characterized in that, described toughner is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer.
8. a kind of fire-retardant enhancing resistance to warpage PBT/PTT alloy material as claimed in claim 1, is characterized in that, described coupling agent is one or both in titanate coupling agent, silane coupling agent.
9. a preparation method for fire-retardant enhancing resistance to warpage PBT/PTT alloy material as claimed in claim 1, is characterized in that, comprise the following steps:
By polybutylene terephthalate PBT and Poly(Trimethylene Terephthalate) PTT respectively at forced air drying at 130 DEG C 3 hours; Take dried PBT, PTT by weight ratio, lubricant, ester exchange inhibitor, oxidation inhibitor, nucleator, fire retardant, fire retarding synergist, toughner, mineral powder mix in high-speed mixer; By the material that mixes in twin screw extruder with glass fibre blending, carry out extruding pelletization; The temperature of twin screw extruder is 190-245 DEG C.
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| CN201010619046.3A CN102532824B (en) | 2010-12-28 | 2010-12-28 | Flame-retardant reinforced warping-resistance PBT/PTT (polybutylene terephthalate/polytrimethylene terephthalate) alloy material and preparation method thereof |
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| CN201010619046.3A CN102532824B (en) | 2010-12-28 | 2010-12-28 | Flame-retardant reinforced warping-resistance PBT/PTT (polybutylene terephthalate/polytrimethylene terephthalate) alloy material and preparation method thereof |
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| CN102838853A (en) * | 2012-09-26 | 2012-12-26 | 东莞市松燊塑料科技有限公司 | Warping-resisting glass fiber reinforced flame-retardant PBT (polybutylece terephthalate) material and preparation method thereof |
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| CN111100432B (en) * | 2019-12-12 | 2022-03-22 | 会通新材料股份有限公司 | PBT/PTT composition and preparation method thereof |
| CN111961341B (en) * | 2020-08-25 | 2022-10-21 | 宁波公牛电器有限公司 | Composite material, preparation method thereof, fixing frame and wall switch |
| CN112552653B (en) * | 2020-10-30 | 2022-03-01 | 金发科技股份有限公司 | Low-smoke high-toughness halogen-free flame-retardant PBT/PTT composite and preparation method and application thereof |
| CN114350122A (en) * | 2022-01-19 | 2022-04-15 | 佛山市汉纬新材料有限公司 | High-strength high-fluidity PBT material and preparation method thereof |
| CN115058102A (en) * | 2022-07-15 | 2022-09-16 | 中钢集团马鞍山矿山研究总院股份有限公司 | Glass fiber reinforced PBT/PET alloy material with smooth surface and preparation method thereof |
| CN115926399A (en) * | 2023-01-03 | 2023-04-07 | 亚瀚材料科技(上海)有限公司 | Low-warpage ultrasonic welding material and preparation process thereof |
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