CN110128799A - A kind of PBT composite and preparation method - Google Patents
A kind of PBT composite and preparation method Download PDFInfo
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- CN110128799A CN110128799A CN201910469270.XA CN201910469270A CN110128799A CN 110128799 A CN110128799 A CN 110128799A CN 201910469270 A CN201910469270 A CN 201910469270A CN 110128799 A CN110128799 A CN 110128799A
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Abstract
The invention discloses a kind of PBT composite and preparation methods, belong to polymeric material field, are grouped as by each group of following parts by weight；PBT resin 40~70；Glass fibre 20~40；Modified filler 4~10；Conductive agent 1~4；Toughener 3~4；Antioxidant 0.4~1.0；Lubricant 0.4~1.0, the conductive agent are carbon nanotube and/or graphene；The modified filler is by surfactant treated one or more of wollastonite, whisker, mine fibre.Using enhancing PBT prepared by the present invention, there is good warpage preventing function, is able to satisfy the product of Precision Machining requirement, has good conductive property and mechanical property, and antistatic effect is excellent, can be widely applied to various to the demanding product of electrostatic.
Description
Technical field
The present invention relates to polymeric material field more particularly to a kind of PBT composites and preparation method.
Background technique
Polybutylene terephthalate (PBT) has high rigidity, high intensity, highly crystalline speed and excellent chemical-resistant resistance
Performance and electrical property are a kind of thermoplastic engineering plastics haveing excellent performance, be used primarily in automobile, electronic apparatus, component of machine,
Clothes etc..But the disadvantages of that there is also crystallization shrinkages is big by PBT, poor dimensional stability, notch sensitive.After product is made, warp
Warping phenomenon is often generated, although the biggish improvement of energy after glass fiber reinforcement is added, requires stringent product for some,
Still it is unable to satisfy its product requirement.And its product surface resistivity is very high, is easy to produce static focus effect in use, limitation
Its use scope, especially some antistatic demanding occasions.
The main path for improving antistatic property is to apply one layer of antistatic agent in PBT product surface or add in PBT product
Add antistatic agent filler.The former is easy failure by antistatic property, not enough persistently；And the latter is due to using traditional additive, in order to
Achieve the effect that antistatic, additive is excessive, the mechanical property of material is influenced, using also receiving certain limitation.
Graphene and carbon nanotube are the very excellent nano materials of comprehensive performance.The specific surface area of graphene is high, has
Excellent heating conduction, mechanical property and the electron mobility of high speed at room temperature.Carbon nanotube has excellent electric property
And mechanical property, how it is dissolved into a variety of materials, shows its superiority preferably, it has also become contemporary material
A modified heat subject.
Summary of the invention
Of the invention is currently that the above-mentioned prior art and application existing defect and providing is overcome to prepare a kind of low warpage, good
The excellent PBT composite of good electric conductivity and antistatic effect, after mainly selecting special type filler and glass fibre processing
Compounding enhancing is carried out, realizes warpage preventing requirement；By being added after carbon nanotube and graphene combined processing, antistatic effect is ensured
While keep better mechanical property.It is realized especially by following technical scheme:
A kind of PBT composite, which is characterized in that be grouped as by each group of following parts by weight；PBT resin 40~70；Glass
Glass fiber 20~40；Modified filler 4~10；Conductive agent 1~4；Toughener 3~4；Antioxidant 0.4~1.0；Lubricant 0.4~
1.0
The conductive agent is carbon nanotube and/or graphene；
The modified filler is by surfactant treated one of wollastonite, whisker, mine fibre or more
Kind, the surfactant liquids surfactant and solid surfactant；The liquid surfactant is selected from silane
Coupling agent or titanate coupling agent；The solid surfactant is selected from stearic acid, neopelex or fluorine-containing poly- third
Olefin(e) acid ester, the liquid surfactant and the surface of solids agent mass ratio are 1:1-3.
Further, the surfactant is silane coupling agent and stearic acid.
The toughener is ethylene-methyl acrylate-glyceryl methacrylate terpolymer, ethylene-propylene
Butyl acrylate copolymer, ethylene-octene copolymer connect one of glycidyl methacrylate copolymer or a variety of.
The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and phosphorous acid three
(2,4- di-tert-butyl-phenyl) ester antioxidant, mass ratio 2:1.
The lubricant is pentaerythritol stearate, ethylene bis-fatty acid amides, one in ethylene bis stearamide
Kind is a variety of.
Further, the modified filler passes through the method for surfactant processing are as follows: by silane coupling agent with organic
After solvent dissolved dilution, atomization is added in the modified filler in high-speed mixer, and silane coupling agent dosage is modified quality of material
4%, coupling agent be added after carry out fluidized bed drying reaction；Stearic acid is added by with the mass ratio of silane coupling agent 1:2 again afterwards
Carry out fluidized bed homogenizing reaction, wherein atomization speed is 20~30g/min；High speed mix machine mixing velocity be 500~600 turns/
min；Fluidized bed drying temperature is 75~85 DEG C.
The conductive agent is the compound that carbon nanotube and graphene form, and the mass ratio of carbon nanotube and graphene is 3-
5:1.The compound is handled with the following method: carbon nanotube and graphene being added in organic solvent and dispersed, is added ten
Six alkyl trimethyl ammonium chloride surfactants, are then added iron nitrate solution, heating water bath, and re-ultrasonic dispersion obtains after separation
To conductive agent compound.
Further, the compound of the carbon nanotube and graphene composition is handled with the following method: by carbon nanometer
Pipe and graphene are added in the solution of dehydrated alcohol by 4:1 mass ratio, and it is living as surface that hexadecyltrimethylammonium chloride is added
Property agent, be added with stirring after 6% iron nitrate solution sufficiently reacts in hot bath, carry out the isolated conduction of ultrasonic wave decentralized processing
Agent compound.
Further, the parts by weight of the PBT composite each component and each component are as follows: PBT resin 56.9；Glass fibers
Dimension 30；Modified filler 6；Conductive agent 3；Toughener 3；Antioxidant 0.6；Lubricant 0.5.Wherein, the modified filler is silicon ash
Stone；Conductive agent is carbon nanotube and graphene；Toughener is ethylene-methyl acrylate-glyceryl methacrylate ternary
Copolymer；Antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and (bis- uncle of 2,4- of phosphorous acid three
Butyl phenyl) ester antioxidant combination；Lubricant is pentaerythritol stearate.
Another aspect of the present invention additionally provides the preparation method of above-mentioned PBT composite, comprising the following steps:
(1) it stocks up according to such as above-mentioned component and parts by weight；
(2) PBT got ready and toughener are added in high speed mixing tank, 400~500RPM of revolving speed, incorporation time 1~
2min；
(3) antioxidant, lubricant, filler and conductive agent is added in step (2) and mixing 2-4min is added；
(4) by mixed raw material double screw extruder, from adding fine mouth to be added glass fibre, glass fibre be added before
In 120 DEG C of air dry ovens after drying and processing 2h, then by the coupling agent (with dehydrated alcohol 1:5) of dilute analysis be sprayed at glass surface into
It is added after row processing, melting extrusion, cooling blank obtains composite material.
Further, the double screw extruder heating temperature is 10 sections, temperature is respectively as follows: 220,230,235,240,
240,235,235,230,235,245 DEG C, screw speed is 450 turns/min.
The invention has the benefit that
Using enhancing PBT prepared by the present invention, there is good warpage preventing function, is able to satisfy the production of Precision Machining requirement
Product, have good conductive property and mechanical property, and antistatic effect is excellent, can be widely applied to various to electrostatic requirement
High product.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
The material selected in following embodiment and comparative example are as follows:
PBT resin is Sinopec Yizheng Fiber Optical plant 1100.
Glass fibre is Jiujiang megalith 988A.
Modified filler is that the wollastonite, whisker, mine of Jiangxi Guang Yuan Chemical Co., Ltd. are fine；Coupling agent is the silicon of Nanjing dawn
The stearic acid of alkane coupling agent KH570 and Shanghai times specialization work.
Conductive agent is multi-walled carbon nanotube (LG chemistry LUCAN CP1002M), (Chinese Academy of Sciences's Chengdu chemistry has graphene
Limit company's T NPRGO), conductive black (AC-80 of Beijing Ai Gefu scientific & technical corporation).
Toughener be ethylene-methyl acrylate-glyceryl methacrylate terpolymer (A Kema AX8900),
Ethylene-butyl acrylate copolymer (Du Pont AC3427), ethylene-octene copolymer connect glycidyl methacrylate copolymer
(Jia Yirong compatilizer Jiangsu Co. SBG-002).
Antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester (BASF antioxidant 1076)
With phosphorous acid three (2,4- di-tert-butyl-phenyl) ester antioxidant (BASF irgasfos 168), its ratio be 2:1 to be used in compounding.
Lubricant is pentaerythritol stearate, ethylene bis-fatty acid amides, ethylene bis stearamide.
Embodiment 1
Each component is weighed by weight:
PBT resin is 67g；Glass fibre is 20g；Modified filler is wollastonite 8g；Conductive agent is graphene 1g；Toughener
For ethylene-methyl acrylate-glyceryl methacrylate terpolymer 3g；Antioxidant is β-(3,5- di-t-butyl -4-
Hydroxy phenyl) propionic acid n-octadecyl alcohol ester 0.4g, (2,4- di-tert-butyl-phenyl) the ester antioxidant of phosphorous acid three 0.2g；Lubricant is
Pentaerythritol stearate 0.4g, silane coupling agent KH5700.32g, stearic acid 0.32g.
Wherein wollastonite first passes through silane coupling agent in advance, stearic acid is surface-treated, specific processing method are as follows: by silane
After coupling agent dehydrated alcohol dissolved dilution, atomization is added in the wollastonite in high-speed mixer, and silane coupling agent is added laggard
Row fluidized bed drying reacts 2h；After add stearic acid carry out fluidized bed homogenizing reaction, after having reacted 1h, can be obtained and be modified
Spare filler.Wherein, atomization speed 20g/min；The mixing velocity that high speed mixes machine is 500 turns/min；Fluidized bed drying temperature
Degree is 75 DEG C.
PBT composite the preparation method comprises the following steps: (revolving speed in high speed mixing tank is added in load weighted PBT and toughener
400RPM), 1min is mixed；Then mixing 2min is added in antioxidant, lubricant, filler and conductive agent.By mixed raw material
It is added in double screw extruder, from adding fine mouth to be added, glass fibre dries in 120 DEG C of air dry ovens glass fibre before being added
After dry-cure 2h, then the coupling agent (with dehydrated alcohol 1:5) of dilute analysis is sprayed at glass surface and is handled, it is cold after melting extrusion
But blank obtains composite material.Wherein double screw extruder heating temperature is 10 sections, temperature is respectively as follows: 220,230,235,240,
240,235,235,230,235,245 DEG C, screw speed is 450 turns/min.
Producing the material come, injection molding prepares test bars after dry 4h in 120 DEG C of air blast baking material buckets.
Embodiment 2
PBT resin is 64.9g；Glass fibre is 25g；Modified filler is whisker 4g；Conductive agent is carbon nanotube 2g；Toughening
Agent is ethylene-butyl acrylate copolymer 3g；Antioxidant is the positive octadecanol of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid
Ester 0.4g, (2,4- di-tert-butyl-phenyl) the ester antioxidant of phosphorous acid three 0.2g；Lubricant is ethylene bis-fatty acid amides 0.5g, silicon
Alkane coupling agent KH570 0.16g, stearic acid 0.16g.
Wherein whisker first passes through silane coupling agent in advance, stearic acid is surface-treated, specific processing method are as follows: by silane idol
After joining agent dehydrated alcohol dissolved dilution, atomization is added in the whisker in high-speed mixer, and silane coupling agent is flowed after being added
Change bed dry reaction 2h；After add stearic acid carry out fluidized bed homogenizing reaction, after having reacted 1h, can be obtained be modified it is standby
Use filler.Wherein, atomization speed 30g/min；The mixing velocity that high speed mixes machine is 600 turns/min；Fluidized bed drying temperature is
80℃。
PBT composite the preparation method comprises the following steps: (revolving speed in high speed mixing tank is added in load weighted PBT and toughener
500RPM), 1min is mixed；Then mixing 2min is added in antioxidant, lubricant, filler and conductive agent.By mixed raw material
It is added in double screw extruder, from adding fine mouth to be added, glass fibre dries in 120 DEG C of air dry ovens glass fibre before being added
After dry-cure 2h, then the coupling agent (with dehydrated alcohol 1:5) of dilute analysis is sprayed at glass surface and is handled, it is cold after melting extrusion
But blank obtains composite material.Wherein double screw extruder heating temperature is 10 sections, temperature is respectively as follows: 220,230,235,240,
240,235,235,230,235,245 DEG C, screw speed is 450 turns/min.
Producing the material come, injection molding prepares test bars after dry 4h in 120 DEG C of air blast baking material buckets.
Embodiment 3
PBT resin is 59.6g；Glass fibre is 30g；Modified filler is wollastonite 6g；Conductive agent is carbon nanotube 2.4g/
Graphene 0.6g；Toughener is ethylene-methyl acrylate-glyceryl methacrylate terpolymer 3g；Antioxidant is
β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester 0.4g, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester
Antioxidant 0.2g；Lubricant is pentaerythritol stearate 0.5g, silane coupling agent KH570 0.24g, stearic acid 0.48g.
Wherein wollastonite first passes through silane coupling agent in advance, stearic acid is surface-treated, specific processing method are as follows: by silane
After coupling agent KH570 dehydrated alcohol dissolved dilution, atomization is added in the wollastonite in high-speed mixer, silane coupling agent
KH570 carries out fluidized bed drying after being added and reacts 2h；After add stearic acid carry out fluidized bed homogenizing reaction, after having reacted 1h,
The spare filler being modified can be obtained.Wherein, atomization speed 20g/min；High speed mix machine mixing velocity be 550 turns/
min；Fluidized bed drying temperature is 80 DEG C.
Carbon nanotube and graphene are added in the solution of dehydrated alcohol, hexadecyltrimethylammonium chloride is added as table
Face activating agent is instilled after 6% iron nitrate solution sufficiently reacts 1h under 40 DEG C of stirring in water bath, reacted product is placed into super
Ultrasonic wave decentralized processing 2h is carried out in sound wave water bath containers, will obtain conduction after the product being ultrasonically treated washing, filtering, drying
Agent compound.
PBT composite the preparation method comprises the following steps: (revolving speed in high speed mixing tank is added in load weighted PBT and toughener
450RPM), 1min is mixed；Then mixing 2min is added in antioxidant, lubricant, filler and conductive agent.By mixed raw material
It is added in double screw extruder, from adding fine mouth to be added, glass fibre dries in 120 DEG C of air dry ovens glass fibre before being added
After dry-cure 2h, then the coupling agent (with dehydrated alcohol 1:5) of dilute analysis is sprayed at glass surface and is handled, it is cold after melting extrusion
But blank obtains composite material.Wherein double screw extruder heating temperature is 10 sections, temperature is respectively as follows: 220,230,235,240,
240,235,235,230,235,245 DEG C, screw speed is 450 turns/min.
Producing the material come, injection molding prepares test bars after dry 4h in 120 DEG C of air blast baking material buckets.
Embodiment 4
PBT resin is 61.9g；Glass fibre is 25g；Modified filler is wollastonite 6g；Conductive agent is carbon nanotube 2.5g/
Graphene 0.5g；Toughener is ethylene-methyl acrylate-glyceryl methacrylate terpolymer 3g；Antioxidant is
β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester 0.4g, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester
Antioxidant 0.2g；Lubricant is pentaerythritol stearate 0.5g, silane coupling agent KH570 0.24g, stearic acid 0.48g.
Wherein wollastonite first passes through silane coupling agent in advance, stearic acid is surface-treated, specific processing method are as follows: by silane
After coupling agent KH570 dehydrated alcohol dissolved dilution, atomization is added in the wollastonite in high-speed mixer, silane coupling agent
KH570 carries out fluidized bed drying after being added and reacts 2h；After add stearic acid carry out fluidized bed homogenizing reaction, after having reacted 1h,
The spare filler being modified can be obtained.Wherein, atomization speed 25g/min；High speed mix machine mixing velocity be 550 turns/
min；Fluidized bed drying temperature is 85 DEG C.
Carbon nanotube and graphene are added in the solution of dehydrated alcohol, hexadecyltrimethylammonium chloride is added as table
Face activating agent is instilled after 6% iron nitrate solution sufficiently reacts 1h under 40 DEG C of stirring in water bath, reacted product is placed into super
Ultrasonic wave decentralized processing 2h is carried out in sound wave water bath containers, will obtain conduction after the product being ultrasonically treated washing, filtering, drying
Agent compound.
PBT composite the preparation method comprises the following steps: (revolving speed in high speed mixing tank is added in load weighted PBT and toughener
400RPM), 2min is mixed；Then mixing 4min is added in antioxidant, lubricant, filler and conductive agent.By mixed raw material
It is added in double screw extruder, from adding fine mouth to be added, glass fibre dries in 120 DEG C of air dry ovens glass fibre before being added
After dry-cure 2h, then the coupling agent (with dehydrated alcohol 1:5) of dilute analysis is sprayed at glass surface and is handled, it is cold after melting extrusion
But blank obtains composite material.Wherein double screw extruder heating temperature is 10 sections, temperature is respectively as follows: 220,230,235,240,
240,235,235,230,235,245 DEG C, screw speed is 450 turns/min.
Producing the material come, injection molding prepares test bars after dry 4h in 120 DEG C of air blast baking material buckets.
Embodiment 5
PBT resin is 63.9g；Glass fibre is 25g；Modified filler is mine fibre 5g；Conductive agent is graphene 2g；Toughener
Glycidyl methacrylate copolymer 3g is met for ethylene-octene copolymer；Antioxidant is β-(3,5- di-t-butyl -4- hydroxyl
Base phenyl) propionic acid n-octadecyl alcohol ester 0.4g, (2,4- di-tert-butyl-phenyl) the ester antioxidant of phosphorous acid three 0.2g；Lubricant is season
Penta tetrol stearate 0.5g, silane coupling agent KH570 0.2g, stearic acid 0.6g.
Its chats fibre first passes through silane coupling agent in advance, stearic acid is surface-treated, specific processing method are as follows: by silane idol
After joining agent KH570 dehydrated alcohol dissolved dilution, atomization is added in the mine fibre in high-speed mixer, and silane coupling agent KH570 adds
Fluidized bed drying is carried out after entering reacts 2h；After add stearic acid carry out fluidized bed homogenizing reaction, after having reacted 1h, can be obtained
The spare filler being modified.Wherein, atomization speed 25g/min；The mixing velocity that high speed mixes machine is 580 turns/min；Fluidized bed
Drying temperature is 75 DEG C.
PBT composite the preparation method comprises the following steps: (revolving speed in high speed mixing tank is added in load weighted PBT and toughener
450RPM), 2min is mixed；Then mixing 1.5min is added in antioxidant, lubricant, filler and conductive agent.By mixed original
Material is added in double screw extruder, and from adding fine mouth to be added, glass fibre is added preceding in 120 DEG C of air dry ovens glass fibre
After drying and processing 2h, then the coupling agent (with dehydrated alcohol 1:5) of dilute analysis is sprayed at glass surface and is handled, after melting extrusion
Cooling blank obtains composite material.Wherein double screw extruder heating temperature is 10 sections, temperature is respectively as follows: 220,230,235,
240,240,235,235,230,235,245 DEG C, screw speed is 450 turns/min.
Producing the material come, injection molding prepares test bars after dry 4h in 120 DEG C of air blast baking material buckets.
Embodiment 6
PBT resin is 40g；Glass fibre is 40g；Modified filler is wollastonite 10g；Conductive agent is carbon nanotube 3g/ stone
Black alkene 1g；Toughener is that ethylene-octene copolymer meets glycidyl methacrylate copolymer 4g；Antioxidant is β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester 0.5g, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester antioxidant
0.5g；Lubricant is pentaerythritol stearate 1g, silane coupling agent KH570 0.4g, stearic acid 0.8g.
Wherein wollastonite first passes through silane coupling agent in advance, stearic acid is surface-treated, specific processing method are as follows: by silane
After coupling agent KH570 dehydrated alcohol dissolved dilution, atomization is added in the wollastonite in high-speed mixer, silane coupling agent
KH570 carries out fluidized bed drying after being added and reacts 2h；After add stearic acid carry out fluidized bed homogenizing reaction, after having reacted 1h,
The spare filler being modified can be obtained.Wherein, atomization speed 28g/min；High speed mix machine mixing velocity be 530 turns/
min；Fluidized bed drying temperature is 72 DEG C.
Carbon nanotube and graphene are added in the solution of dehydrated alcohol, hexadecyltrimethylammonium chloride is added as table
Face activating agent is instilled after 6% iron nitrate solution sufficiently reacts 1h under 40 DEG C of stirring in water bath, reacted product is placed into super
Ultrasonic wave decentralized processing 2h is carried out in sound wave water bath containers, will obtain conduction after the product being ultrasonically treated washing, filtering, drying
Agent compound.
PBT composite the preparation method comprises the following steps: (revolving speed in high speed mixing tank is added in load weighted PBT and toughener
450RPM), 1min is mixed；Then mixing 2min is added in antioxidant, lubricant, filler and conductive agent.By mixed raw material
It is added in double screw extruder, from adding fine mouth to be added, glass fibre dries in 120 DEG C of air dry ovens glass fibre before being added
After dry-cure 2h, then the coupling agent (with dehydrated alcohol 1:5) of dilute analysis is sprayed at glass surface and is handled, it is cold after melting extrusion
But blank obtains composite material.Wherein double screw extruder heating temperature is 10 sections, temperature is respectively as follows: 220,230,235,240,
240,235,235,230,235,245 DEG C, screw speed is 450 turns/min.
Producing the material come, injection molding prepares test bars after dry 4h in 120 DEG C of air blast baking material buckets.
Embodiment 7
PBT resin is 70g；Glass fibre is 29.6g, and antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid
Positive octadecanol ester 0.3g, (2,4- di-tert-butyl-phenyl) the ester antioxidant of phosphorous acid three 0.15g；Lubricant is that pentaerythrite is stearic
Acid esters 0.4g.
PBT composite the preparation method comprises the following steps: (revolving speed in high speed mixing tank is added in load weighted PBT and toughener
500RPM), 2min is mixed；Then mixing 4min is added in antioxidant.Mixed raw material is added in double screw extruder, glass
Glass fiber from adding fine mouth to be added, glass fibre be added before in 120 DEG C of air dry ovens after drying and processing 2h, then by the idol of dilute analysis
Connection agent (with dehydrated alcohol 1:5) is sprayed at glass surface and is handled, and cooling blank obtains composite material after melting extrusion.Wherein
Double screw extruder heating temperature is 10 sections, and temperature is respectively as follows: 220,230,235,240,240,235,235,230,235,245
DEG C, screw speed is 450 turns/min.
Producing the material come, injection molding prepares test bars after dry 4h in 120 DEG C of air blast baking material buckets.
Embodiment 8
PBT resin is 56.9g；Glass fibre is 25g；Modified filler is whisker 6g；Conductive agent is conductive black 8g；Toughening
Agent is ethylene-butyl acrylate copolymer 3g；Antioxidant is the positive octadecanol of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid
Ester 0.4g, (2,4- di-tert-butyl-phenyl) the ester antioxidant of phosphorous acid three 0.2g；Lubricant is ethylene bis-fatty acid amides 0.5g, silicon
Alkane coupling agent KH570 0.24g, stearic acid 0.72g.
Wherein whisker first passes through silane coupling agent in advance, stearic acid is surface-treated, specific processing method are as follows: by silane idol
After joining agent KH570 dehydrated alcohol dissolved dilution, atomization is added in the whisker in high-speed mixer, and silane coupling agent KH570 adds
Fluidized bed drying is carried out after entering reacts 2h；After add stearic acid carry out fluidized bed homogenizing reaction, after having reacted 1h, can be obtained
The spare filler being modified.Wherein, atomization speed 30g/min；The mixing velocity that high speed mixes machine is 600 turns/min；Fluidized bed
Drying temperature is 75 DEG C.
PBT composite the preparation method comprises the following steps: (revolving speed in high speed mixing tank is added in load weighted PBT and toughener
450RPM), 1.5min is mixed；Then mixing 3min is added in antioxidant, lubricant, filler and conductive agent.By mixed original
Material is added in double screw extruder, and from adding fine mouth to be added, glass fibre is added preceding in 120 DEG C of air dry ovens glass fibre
After drying and processing 2h, then the coupling agent (with dehydrated alcohol 1:5) of dilute analysis is sprayed at glass surface and is handled, after melting extrusion
Cooling blank obtains composite material.Wherein double screw extruder heating temperature is 10 sections, temperature is respectively as follows: 220,230,235,
240,240,235,235,230,235,245 DEG C, screw speed is 450 turns/min.
Producing the material come, injection molding prepares test bars after dry 4h in 120 DEG C of air blast baking material buckets.
The recipe ingredient table of 1 specific embodiment of table
In each embodiment, the specific refinement of each component is selected without limitation, those skilled in the art are according to invention
The selection that content can be made is applicable.
By Examples 1 to 8 it is modified be granulated the injection molding in 220-245 DEG C of injection molding machine of obtained particle stretch, it is curved
Bent, impact batten, is tested for the property batten by GB standard.Test bars are before testing first in (23 ± 2) DEG C, humidity
88h is placed in the environment of (50 ± 10) %.
Tensile bars size:
| Length (mm) | Width (mm) | Thickness (mm) |
| 150±2 | 10±0.2 | 4±0.2 |
It is bent batten size:
| Length (mm) | Width (mm) | Thickness (mm) |
| 80±2 | 10±0.2 | 4±0.2 |
Notch shock batten size:
| Length (mm) | Width (mm) | Thickness (mm) | Notch residue width (mm) |
| 80±2 | 10±0.2 | 4±0.2 | 8±0.2 |
Non-notch impacts batten size:
| Length (mm) | Width (mm) | Thickness (mm) |
| 80±2 | 10±0.2 | 4±0.2 |
Antistatic property mainly by test be molded by come specimen surface resistance come measure judge.By antistatic raw material
It is molded into 2mm thickness colour table, places after 48h at 25 DEG C ± 2 DEG C of temperature, sheet resistance is used under the conditions of relative humidity 55%~60%
Instrument is tested.
Warpage preventing performance is by measuring the amount of warpage being molded by come the plane of product product and horizontal plane.Product is molded by
At 25 DEG C ± 2 DEG C after coming, tested after placing 48h under the conditions of relative humidity 55%~60%.Angularity be maximum amount of warpage/
Product projector distance.
2 actual test performance table of table
From test result analysis it can be seen that
1) increase with conductive agent ratio, material be can be seen that from embodiment 1, embodiment 2, embodiment 3 and embodiment 4
Sheet resistance gradually become smaller, antistatic effect is better；With the raising of glass fibre and filler, warpage preventing effect is better；
But the physical property of material can also be declined, and therefore, the PBT resin of embodiment 4, glass fibre and filling powder ratio are best.
2) from embodiment 2, embodiment 4, embodiment 5 and embodiment 6 it can be seen that the addition meeting of modified filler and conductive agent
Reduce the impact strength and fluidity of molten of material.On the other hand, with the increase of filler, warping coefficient becomes smaller, but mechanics
Performance can be declined.Case study on implementation is made a general survey of, 3 material proportion of embodiment is optimal warpage preventing anti-static material.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (14)
1. a kind of PBT composite, which is characterized in that be grouped as by each group of following parts by weight；PBT resin 40~70；Glass
Fiber 20~40；Modified filler 4~10；Conductive agent 1~4；Toughener 3~4；Antioxidant 0.4~1.0；Lubricant 0.4~1.0,
The conductive agent is carbon nanotube and/or graphene；
The modified filler is by surfactant treated one or more of wollastonite, whisker, mine fibre, institute
The surfactant stated includes liquid surfactant and solid surfactant；It is even that the liquid surfactant is selected from silane
Join agent or titanate coupling agent；The solid surfactant is selected from stearic acid, neopelex or fluorine-containing polypropylene
Acid esters, the liquid surfactant and the surface of solids agent mass ratio are 1:1-3.
2. PBT composite according to claim 1, which is characterized in that the surfactant is silane coupling agent
And stearic acid.
3. PBT composite according to claim 1, which is characterized in that the toughener is ethylene-methyl acrylate-
Glycidyl methacrylate terpolymer, ethylene-butyl acrylate copolymer, ethylene-octene copolymer connect methyl-prop
One of olefin(e) acid glycidyl ester copolymer is a variety of.
4. PBT composite according to claim 1, which is characterized in that the antioxidant is β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyl) propionic acid n-octadecyl alcohol ester and phosphorous acid three (2,4- di-tert-butyl-phenyl) ester antioxidant, mass ratio 2:
1。
5. PBT composite according to claim 1, which is characterized in that the lubricant is pentaerythrite stearic acid
One of ester, ethylene bis-fatty acid amides, ethylene bis stearamide are a variety of.
6. -5 any PBT composite according to claim 1, which is characterized in that the conductive agent be carbon nanotube and
The mass ratio of the compound of graphene composition, carbon nanotube and graphene is 3-5:1.
7. PBT composite according to claim 6, which is characterized in that the compound is handled with the following method:
Carbon nanotube and graphene are added in organic solvent and dispersed, hexadecyltrimethylammonium chloride is added, ferric nitrate is then added
Solution, heating water bath, re-ultrasonic dispersion obtain conductive agent compound after separation.
8. PBT composite according to claim 7, which is characterized in that the compound is handled with the following method:
Carbon nanotube and graphene are added in the solution of dehydrated alcohol by 4:1 mass ratio, hexadecyltrimethylammonium chloride is added,
Hot bath is added with stirring after iron nitrate solution sufficiently reacts, and carries out the isolated conductive agent compound of ultrasonic wave decentralized processing.
9. PBT composite according to claim 1, which is characterized in that be grouped as by each group of following parts by weight: PBT
Resin 56.9；Glass fibre 30；Modified filler 6；Conductive agent 3；Toughener 3；Antioxidant 0.6；Lubricant 0.5.
10. PBT composite according to claim 9, which is characterized in that the modified filler is wollastonite；It is conductive
Agent is carbon nanotube and graphene；Toughener is ethylene-methyl acrylate-glyceryl methacrylate terpolymer；
Antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester and (the 2,4- di-tert-butyl of phosphorous acid three
Base) ester antioxidant combination；Lubricant is pentaerythritol stearate.
11. PBT composite according to claim 1, which is characterized in that the modified filler passes through surfactant
The method of processing are as follows: after silane coupling agent organic solvent dissolved dilution, the modified filler in high-speed mixer is added in atomization
In, silane coupling agent dosage is modified quality of material, and coupling agent carries out fluidized bed drying reaction after being added；It presses again afterwards and silane
The mass ratio of coupling agent is added stearic acid and carries out fluidized bed homogenizing reaction, wherein atomization speed is 20~30g/min；High speed is mixed
The mixing velocity of machine is 500~600 turns/min；Fluidized bed drying temperature is 75~85 DEG C.
12. a kind of preparation method of PBT composite, comprising the following steps:
(1) according to the component and parts by weight stock as described in claim 1-11 is any；
(2) PBT and toughener are added in high speed mixing tank, 400~500RPM of revolving speed, 1~2min of incorporation time；
(3) antioxidant, lubricant, modified material and conductive agent is added in step (2) and mixing 2-4min is added；
(4) glass fibre, melting extrusion in mixed raw material double screw extruder, will be added, cooling blank obtains composite wood
Material.
13. preparation method according to claim 12, which is characterized in that the glass fibre is in 120 DEG C of forced air dryings
In case after drying and processing 2h, then 1:5 is sprayed at glass surface and handles by volume by the coupling agent of dilute analysis and dehydrated alcohol
After add in raw material double screw extruder.
14. preparation method according to claim 12, which is characterized in that the double screw extruder heating temperature is 10
Section, temperature are respectively as follows: 220,230,235,240,240,235,235,230,235,245 DEG C, and screw speed is 450 turns/min.
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| CN114149666A (en) * | 2021-12-28 | 2022-03-08 | 会通新材料股份有限公司 | PBT composite material and preparation method thereof |
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Application publication date: 20190816 |