CN104693768B - PC/PBT alloy materials and its preparation method and application - Google Patents
PC/PBT alloy materials and its preparation method and application Download PDFInfo
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- CN104693768B CN104693768B CN201410815771.6A CN201410815771A CN104693768B CN 104693768 B CN104693768 B CN 104693768B CN 201410815771 A CN201410815771 A CN 201410815771A CN 104693768 B CN104693768 B CN 104693768B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Abstract
The invention discloses a kind of PC/PBT alloy materials and its preparation method and application, in terms of mass fraction, include 50~70 parts of PC, 20~30 parts of PBT, 2~6 parts of SEBS, 5~15 parts of toughener, 0.5~2 part of compatilizer, 0.8~2 part of ester exchange inhibitor, 0.1~1 part of antioxidant and 0.1~1 part of lubricant, wherein, toughener is polysiloxanes methylmethacrylate copolymer, compatilizer is SBS MAH, ester exchange inhibitor is phosphoric acid class ester exchange inhibitor, antioxidant is Hinered phenols antioxidant or phosphite ester kind antioxidant, lubricant is silicone powder.The PC/PBT alloy materials stable performance.In addition, additionally provide a kind of preparation method and application of the PC/PBT alloy materials.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of PC/PBT alloy materials and preparation method thereof and
Using.
Background technology
Makrolon (PC) is a kind of almost colourless glassy amorphous polymer of line style, has impact strength good
The advantages that good, electrical insulation capability is excellent, and use temperature range is wide and product size stability is good, but PC molecules contain substantial amounts of benzene
Ring, molecular rigidity and steric hindrance are all larger, therefore its melting temperature is higher, and stress easily occurs for poor mobile performance during processing, product
Cracking, residual stress is larger, wears no resistance, and to notch sensitive, these all make it be restricted in production application.
Polybutylene terephthalate (PBT) (PBT) is the engineering material of excellent combination property, there is extraordinary chemically stable
Property, mechanical strength, electrical insulation characteristics and heat endurance.Its crystalline rate is fast, can high-speed molding, there is excellent solvent resistant, resistance to
Hot, toughness and wearability and relatively low water absorption rate, various superperformances are remained in that in a humidity environment, be electrically insulated
Property is good, but volume resistance, dielectric loss are big, and finished product molding shrinkage is larger, there is notch impact strength is low, hydrolytic resistance
Difference, crystallize rapidly under low temperature, the features such as high temperature rigid deficiency.PC and PBT is carried out blending and modifying, the PC of preparation by current method
It is unstable with PBT alloy material property.
The content of the invention
Based on this, there is provided PC/PBT alloy materials of a kind of stable performance and its preparation method and application.
A kind of PC/PBT alloy materials, in terms of mass fraction, include 50~70 parts of PC, 20~30 parts of PBT, 2~6 parts
SEBS, 5~15 parts of toughener, 0.5~2 part of compatilizer, 0.8~2 part of ester exchange inhibitor, 0.1~1 part of antioxygen
Agent and 0.1~1 part of lubricant, wherein, toughener is polysiloxanes-methylmethacrylate copolymer, compatilizer SBS-
MAH, ester exchange inhibitor are phosphoric acid class ester exchange inhibitor, and antioxidant is Hinered phenols antioxidant or phosphorous acid esters antioxygen
Agent, lubricant are silicone powder.
In one of the embodiments, the PC is bisphenol-A aromatic copolycarbonate, number-average molecular weight is 18000~
27000。
In one of the embodiments, the inherent viscosity of the PBT is 0.82dL/g~1.3dL/g.
In one of the embodiments, the mass content of styrene is 15%~65% in the SEBS.
In one of the embodiments, the polysiloxanes-methylmethacrylate copolymer is the compound grain of core shell structure
Son, wherein stratum nucleare are polysiloxanes, and shell is methyl methacrylate.
A kind of preparation method of above-mentioned PC/PBT alloy materials, comprises the following steps：
According to above-mentioned mass fraction by each component raw material；
The PC, PBT, SEBS, toughener, compatilizer, ester exchange inhibitor, antioxidant and lubricant are premixed
Close, obtain premix；And
By the premix extruding pelletization, PC/PBT alloy materials are obtained.
In one of the embodiments, the device premix extruding pelletization used is double for double screw extruder
Screw extruder is divided into an area to nine Gong Jiuge areas of area according to charge order, an area is the region fed at first, and head is last
The region of charging, the temperature setting that each section of double screw extruder are respectively：One 205~215 DEG C of area, two 235~245 DEG C of areas, three
235~245 DEG C of area, four 235~245 DEG C of areas, five 225~235 DEG C of areas, six 225~235 DEG C of areas, seven 225~235 DEG C of areas, 8th area
225~235 DEG C, nine 225~235 DEG C of areas, 225~235 DEG C of head.
In one of the embodiments, the temperature of each section of double screw extruder, which is set, is respectively：One 210 DEG C of area, two areas 240
DEG C, three 240 DEG C of areas, four 240 DEG C of areas, five 230 DEG C of areas, six 230 DEG C of areas, seven 230 DEG C of areas, eight 230 DEG C of areas, nine 230 DEG C of areas, head
230℃。
In one of the embodiments, the rotating speed of double screw extruder is 150~550rpm.
A kind of application of above-mentioned PC/PBT alloy materials in automobile case and bumper.
Above-mentioned PC/PBT alloy materials stable performance, overcome the shortcomings of PC processing flowabilities difference and wearability, while more
Mend the shortcomings that PBT impact resistances are low, notch impact strength is not high.In addition, additionally provide a kind of PC/PBT alloy materials
Preparation method and application.
Embodiment
For the ease of understanding the present invention, the present invention is described more fully below.And give the preferable of the present invention
Embodiment.But the present invention can realize in many different forms, however it is not limited to embodiment described herein.Phase
Instead, there is provided the purpose of these embodiments is to make the understanding more thorough and comprehensive to the disclosure.
The PC/PBT alloy materials of one embodiment, in terms of mass fraction, include 50~70 parts of PC, 20~30 parts
PBT, (using polystyrene as end segment, the ethylene-butene copolymer for being hydrogenated with to obtain using polybutadiene is centre to 2~6 parts of SEBS
The linear tri-block copolymer of elastomeric block), 5~15 parts of toughener, 0.5~2 part of compatilizer, 0.8~2 part of ester exchange suppression
Preparation, 0.1~1 part of antioxidant and 0.1~1 part of lubricant, wherein, toughener is polysiloxanes-methyl methacrylate
Copolymer, compatilizer are the SBS-MAH styrene-butadiene-styrene of grafting (maleic anhydride), ester exchange inhibitor
For phosphoric acid class ester exchange inhibitor, antioxidant is Hinered phenols antioxidant or phosphite ester kind antioxidant, and lubricant is silicone powder.
Preferably, PC is bisphenol-A aromatic copolycarbonate, and number-average molecular weight is 18000~27000.
Preferably, PBT inherent viscosity is 0.82dL/g~1.3dL/g.
Preferably, the mass content of styrene is 15%~65% in SEBS.
Preferably, polysiloxanes-methylmethacrylate copolymer is core shell structure compound particle, and wherein stratum nucleare is poly- silicon
Oxygen alkane, shell are methyl methacrylate.
Further, the particle diameter of polysiloxanes-methylmethacrylate copolymer is 90nm~200nm.Preferably, ester is handed over
Inhibitor is changed as at least one of sodium dihydrogen phosphate, ammonium dihydrogen phosphate, triphenyl phosphite and di (isooctyl) phosphate.PC and
Ester exchange reaction can occur between PBT, on the one hand, product of transesterification reaction serves as bulking agent, can improve PBT and PC two is alternate
Interface, on the other hand, ester exchange reaction occurs between PC and PBT, can be decreased obviously the crystallizing power of PBT component, product face
Discoloration is yellow, and produces carbon dioxide, so as to cause the heat distortion temperature of alloy material, mechanical property etc. substantially to deteriorate.Therefore, select
Select suitable ester exchange agent and its content and effectively to control the ester exchange reaction degree between PC and PBT to keeping PBT/PC alloys
Excellent combination property is most important.
Preferably, compatilizer SBS-MAH grafting rate is 0.3%~0.6.After MAH grafting SBS, product SBS-MAH and PC
And PBT generates preferable compatibility, so as to enhance SBS-MAH and PC and SBS-MAH and PBT interfacial adhesion.
Further, Hinered phenols antioxidant 2,6- three-level butyl -4- methylphenols, double (3,5- three-level butyl -4- hydroxyls
Base phenyl) at least one of thioether and four (β-(3,5- three-level butyl -4- hydroxy phenyls) propionic acid) pentaerythritol esters.
Phosphite ester kind antioxidant be three (2,4- di-tert-butyl-phenyls) phosphite esters, it is double [2- methyl -4,6- two (1,1, -
Dimethyl ethyl) phenol] ethyl ester, four (alkoxy -4,4- xenyls of 2,4- di-t-butyls eight) phosphates and (2,4,6-
At least one of tri-tert phenyl -2- butyl -2- ethyls) -1,3- diol phosphites.
Active principle content 99% in silicone powder, pH are 6~8.Silicone powder is used to improve product in PC/PBT alloy materials
Mobility, promote crystallization, improve surface floating fiber, improve impact strength.
The PC/PBT alloy materials have good combination property.Elongation at break and resistance to low temperature are good, -40
Still there is good impact strength under DEG C low temperature, overcome the deficiency of PC processing flowabilities difference and wearability, compensate for simultaneously
The shortcomings that PBT impact resistances are low, notch impact strength is not high.
The preparation method of the PC/PBT alloy materials of one embodiment, comprises the following steps：
According to above-mentioned mass fraction by each component raw material；
The PC, PBT, SEBS, toughener, compatilizer, ester exchange inhibitor, antioxidant and lubricant are premixed
Close, obtain premix；And
By the premix extruding pelletization, PC/PBT alloy materials are obtained.
Further, the device premix extruding pelletization used is double screw extruder, in twin-screw extrusion
Machine melts, extruding pelletization.It is to feed at first that double screw extruder is divided into an area to nine Gong Jiuge areas of area, an area according to charge order
Region, head is the region finally fed.The temperature that each section of double screw extruder is set：One 205~215 DEG C of area,
Two 235~245 DEG C of areas, three 235~245 DEG C of areas, four 235~245 DEG C of areas, five 225~235 DEG C of areas, six 225~235 DEG C of areas, seven
225~235 DEG C of area, eight 225~235 DEG C of areas, nine 225~235 DEG C of areas, 225~235 DEG C of head.
Preferably, the temperature of each section of double screw extruder, which is set, is respectively：One 210 DEG C of area, two 240 DEG C of areas, three areas 240
DEG C, four 240 DEG C of areas, five 230 DEG C of areas, six 230 DEG C of areas, seven 230 DEG C of areas, eight 230 DEG C of areas, nine 230 DEG C of areas, 230 DEG C of head.
The rotating speed of double screw extruder is 150~550rpm (rev/min).
The preparation method of the PC/PBT alloy materials is simple, and easy to operate, cost is low.The PC/PBT alloys being prepared
Material has good combination property.Elongation at break and resistance to low temperature are good, still have good rush under -40 DEG C of low temperature
Hit intensity, overcomes the deficiency of PC processing flowabilities difference and wearability, while compensate for that PBT impact resistances are low, notch shock
The shortcomings that intensity is not high.
Above-mentioned PC/PBT alloy materials can be applied in automobile case and bumper.The PC/PBT alloy materials tool
There is good combination property.Elongation at break and resistance to low temperature are good, still have good impact strong under -40 DEG C of low temperature
Degree, therefore lost applied to that in automobile case and bumper, can reduce caused by automobile is collided.
Above-mentioned PC/PBT alloy materials can also be applied to medicine equipment, cosmetic package, Key works Drug packing, oil product bag
Dress, IT industries, auto industry, electric, daily electrical home appliance and stationery industry.
It is specific embodiment below.
Embodiment 1
By the PC by drying pretreated 70Kg, 20Kg PBT, 2Kg SEBS, 6Kg polysiloxanes-methyl-prop
E pioic acid methyl ester copolymer, 0.5Kg SBS-MAH, 0.8Kg sodium dihydrogen phosphate, 0.1Kg 2,6- three-level butyl -4- methylbenzenes
Phenol and 0.1Kg silicone powder, which are added in homogenizer, to be pre-mixed, and obtains premix.The premixing that will be mixed
Thing is placed in double screw extruder and melted, extruding pelletization, and the temperature setting that each section of double screw extruder is respectively：One 215 DEG C of area,
Two 235 DEG C of areas, three 245 DEG C of areas, four 245 DEG C of areas, five 235 DEG C of areas, six 235 DEG C of areas, seven 235 DEG C of areas, eight 225 DEG C of areas, nine areas 235
DEG C, 235 DEG C of head, obtain PC/PBT alloy materials.
Comparative example and embodiment 2~5, implementation is same as Example 1, and design parameter and technique are referring to table 1：
Table 1
The PBT/PC alloy materials that comparative example in table 1 and embodiment 1~5 are prepared carry out performance test.
Each specific method of testing of index is as follows：Notch impact strength according to ASTM D256 notch impact strengths method of testings 23 DEG C with-
Tested respectively under the conditions of 40 DEG C, bending strength is tested by ASTM D790 bending strength method of testings, and bending modulus is pressed
ASTM D790 bending modulus method of testings are tested, and tensile strength is surveyed by ASTM D638 tensile strength method of testings
Examination, elongation at break are tested by ASTM D638 elongation at break method of testings, and heat distortion temperature presses ASTM D648 thermal changes
Shape temperature testing method is tested.Test result is seen the above table.
As it can be seen from table 1 the PC/PBT alloy materials that the embodiment of the present invention 1~5 is prepared, with comparative example phase
Than, bending strength, bending modulus and tensile strength smaller range change in the case of, PC/PBT alloy materials at 23 DEG C
With -40 DEG C under the conditions of notch impact strength numerical value increase, particularly under -40 DEG C of cryogenic conditions, improve it is obvious that explanation
The low temperature impact ability enhancing of the PC/PBT alloy materials；Elongation at break significantly increases simultaneously, and up to 180%.
Thermoplastic elastomer (TPE) SEBS is added in PC and PBT, and using core shell structure polysiloxanes-methyl methacrylate
Copolymer is the cold tolerance that toughener increases material, and SBS-MAH forms preferable interface transition layer as compatilizer, realizes SEBS
The toughening effect of elastic particle, high impact strength and cold resistance are obtained, realize each mechanical performance of PC/PBT alloy materials
Balance, obtained PC/PBT alloy material stable performances.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (9)
- A kind of 1. PC/PBT alloy materials, it is characterised in that in terms of mass fraction, include 50~70 parts of PC, 20~30 parts PBT, 2~6 parts of SEBS, 5~15 parts of toughener, 0.5~2 part of compatilizer, 0.8~2 part of ester exchange inhibitor, 0.1 ~1 part of antioxidant and 0.1~1 part of lubricant, wherein, toughener is polysiloxanes-methylmethacrylate copolymer, phase Appearance agent is SBS-MAH, and ester exchange inhibitor is phosphoric acid class ester exchange inhibitor, and antioxidant is Hinered phenols antioxidant or phosphorous acid Esters antioxidant, lubricant are silicone powder, and the mass content of styrene is 15%~65% in the SEBS, the poly- silica The particle diameter of alkane-methylmethacrylate copolymer is 90nm~200nm.
- 2. PC/PBT alloy materials according to claim 1, it is characterised in that the PC is bisphenol-A aromatic polycarbonate Ester, number-average molecular weight are 18000~27000.
- 3. PC/PBT alloy materials according to claim 1, it is characterised in that the inherent viscosity of the PBT is 0.82dL/ G~1.3dL/g.
- 4. PC/PBT alloy materials according to claim 1, it is characterised in that the polysiloxanes-methyl methacrylate Ester copolymer is core shell structure compound particle, and wherein stratum nucleare is polysiloxanes, and shell is methyl methacrylate.
- 5. a kind of preparation method of PC/PBT alloy materials as claimed in claim 1, it is characterised in that comprise the following steps：Mass fraction according to claim 1 weighs each component raw material；The PC, PBT, SEBS, toughener, compatilizer, ester exchange inhibitor, antioxidant and lubricant are pre-mixed, obtained To premix；AndBy the premix extruding pelletization, PC/PBT alloy materials are obtained.
- 6. the preparation method of PC/PBT alloy materials according to claim 5, it is characterised in that squeeze the premix Go out to be granulated the device used for double screw extruder, double screw extruder is divided into totally nine, an area to 9th area according to charge order Area, an area are the regions fed at first, and head is the region finally fed, the temperature setting difference that each section of double screw extruder For：One 205~215 DEG C of area, two 235~245 DEG C of areas, three 235~245 DEG C of areas, four 235~245 DEG C of areas, five areas 225~235 DEG C, six 225~235 DEG C of areas, seven 225~235 DEG C of areas, eight 225~235 DEG C of areas, nine 225~235 DEG C of areas, head 225~235 ℃。
- 7. the preparation method of PC/PBT alloy materials according to claim 6, it is characterised in that each section of double screw extruder Temperature setting be respectively：One 210 DEG C of area, two 240 DEG C of areas, three 240 DEG C of areas, four 240 DEG C of areas, five 230 DEG C of areas, six 230 DEG C of areas, Seven 230 DEG C of areas, eight 230 DEG C of areas, nine 230 DEG C of areas, 230 DEG C of head.
- 8. the preparation method of PC/PBT alloy materials according to claim 6, it is characterised in that double screw extruder turns Speed is 150~550rpm.
- A kind of 9. application of the PC/PBT alloy materials in automobile case and bumper as claimed in claim 1.
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| CN105860474A (en) * | 2016-04-12 | 2016-08-17 | 东莞市奥能工程塑料有限公司 | Heat and solvent resisting lightweight alloy and preparation method thereof |
| CN106084711A (en) * | 2016-05-04 | 2016-11-09 | 无锡市嘉邦电力管道厂 | A kind of low gloss PC/PBT alloy material and preparation method thereof |
| CN106336640A (en) * | 2016-08-26 | 2017-01-18 | 青岛海尔新材料研发有限公司 | PC-PBT alloy modified material and preparation method thereof |
| CN106317808A (en) * | 2016-10-17 | 2017-01-11 | 蒙宇 | Lightweight compound material for notebook computer shells |
| CN107141752A (en) * | 2017-05-06 | 2017-09-08 | 广东威林工程塑料股份有限公司 | A kind of alloy material that can be tested by organic solution stress cracking and preparation method thereof |
| CN108329672A (en) * | 2017-12-25 | 2018-07-27 | 福建华塑新材料有限公司 | A kind of low temperature impact PBT and PC alloy materials and preparation method thereof |
| CN109880336B (en) * | 2019-01-10 | 2021-06-01 | 金发科技股份有限公司 | Polycarbonate alloy and preparation method and application thereof |
| CN110643163A (en) * | 2019-10-12 | 2020-01-03 | 东莞市高能高分子材料有限公司 | PC/PBT alloy material and preparation method thereof |
| CN111253728A (en) * | 2020-04-07 | 2020-06-09 | 广东圆融新材料有限公司 | Polycarbonate composition and preparation method thereof |
| CN113637311B (en) * | 2021-08-17 | 2022-08-19 | 金发科技股份有限公司 | Green and environment-friendly polycarbonate alloy composition and preparation method and application thereof |
| CN114806124A (en) * | 2022-03-31 | 2022-07-29 | 金发科技股份有限公司 | Weather-resistant PC/polyester alloy material and preparation method and application thereof |
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