CN106084716B - Weather-proof bloom is exempted to spray PC/ASA alloy material and preparation method thereof - Google Patents
Weather-proof bloom is exempted to spray PC/ASA alloy material and preparation method thereof Download PDFInfo
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- CN106084716B CN106084716B CN201610414354.XA CN201610414354A CN106084716B CN 106084716 B CN106084716 B CN 106084716B CN 201610414354 A CN201610414354 A CN 201610414354A CN 106084716 B CN106084716 B CN 106084716B
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Classifications
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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
-
- 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
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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
-
- 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
Abstract
Exempt to spray PC/ASA alloy material and preparation method thereof the present invention relates to a kind of weather-proof bloom, the alloy material includes each component of following parts by weight: 40~60 parts of PC resin, 20~38 parts of ASA resin, 5~20 parts of PBT resin, 0.1~1 part of weather resisting agent, 0.1~1 part of antioxidant, 0.1~1 part of lubricant, 2~5 parts of black masterbatch.The preparation method of the alloy material includes: that PC resin, PBT resin, antioxidant and mix lubricant are obtained mixture a, and ASA, weather resisting agent and black masterbatch mix to obtain mixture b；By the main spout feeding of mixture a, the feeding of mixture b side spout；Melting extrusion is granulated to obtain the final product.The present invention improves the mobility of entire material by the way that PBT is added, and has excellent copy mold ability；By side feed ASA, weather resisting agent and black masterbatch, the temperature of side feed mouth is reduced, using viscosity than matching, dispersion is improved, obtains weather-proof bloom and exempt to spray PC/ASA alloy material.
Description
Technical field
The invention belongs to polymer blended, Polymer Processing fields, and in particular to a kind of bloom is exempted to spray PC/ASA
Alloy material and preparation method thereof.
Background technique
PC/ASA alloy material is widely used and automobile and electricity due to its excellent shock resistance, heat resistance, weather resistance
The fields such as sub- product.With the development of automobile, a kind of trend will be become by exempting from primary coat environment-friendly materials.
For PC/ASA due to the poor flow quality of ASA, the general flow of material is not high, is unable to satisfy bloom and exempts from wanting for spraying
It asks.The method for usually improving PC/ASA mobility is the molecular weight by reducing PC, but the mobility that the method improves material has
Limit.
The bloom that automobile uses exempts to spray PC/ASA additional requirement is that weather-proof, and ASA is due to its excellent weather resistance, usually
Specially treated is not done when use, is unable to satisfy the requirement of high durable component, such as grid exterior trimming parts.The more low-L value how to obtain
And exempt to spray the technological difficulties that PC/ASA needs to solve.
In the prior art, in 102532849 A of patent document CN, disclose a kind of PC/ASA/PBT alloy material and its
Preparation method, by polycarbonate, acrylonitrile-styrene-acrylic ester graft copolymer, polybutylene terephthalate (PBT), increasing
Tough dose and antioxidant composition；25-65 parts of the polycarbonate；Acrylonitrile-styrene-acrylic ester graft copolymer 10-25
Part；20-55 parts of polybutylene terephthalate (PBT)；2-10 parts of elastomer flexibilizer.Product of the present invention has excellent impact
Can, good heat resistance and mechanical performance can be used for inner and outer decorative parts of automobile etc..But the alloy material weatherability of this method preparation is still
It is not high, and it is unable to satisfy the requirement that bloom exempts from spraying.
Summary of the invention
For the defects in the prior art, exempt to spray PC/ASA alloy the purpose of the present invention is to provide a kind of weather-proof bloom
Material and preparation method thereof, weather-proof bloom of the invention, which exempts to spray PC/ASA alloy material, has that weather resistance is excellent, bloom, black
Bright feature again.
The purpose of the present invention is what is be achieved through the following technical solutions:
Exempt to spray PC/ASA alloy material, each group comprising following parts by weight the present invention provides a kind of weather-proof bloom
Point:
Preferably, the relative molecular weight of the PC resin is 10000~20000g/mol, and glass transition temperature is 140~150
℃。
Preferably, the ASA resin is Acrylate-styrene bipolymer-acrylonitrile composition graft copolymer, acrylate rubber
The weight percentage of glue is 40-75%.
Preferably, intrinsic viscosity of the PBT resin when measuring ortho-chloro phenol solution for 25 DEG C is 0.45-1.20.It adopts
With the PBT resin of the viscosity, PBT can be made in injection molding in article surface precedence partition.If viscosity is excessively high, mobility drop will lead to
It is low, it can not preferably be distributed in article surface；If viscosity is too low, toughness of material decline will lead to.
Preferably, the weather resisting agent includes the mixing of one or both of benzotriazole, triazine.
Preferably, the antioxidant is bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic acid of triethylene-glycol
Ester], four [β-(3,5- di-t-butyl 4- hydroxy phenyl) propionic acid] pentaerythritol esters, three (2,4- di-tert-butyl-phenyl) phosphorous acid
The mixing of one or more of ester, double stearyl alcohol pentaerythritol diphosphites.
Preferably, the lubricant is silane polymer, solid paraffin, atoleine, fatty acid salt, calcium stearate fat
In sour amide, calcium stearate, zinc stearate, stearic amide, methylene bis stearic amide and N, N- ethylene bis stearic acid amide
One or more of mixing.
Preferably, the black masterbatch is the master batch that content of carbon black is 30-70%, and master batch carrier is PE wax.Black masterbatch
Addition can get the black effect of bloom.Black masterbatch additional amount is excessive, and it is uneven to will lead to carbon black dispersion；Additional amount is very few,
It is inadequate to will lead to blackness.
Exempt to spray the preparation method of PC/ASA alloy material the present invention also provides a kind of weather-proof bloom, including as follows
Step:
S1, PC resin, PBT resin, antioxidant and lubricant are carried out to mixing acquisition mixture a, ASA, weather resisting agent and charcoal
Black masterbatch obtains mixture b by mixing；
S2, mixture a is fed by the main spout of double screw extruder, mixture b passes through double screw extruder
The side spout of 6th area's cylinder is fed；
S3, melting extrusion are granulated and exempt to spray PC/ASA alloy material up to weather-proof bloom.
Preferably, the 10 section barrel temperature of double screw extruder set gradually for 200 DEG C, 240 DEG C, 260 DEG C, 260 DEG C,
260 DEG C, 240 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 260 DEG C, double-screw extruder screw revolving speed are 500~800rpm.
The prior art is compared, and the present invention, the utility model has the advantages that by adding a certain amount of PBT, improves entire with following
The mobility of material has excellent copy mold ability；By side feed ASA, weather resisting agent and black masterbatch, by the temperature of side feed mouth
Degree reduces, and using viscosity than matching, improves dispersion, obtains weather-proof bloom and exempt to spray PC/ASA alloy material.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
The L-1250WS of the PC selected in following embodiment and comparative example Di Ren Asahi Chemical Industry, ASA kumho company of South Korea
XC-400, PBT select the Yizheng Gou Zi petro-chemical corporation production, viscosity be 0.6 PBT；Antioxidant is the Irganox of Ciba company
1076 and Irganox 168, weight ratio 1:1；Lubricant is commercially available pentaerythrite stearic acid, and weather resisting agent is Basf
The Kemisorb 102 of company, black masterbatch be Cabot I-940.
The weather-proof bloom used in the examples is exempted to spray the preparation method of PC/ASA alloy material, including walks as follows
It is rapid:
S1, PC resin, PBT resin, antioxidant and lubricant are carried out to mixing acquisition mixture a, ASA, weather resisting agent and charcoal
Black masterbatch obtains mixture b by mixing；
S2, mixture a is fed by the main spout of double screw extruder, mixture b passes through double screw extruder
The side spout of 6th area's cylinder is fed；
S3, melting extrusion are granulated and exempt to spray PC/ASA alloy material up to weather-proof bloom.
The 10 section barrel temperature of double screw extruder set gradually for 200 DEG C, 240 DEG C, 260 DEG C, 260 DEG C, 260 DEG C,
240 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 260 DEG C, double-screw extruder screw revolving speed are 500~800rpm.
Comparative example 1
A kind of weather-proof bloom is exempted to spray PC/ASA alloy material and preparation method thereof, method includes the following steps:
(1) each component is weighed by weight: PC:40, ASA:38, PBT:20, black masterbatch: 2；Antioxidant 1010 0.1,
Irgasfos 168 0.1, lubricant 0.3, weather resisting agent 0.5；
(2) raw material are all fed from main spout, the melting extrusion at 200~260 DEG C, screw extruder revolving speed is
500rpm is granulated getting the product by melting extrusion.
Comparative example 2
A kind of weather-proof bloom is exempted to spray PC/ASA alloy material and preparation method thereof, method includes the following steps:
(1) each component is weighed by weight: PC:60, ASA:38, black masterbatch: 2；Antioxidant 1010 0.1, antioxidant
168 0.1, lubricant 0.3, weather resisting agent 0.5
(2) PC resin, PBT resin, antioxidant and lubricant are added in mixing and blending machine and carry out mixing acquisition mixture
1, remaining ASA, weather resisting agent and black masterbatch are mixed by blender and obtain mixture 2；
(3) mixture 1 is fed by the main spout of double screw extruder, the 6th area cylinder that mixture 2 passes through extruder
The side feed mouth of body is fed；Barrel temperature is set as 200-240-260-260-260-240-240-250-260-260, and melting is squeezed
Out, it is granulated getting the product, weather-proof bloom is made and exempts to spray PC/ASA alloy material.
Embodiment 1
A kind of weather-proof bloom is exempted to spray PC/ASA alloy material and preparation method thereof, method includes the following steps:
(1) each component is weighed by weight: PC:40, ASA:38, PBT:20, black masterbatch: 2；Antioxidant 1010 0.1,
Irgasfos 168 0.1, lubricant 0.3, weather resisting agent 1
(2) PC resin, PBT resin, antioxidant and lubricant are added in mixing and blending machine and carry out mixing acquisition mixture
1, remaining ASA, weather resisting agent and black masterbatch are mixed by blender and obtain mixture 2；
(3) mixture 1 is fed by the main spout of double screw extruder, the 6th area cylinder that mixture 2 passes through extruder
The side feed mouth of body is fed；Barrel temperature is set as 200-240-260-260-260-240-240-250-260-260, and melting is squeezed
Out, it is granulated getting the product, weather-proof bloom is made and exempts to spray PC/ASA alloy material.
Embodiment 2
A kind of weather-proof bloom is exempted to spray PC/ASA alloy material and preparation method thereof, method includes the following steps:
(1) each component is weighed by weight: PC:60, ASA:30, PBT:5, black masterbatch: 5；Antioxidant 1010 0.1 resists
Oxygen agent 168 0.1, lubricant 0.3, weather resisting agent 0.5
(2) PC resin, PBT resin, antioxidant and lubricant are added in mixing and blending machine and carry out mixing acquisition mixture
1, remaining ASA, weather resisting agent and black masterbatch are mixed by blender and obtain mixture 2；
(3) mixture 1 is fed by the main spout of double screw extruder, the 6th area cylinder that mixture 2 passes through extruder
The side feed mouth of body is fed；Barrel temperature is set as 200-240-260-260-260-240-240-250-260-260, and melting is squeezed
Out, it is granulated getting the product, weather-proof bloom is made and exempts to spray PC/ASA alloy material.
Embodiment 3
A kind of weather-proof bloom is exempted to spray PC/ASA alloy material and preparation method thereof, method includes the following steps:
(1) each component is weighed by weight: PC:60, ASA:20, PBT:15, black masterbatch: 5；Antioxidant 1010 0.1,
Irgasfos 168 0.1, lubricant 0.3, weather resisting agent 0.5
(2) PC resin, PBT resin, antioxidant and lubricant are added in mixing and blending machine and carry out mixing acquisition mixture
1, remaining ASA, weather resisting agent and black masterbatch are mixed by blender and obtain mixture 2；
(3) mixture 1 is fed by the main spout of double screw extruder, the 6th area cylinder that mixture 2 passes through extruder
The side feed mouth of body is fed；Barrel temperature is set as 200-240-260-260-260-240-240-250-260-260, and melting is squeezed
Out, it is granulated getting the product, weather-proof bloom is made and exempts to spray PC/ASA alloy material.
Comparative example 3
A kind of weather-proof bloom is exempted to spray PC/ASA alloy material and preparation method thereof, method includes the following steps:
(1) each component is weighed by weight: PC:60, ASA:30, PBT:5, black masterbatch: 5；Antioxidant 1010 0.1 resists
Oxygen agent 168 0.1, lubricant 0.3, weather resisting agent 0.5
(2) PC resin, PBT resin, antioxidant and lubricant are added in mixing and blending machine and carry out mixing acquisition mixture
1, remaining ASA, weather resisting agent and black masterbatch are mixed by blender and obtain mixture 2；
(3) mixture 1 is fed by the main spout of double screw extruder, the 6th area cylinder that mixture 2 passes through extruder
The side feed mouth of body is fed；Barrel temperature is set as 200-240-260-260-260-260-260-260-260-260, and melting is squeezed
Out, it is granulated getting the product, weather-proof bloom is made and exempts to spray PC/ASA alloy material.
Embodiment 4, implementation result
Before preparing batten, abundant drying particulate is prepared to place after batten and be tested afterwards for 24 hours.
It carries out injecting all kinds of test bars and bloom colour table using extra large day injection molding machine.
Izod impact strength is carried out according to ISO-180 standard, and temperature is 23 DEG C；
Vicat softening point is carried out according to ISO-306 standard, and the condition used is 5kg, and 50 DEG C/h
Ocular estimate is as follows: injection molding bloom colour table observes surface having a size of 100*100*3.With the color of Konica Minolta
Poor instrument surveys L value.L value is lower, illustrates that blackness is higher.
Weather-proof test is carried out according to PV1303,5 periods, evaluates color fastness.
1 Examples 1 to 3 of table and comparative example 1-3 product test result
Note: ★ more multilist presentation surface bloom effect is better.
As shown in Table 1, the alloy material of embodiment preparation has impact excellent, and surface bloom effect is good, weather-proof good, blackness
High effect, hence it is evident that better than the result of comparative example 1-3.And the resultant effect of embodiment 3 is best.
In conclusion the present invention improves the mobility of entire material by PBT, there is excellent copy mold ability；
By side feed ASA, weather resisting agent and black masterbatch, the temperature of side feed mouth is reduced, using viscosity than matching, dispersion is improved, obtains
Weather-proof bloom was obtained to exempt to spray PC/ASA alloy material.
There are many concrete application approach of the present invention, the above is only a preferred embodiment of the present invention.More than it should be pointed out that
Embodiment is merely to illustrate the present invention, and the protection scope being not intended to restrict the invention.For the common skill of the art
For art personnel, without departing from the principle of the present invention, several improvement can also be made, these improvement also should be regarded as this hair
Bright protection scope.
Claims (8)
1. a kind of weather-proof bloom is exempted to spray the preparation method of PC/ASA alloy material, which comprises the steps of:
S1, PC resin, PBT resin, antioxidant and lubricant are carried out to mixing acquisition mixture a, ASA, weather resisting agent and carbon black mother
Grain obtains mixture b by mixing；
S2, mixture a is fed by the main spout of double screw extruder, mixture b passes through the 6th area of double screw extruder
The side spout of cylinder is fed；
S3, melting extrusion are granulated and exempt to spray PC/ASA alloy material up to weather-proof bloom；
The 10 section barrel temperature of double screw extruder sets gradually as 200 DEG C, 240 DEG C, 260 DEG C, 260 DEG C, 260 DEG C, 240
DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 260 DEG C, double-screw extruder screw revolving speed be 500~800rpm；
The alloy material includes each component of following parts by weight:
2. weather-proof bloom according to claim 1 is exempted to spray the preparation method of PC/ASA alloy material, which is characterized in that institute
The relative molecular weight for stating PC resin is 10000~20000g/mol, and glass transition temperature is 140~150 DEG C.
3. weather-proof bloom according to claim 1 is exempted to spray the preparation method of PC/ASA alloy material, which is characterized in that institute
Stating ASA resin is Acrylate-styrene bipolymer-acrylonitrile composition graft copolymer, the weight percentage of acrylic rubber
For 40-75%.
4. weather-proof bloom according to claim 1 is exempted to spray the preparation method of PC/ASA alloy material, which is characterized in that institute
Intrinsic viscosity of the PBT resin stated when measuring ortho-chloro phenol solution for 25 DEG C is 0.45-1.20.
5. weather-proof bloom according to claim 1 is exempted to spray the preparation method of PC/ASA alloy material, which is characterized in that institute
The weather resisting agent stated includes the mixing of one or both of benzotriazole, triazine.
6. weather-proof bloom according to claim 1 is exempted to spray the preparation method of PC/ASA alloy material, which is characterized in that institute
Stating antioxidant is triethylene-glycol bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic esters], four [β-(3,5- bis- uncles
Butyl 4- hydroxy phenyl) propionic acid] pentaerythritol ester, three (2,4- di-tert-butyl-phenyl) phosphite esters, double stearyl alcohol seasons penta
The mixing of one or more of tetrol diphosphites.
7. weather-proof bloom according to claim 1 is exempted to spray the preparation method of PC/ASA alloy material, which is characterized in that institute
State lubricant be silane polymer, solid paraffin, atoleine, fatty acid salt, stearic amide, methylene bis stearic amide and
The mixing of one or more of N, N- ethylene bis stearic acid amide.
8. weather-proof bloom according to claim 1 is exempted to spray the preparation method of PC/ASA alloy material, which is characterized in that institute
Stating black masterbatch is the master batch that content of carbon black is 30-70%, and master batch carrier is PE wax.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111675892B (en) * | 2020-05-28 | 2022-12-23 | 嘉兴敏惠汽车零部件有限公司 | High-heat-resistance electroplating-free PC/ASA alloy material for automotive heat dissipation grating |
| CN112375366A (en) * | 2020-12-01 | 2021-02-19 | 上海中镭新材料科技有限公司 | Highlight spray-free ultra-black PC/ASA alloy material and preparation method thereof |
| CN112831170A (en) * | 2021-01-05 | 2021-05-25 | 上海中镭新材料科技有限公司 | Spraying-free matte PC/ASA alloy resin and preparation method thereof |
| CN113736268A (en) * | 2021-08-20 | 2021-12-03 | 贵州省材料产业技术研究院 | High-weather-resistance and high-cold-resistance highlight spraying-free PC/ASA material and preparation method thereof |
| CN116218186A (en) * | 2023-02-22 | 2023-06-06 | 金旸（厦门）新材料科技有限公司 | Piano black spraying-free PC/MS alloy material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532849A (en) * | 2011-12-26 | 2012-07-04 | 上海普利特复合材料股份有限公司 | PC/ASA/PBT (poly carbonate/ acrylonitrile-styrene-acrylate/polybutylene terephthalate) alloy material and preparation method thereof |
| CN103360670A (en) * | 2013-06-03 | 2013-10-23 | 广东波斯科技股份有限公司 | Universal high-gloss black masterbatch |
| CN105504753A (en) * | 2015-12-30 | 2016-04-20 | 上海普利特复合材料股份有限公司 | High-performance anti-ultraviolet PC/PBT/ASA (polycarbonate/polybutylene terephthalate/acrylonitrile-styrene-acrylate copolymer) composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532849A (en) * | 2011-12-26 | 2012-07-04 | 上海普利特复合材料股份有限公司 | PC/ASA/PBT (poly carbonate/ acrylonitrile-styrene-acrylate/polybutylene terephthalate) alloy material and preparation method thereof |
| CN103360670A (en) * | 2013-06-03 | 2013-10-23 | 广东波斯科技股份有限公司 | Universal high-gloss black masterbatch |
| CN105504753A (en) * | 2015-12-30 | 2016-04-20 | 上海普利特复合材料股份有限公司 | High-performance anti-ultraviolet PC/PBT/ASA (polycarbonate/polybutylene terephthalate/acrylonitrile-styrene-acrylate copolymer) composite material and preparation method thereof |
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