CN106674956B - A kind of weather-proof and excellent PC/ABS/LDPE alloy of mechanical performance and preparation method thereof - Google Patents
A kind of weather-proof and excellent PC/ABS/LDPE alloy of mechanical performance and preparation method thereof Download PDFInfo
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- CN106674956B CN106674956B CN201611144095.XA CN201611144095A CN106674956B CN 106674956 B CN106674956 B CN 106674956B CN 201611144095 A CN201611144095 A CN 201611144095A CN 106674956 B CN106674956 B CN 106674956B
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
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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
- C08L2205/03—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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- Health & Medical Sciences (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to polymeric material fields, specifically a kind of weather-proof and excellent PC/ABS/LDPE alloy of mechanical performance, it is made of following component by following parts by weight: 40~80 parts of PC, 10~30 parts of ABS, 5~30 parts of LDPE, 2~10 parts of toughener, 0.5~5 part of compatilizer, 0.1~1 part of lubricant, 0.1~1 part of antioxidant, 0.1~3 part of weather resisting agent.The present invention is promoted by weatherability aspect of the addition LDPE to PC/ABS, and passes through the use of EMA compatilizer, and the lamination in the case of effectivelying prevent high-content LDPE to add ensure that the impact property of material.
Description
Technical field
The present invention relates to polymeric material fields, specifically, being a kind of weather-proof and excellent PC/ABS/LDPE of mechanical performance
Alloy and preparation method thereof.
Background technique
Polycarbonate/styrene-butadiene-acrylonitrile has excellent mechanical property, heat resistance etc., is to be widely used
Engineering plastics.But in automobile exterior trimming parts application, the unsaturated double-bond that the butadiene in ABS has is easy by ultraviolet light
Irradiation and cause to be broken, so as to cause material jaundice and mechanical property decline.
Chinese patent literature CN102719077A discloses PC/ABS alloy composite and its preparation side of a kind of high durable
Method, the alloy composite include each component of following parts by weight: PC:40~80, ABS:10~50, compatilizer: 0.5~5,
Toughener: 2~10, antioxidant: 0.1~1, lubricant: 0.1~1, weather resisting agent: 0.1~3, weatherable master batch: 0.5~5.The patent
Document discloses the weatherable master batch that EMA-g-GMA and hindered amine are added in PC/ABS alloy, to improve the weatherability of PC/ABS
Energy.But the GMA contained in EMA-g-GMA can reduce the mobility of PC/ABS, so additive amount does not exceed 5%.To raising
The weather resistance of PC/ABS is very limited, so can not meet the performance requirement as exterior part.In addition, hindered amine is basic species
Matter can promote the degradation of PC, so hindered amine is not suitable for PC/ABS alloy system.
Summary of the invention
It is an object of the invention to overcome the weather-proof modified additive technology of traditional single utilization that outer exterior material application is not achieved to want
The defect asked, the additive amount for solving PE was more than 10% the phenomenon that will not generating layers of material, to reach good weather-proof effect
Fruit.
Under normal conditions, since PE and PC/ABS have very poor compatibility, it will lead to lamination, so PE is in PC/ABS
System in addition no more than 3%.Further, since the additive amount of PE is very little, there is significant limitation to the promotion of weatherability.
For the present invention through addition EMA/ compatilizer in PC/ABS/PE alloy (vinyl-acrylate copolymer 24MA009), it is proper to make
PE additive amount can achieve 20% or more in system, and does not have layering and impact the case where reducing.
The first aspect of the present invention provides a kind of weather-proof and excellent PC/ABS/LDPE alloy of mechanical performance, by following component
It is formed by following parts by weight:
Wherein,
The PC is that weight average molecular weight is 17, the bisphenol A polycarbonate of 000~30,000g/mol, vitrifying temperature
Degree is 145~150 DEG C.It is preferred that PC molecular weight is 23,000g/mol.Specific optional Supreme Being people, which is melted into, produces L-1225Y, Tao Shi PC-
PC 2600, PC 2400, the preferably PC-2600 of Cohan wound are created in 201-10, Hunan petrochemical industry PC-1100, PC-1220, Cohan.
The weight average molecular weight of the ABS is 80,000~150,000g/mol.Preferred molecular weight is 120,000g/mol
ABS material.
In the ABS, the weight percent content of rubber is 5~30%, and the weight percent content of acrylonitrile is 10
~30%, the weight percent content of styrene is 40~70%.The ABS of specific optional Korea Gumho Petrochemical Co., Ltd.
P/D150, ABS P/D190, ABS8391, ABS8434 of Gaoqiao Petrochemical Company and the GP-22 of benzene neck；It is preferred that the GP-22 of benzene neck.
The weight average molecular weight of the LDPE is the low density polyethylene (LDPE) of 80,000~1,000,000g/mol.It is preferred that molecule
The low density polyethylene (LDPE) that amount is 100,000.Specifically optional Yangtze petrochemical industry 1801 or 7042, Daqing petrochemical 7144, Ube
J5019.It is preferred that the J5019 of Ube.
The toughener be methyl methacrylate/butadiene/styrene copolymers (MBS), methyl methacrylate/
Acrylic polymer (ACR), acrylic compounds toughener, acrylic acid-silicone rubber kinds toughener, ethylene-methyl acrylate, second
Alkene-butyl acrylate, ethylene-acrylate-glycidyl methacrylate terpolymer or ethene-vinyl acetate copolymerization
Object-functionalization maleic anhydride.It is preferred that MBS.The partial size of the toughener is 50~700nm, and the glue content of the toughener is
40wt%~90wt%.
Specific EXL-2620, EXL-2330 that the M521, ROHM AND HAAS that originate in EM500, Zhong Yuan of LG can be selected；Wherein
EM500, M521, EXL-2620 are Methyl Methacrylate-Butadiene-Styrene Copolymer (MBS), and EXL-2330 belongs to first
Base methyl acrylate/acrylic polymer (ACR)；It is preferred that the EXL-2620 of ROHM AND HAAS.
The compatilizer is EMA.EMA is ethylene-methyl acrylate copolymer.Available compatilizer is Acker Ma
29MA003 and 24MA009, the preferably 24MA009 of Acker Ma.
The antioxidant is one or more of commercially available antioxidant 245, antioxidant 1076, irgasfos 168.It is preferred that
1076 and 168 are used in compounding.
The lubricant is one or more of silicone powder, pentaerythritol ester (PETS), ethylene bis stearic amide.It is excellent
Select pentaerythritol ester.
The weather resisting agent is benzotriazole, ultraviolet absorbing agent (UVP) or hindered amine light stabilizer (HALS).It is preferred that
Benzotriazole weather resisting agent.Specifically optional Basf Tinuvin327, Tinuvin328, Tinuvin324, Tinuvin234 and
Tinuvin770；It is preferred that the 234 of Basf.
The second aspect of the present invention provides above-mentioned weather-proof and the excellent PC/ABS/LDPE alloy of mechanical performance preparation method,
The following steps are included:
It weighs after material is placed in mixing machine and is sufficiently mixed, export is then placed in extruding pelletization in double screw extruder, controls
Screw speed processed be 180~600rpm/min, temperature be 180~260 DEG C to get arrive product.
Preferably, the double screw extruder includes 10 temperature controlled regions, and the temperature in 1st~2 area of temperature control is 180~260 DEG C,
The temperature in 3rd~4 area of temperature control is 180~260 DEG C, and the temperature in 5th~6 area of temperature control is 180~260 DEG C, and the temperature in 7th~8 area of temperature control is
180~260 DEG C, the temperature of temperature control 9~10 is 180~260 DEG C.
Preferably, the double screw extruder is set there are two place is vacuumized, and the end of material conveying section, melting are located at one
The beginning of section, another place's vaccum-pumping equipment are located at metering section.
The present invention is promoted by weatherability aspect of addition polyethylene (PE) to PC/ABS, and compatible by EMA
The use of agent, so that PE additive amount is even more than 10%, the layering that will not lead to the alloy material and impact property are sharply
It reduces.The PC/ABS/LDPE material finally prepared can use as exterior trim grid material and not need to spray.
The PC/ABS of conventional black is in SAE J2527 600kj/m2Weather resistant experiment in, Delt E has reached 4.0.This
The principle of invention is: selecting the LDPE of superelevation flowing, since LDPE itself has stable structure, has good uvioresistant
Effect；In addition, since the LDPE of superelevation flowing can be gathered in parts surface, and will form layer structure, so additive amount
When reaching 5%.It will can play the role of obvious uvioresistant；In addition, passing through the use of EMA compatilizer, further improve
Weather resistance and can effectively prevent high-content LDPE addition in the case of lamination, ensure that the impact property of material.
The present invention is this by especially modified PC/ABS/LDPE material, by 2500kj/m2Weather resistant experiment Delt E
Still there was only 2.2, and impact strength can achieve 48kj/m2, can satisfy public requirement, this material made
For outer exterior material.
Specific embodiment
It elaborates below with reference to embodiment to specific embodiment provided by the invention.
In the following examples, each raw material uses following compositions:
The PC of selection is the PC-2600 of Cohan wound；
The ABS of selection is the GP-22 of benzene neck；
The low density polyethylene (LDPE) of selection is the J5019 of Ube；
The toughener of selection is the EXL-2620 of ROHM AND HAAS；
The compatilizer of selection is the 29MA003 and 24MA009 of Acker Ma；
The antioxidant of selection is that the antioxidant 1076 and 168 of CIBA company production is used in compounding；
The weather resisting agent of selection is Basf Tinuvin234；
The lubricant of selection is pentaerythritol ester (PETS).
Embodiment 1
Raw material is weighed by component ratio in table 1, after being sufficiently mixed in mixing machine, export is then placed in twin-screw extrusion
Extruding pelletization in machine, control screw machine revolving speed be 200rpm, temperature be 225 DEG C to get arrive product.
Embodiment 2
Raw material is weighed by component ratio in table 1, after being sufficiently mixed in mixing machine, export is then placed in twin-screw extrusion
Extruding pelletization in machine, control screw machine revolving speed be 500rpm, temperature be 255 DEG C to get arrive product.
Embodiment 3
Raw material is weighed by component ratio in table 1, after being sufficiently mixed in mixing machine, export is then placed in twin-screw extrusion
Extruding pelletization in machine, control screw machine revolving speed be 400rpm, temperature be 260 DEG C to get arrive product.
Embodiment 4
Raw material is weighed by component ratio in table 1, after being sufficiently mixed in mixing machine, export is then placed in twin-screw extrusion
Extruding pelletization in machine, control screw machine revolving speed be 600rpm, temperature be 200 DEG C to get arrive product.
Embodiment 5
Raw material is weighed by component ratio in table 1, after being sufficiently mixed in mixing machine, export is then placed in twin-screw extrusion
Extruding pelletization in machine, control screw machine revolving speed be 300rpm, temperature be 225 DEG C to get arrive product.
Embodiment 6
Raw material is weighed by component ratio in table 1, after being sufficiently mixed in mixing machine, export is then placed in twin-screw extrusion
Extruding pelletization in machine, control screw machine revolving speed be 180rpm, temperature be 190 DEG C to get arrive product.
Embodiment 7
Raw material is weighed by component ratio in table 1, after being sufficiently mixed in mixing machine, export is then placed in twin-screw extrusion
Extruding pelletization in machine, control screw machine revolving speed be 300rpm, temperature be 180 DEG C to get arrive product.
The component and proportion of 1 embodiment 1-7 of table
The component and proportion of 2 comparative example 1-4 of table
Comparative example 1
Raw material is weighed by component ratio in table 2, after being sufficiently mixed in mixing machine, export is then placed in twin-screw extrusion
Extruding pelletization in machine, control screw machine revolving speed be 300rpm, temperature be 225 DEG C to get.
Comparative example 2
Raw material is weighed by component ratio in table 2, after being sufficiently mixed in mixing machine, export is then placed in twin-screw extrusion
Extruding pelletization in machine, control screw machine revolving speed be 300rpm, temperature be 225 DEG C to get.
Comparative example 3
Raw material is weighed by component ratio in table 2, after being sufficiently mixed in mixing machine, export is then placed in twin-screw extrusion
Extruding pelletization in machine, control screw machine revolving speed be 300rpm, temperature be 225 DEG C to get.
Comparative example 4
Raw material is weighed by component ratio in table 2, after being sufficiently mixed in mixing machine, export is then placed in twin-screw extrusion
Extruding pelletization in machine, control screw machine revolving speed be 300rpm, temperature be 225 DEG C to get.
The evaluation of implementation result
PC/ABS made from above-mentioned comparative example 1~4 and Examples 1 to 7 is carried out dependence test: melting is according to ISO 1133
It is tested；Density is according to ISO 1183；Bending strength is according to ISO 178；Simply supported beam notch impact strength is according to ISO 179；
Weather resistance is tested according to SAE J2527, and △ E is by 2500kj/m2Chromatism data after irradiation.Test result is as follows
Shown in table 3 and table 4:
The test result of 3 comparative example 1~4 of table
| Performance parameter | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Density (g/cm3) | 1.14 | 1.14 | 1.14 | 1.14 |
| Melt flow rate (MFR) (g/10min) | 18 | 14 | 14 | 12 |
| Bending strength (MPa) | 80 | 75 | 75 | 70 |
| 23 DEG C of simply supported beam notch impact strength (J/m) | 55 | 50 | 30 | 25 |
| △E | 10.5 | 9.2 | 8.8 | 8.0 |
The test result of 4 Examples 1 to 7 of table
After AX-8900 and 770D in comparative example 3 are made into master batch in advance, then add and squeezed out in other base-materials.
From the point of view of comparative example 1-4, although EMA-g-GMA and 770, which is added, can be improved weather resistance, due to containing
GMA functional group can greatly reduce the mobility of PC/ABS, so additive amount is no more than 5%, no this material of person does not have
Molding processibility.So the promotion to weatherability has certain limitation, it can not meet the weather resistance requirement of outer exterior material.
Comparative example 4 is compared with from the point of view of embodiment 1, the weather resistance for adding LDPE ratio EMA-g-GMA (AX-8900) is more excellent, this is
Because LDPE has good mobility, it is easier to be formed in material surface, and form sheet distribution after moulding
Form can play the left and right of barrier ultraviolet light line, ultraviolet light is avoided to lead to the discoloration of material to the destruction of butadiene in ABS
The reduction of transitivity.From the point of view of Examples 1 and 2, high flowing LDPE (J5019) is selected, bigger to the contribution of weather resistance, this is
Because low molecular material more readily migrates into material surface.From the point of view of embodiment 2~6, the additive amount of J5019 is improved, can be changed
Kind weather resistance；But additive amount is more than after 10%, since LDPE is incompatible with PC/ABS, so occur that impact reduces asks
Topic.But in embodiment 4~6, be added EMA (24MA009) can not only improve LDPE and PC/ABS compatibility (and then improve
Impact property), and can assist improving weather resistance.So embodiment 5 is Optimal system, Er Qieneng from the point of view of comprehensive performance
Meet public exterior trim material requirements.
The preferred embodiment of the present invention has been described in detail above, but the invention be not limited to it is described
Embodiment, those skilled in the art can also make various equivalent on the premise of not violating the inventive spirit of the present invention
Variation or replacement, these equivalent variation or replacement are all included in the scope defined by the claims of the present application.
Claims (7)
1. a kind of weather-proof and excellent PC/ABS/LDPE alloy of mechanical performance, which is characterized in that press following parts by weight by following component
Composition:
The weight average molecular weight of the LDPE is the linear low density polyethylene of 80,000~1,000,000g/mol；The increasing
Tough dose is methyl methacrylate/butadiene/styrene copolymers, methyl methacrylate/acrylic acid quasi polymer, propylene
Acid-silicone rubber kinds toughener, ethylene-butyl acrylate copolymer, ethylene-acrylate-glycidyl methacrylate three
Membered copolymer or ethylene-vinyl acetate copolymer-functionalization maleic anhydride；The compatilizer is EMA.
2. the according to claim 1 weather-proof and excellent PC/ABS/LDPE alloy of mechanical performance, which is characterized in that described
PC is that weight average molecular weight is 17, the bisphenol A polycarbonate of 000~30,000g/mol, and glass transition temperature is 145~150
℃。
3. the according to claim 1 weather-proof and excellent PC/ABS/LDPE alloy of mechanical performance, which is characterized in that described
The weight average molecular weight of ABS is 80,000~150,000g/mol；In the ABS, the weight percent content of rubber is 5~
30%, the weight percent content of acrylonitrile is 10~30%, and the weight percent content of styrene is 40~70%.
4. the according to claim 1 weather-proof and excellent PC/ABS/LDPE alloy of mechanical performance, which is characterized in that described
Antioxidant is one or more of commercially available antioxidant 245, antioxidant 1076, irgasfos 168.
5. the according to claim 1 weather-proof and excellent PC/ABS/LDPE alloy of mechanical performance, which is characterized in that described
Lubricant is one or more of silicone powder, pentaerythritol ester, ethylene bis stearic amide.
6. the according to claim 1 weather-proof and excellent PC/ABS/LDPE alloy of mechanical performance, which is characterized in that described
Weather resisting agent is benzotriazole or hindered amine light stabilizer.
7. a kind of preparation method of the excellent PC/ABS/LDPE alloy of weather-proof and mechanical performance as described in claim 1-6 is any,
Characterized by comprising the following steps: weighing after material is placed in mixing machine and is sufficiently mixed, export is then placed in twin-screw and squeezes
Extruding pelletization in machine out, control screw speed be 180~600rpm/min, temperature be 180~260 DEG C to get.
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| CN1243056C (en) * | 2002-10-18 | 2006-02-22 | 上海氯碱化工股份有限公司 | Cross blend material based on polycarbonate and its prepn. method |
| CN101787193B (en) * | 2009-10-20 | 2012-07-04 | 上海锦湖日丽塑料有限公司 | PC/ABS alloy with excellent hydrolysis resistance and preparation method thereof |
| CN102372913A (en) * | 2010-08-13 | 2012-03-14 | 上海锦湖日丽塑料有限公司 | Alloy having excellent weather resistance and preparation method thereof |
| CN103772953A (en) * | 2014-01-24 | 2014-05-07 | 南通红石科技发展有限公司 | Impact-resistant PC/ABS (Polycarbonate/Acrylonitrile Butadiene Styrene) alloy and preparation method thereof |
| CN105647149A (en) * | 2016-03-07 | 2016-06-08 | 苏州莱特复合材料有限公司 | PC alloy and preparation method thereof |
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Effective date of registration: 20180828 Address after: 200444 228 yuan Guang road, Baoshan District, Shanghai. Applicant after: SHANGHAI CHANGWEI JINCI ENGINEERING PLASTIC CO., LTD. Address before: 200444 3, 2 yuan 228, Garden Road, Baoshan District, Shanghai. Applicant before: SHANGHAI JIAYUAN BAILI INVESTMENT MANAGEMENT CO., LTD. |
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