CN107189301A - A kind of weather-proof PMMA AS plastic alloys and preparation method thereof - Google Patents
A kind of weather-proof PMMA AS plastic alloys and preparation method thereof Download PDFInfo
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- CN107189301A CN107189301A CN201710379109.4A CN201710379109A CN107189301A CN 107189301 A CN107189301 A CN 107189301A CN 201710379109 A CN201710379109 A CN 201710379109A CN 107189301 A CN107189301 A CN 107189301A
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- 229920003023 plastic Polymers 0.000 title claims abstract description 113
- 239000000956 alloy Substances 0.000 title claims abstract description 111
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 111
- 239000004033 plastic Substances 0.000 title claims abstract description 111
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 108
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 120
- 229920005989 resin Polymers 0.000 claims abstract description 120
- 239000012745 toughening agent Substances 0.000 claims abstract description 64
- 150000002148 esters Chemical class 0.000 claims abstract description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 239000004611 light stabiliser Substances 0.000 claims description 33
- 238000012360 testing method Methods 0.000 claims description 32
- 239000003963 antioxidant agent Substances 0.000 claims description 27
- 230000003078 antioxidant effect Effects 0.000 claims description 27
- 239000000049 pigment Substances 0.000 claims description 23
- 239000000314 lubricant Substances 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 12
- 239000011258 core-shell material Substances 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 9
- -1 acrylic ester Chemical class 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000005491 wire drawing Methods 0.000 claims description 5
- 229920006397 acrylic thermoplastic Polymers 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035939 shock Effects 0.000 abstract description 11
- 230000003014 reinforcing effect Effects 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 18
- 238000005452 bending Methods 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 15
- 238000010998 test method Methods 0.000 description 14
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 11
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- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000001046 green dye Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 206010021703 Indifference Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001657948 Midea Species 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920012128 methyl methacrylate acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of weather-proof PMMA AS plastic alloys and preparation method thereof.A kind of weather-proof PMMA AS plastic alloys, by weight including following components：40~60 parts of PMMA resins, 20~40 parts of AS resins, 10~40 parts of toughener, 1~3 part of additive.Also disclose that a kind of preparation method of weather-proof PMMA AS plastic alloys simultaneously.The present invention is using HI high impact PMMA resins and the general PMMA resins of esters of acrylic acid toughener toughness reinforcing for not containing double bond, have prominent weatherability concurrently again while shock resistance is significantly improved, and with fabulous gloss and hardness, it is adaptable to automobile, household electrical appliances and other field.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of weather-proof PMMA-AS plastic alloys and its preparation
Method.
Background technology
PMMA resins (polymethyl methacrylate) are a kind of common engineering plastics, with the fabulous transparency, prominent
Weatherability, chemical stability and the advantages of high case hardness, be widely used in the fields such as automobile, household electrical appliances, building, space flight.
But compared with other transparent resins (such as PC), the shock resistance of PMMA resins is poor, this just makes its application receive greatly
Ground is limited.
In order to improve the shortcoming of PMMA shock resistances difference, generally solved at this stage using the method for addition toughener.
Such as patent CN105733153A of Hefei Hualing Co., Ltd. and Midea Group Co., Ltd.'s joint application, according to
The method that the patent is provided, using 30~35 parts SBS, MBS or MABS come toughened polymethyl methacrylate (PMMA) resin, final impact strength is reachable
10~15KJ/m2.Such as patent CN101475727A of Shanghai Kumbosunny Plastics CO.,LTD's application, is carried according to the patent again
The method of confession, using 30~70 parts of ABS or MBS come toughened polymethyl methacrylate (PMMA) resin, final impact strength is up to 5~15KJ/m2。
The impact that the method for above-mentioned use MBS, SBS or ABS toughened polymethyl methacrylate (PMMA) resin all drastically increases PMMA resins is strong
Degree, but above-mentioned toughener all contains carbon-carbon double bond, which results in the easy aging of the plastic alloy finally given, so as to limit
Use scope.
Such as patent CN105885320A of Shanghai Kumbosunny Plastics CO.,LTD's application, is provided according to the patent again
Method, using esters of acrylic acid toughener and PVAC toughened polymethyl methacrylate (PMMA) resins, although the impact property of final PMMA resins on
Rise, but still requirement can not be met, also the patent does not consider the very important performance such as its weather-proof, hardness, illustrates final modeling
Material alloy can not accomplish the balance of various aspects of performance.
The content of the invention
It is an object of the invention to provide a kind of weather-proof PMMA-AS plastic alloys and preparation method thereof.
The technical solution used in the present invention is：
A kind of weather-proof PMMA-AS plastic alloys, by weight including following components：40~60 parts of PMMA resins, 20~40
Part AS resins, 10~40 parts of toughener, 1~3 part of additive.
Described PMMA resins include 30~50 parts of general PMMA resins and 10~30 parts of HI high impact PMMA trees by weight
Fat.
It is (10~30) g/ under 230 DEG C, 3.8Kg test conditions that described general PMMA resin melts, which flow speed,
10min, Izod notched impact strength is (1.8~4.0) KJ/m2。
It is (2~6) g/ under 230 DEG C, 3.8Kg test conditions that described HI high impact PMMA resin melts, which flow speed,
10min, Izod notched impact strength is (5.0~10.0) KJ/m2。
The melt flow rate (MFR) of described AS resins is (20~60) g/10min under 220 DEG C, 10Kg test conditions.
Described toughener is the esters of acrylic acid toughener of core shell structure.
In the esters of acrylic acid toughener of the core shell structure, core is the polymer of acrylic ester monomer, and shell is (first
Base) acrylics monomer and styrene monomer or vinyl nitrile monomer homopolymer or copolymer.
The refraction index of the esters of acrylic acid toughener of the core shell structure is 1.47~1.51.
Described additive includes antioxidant, light stabilizer, lubricant and pigment.
A kind of preparation method of weather-proof PMMA-AS plastic alloys, comprises the following steps：
1) PMMA resins and AS resins are dried；
2) step 1) obtained by PMMA resins and AS resins, weigh original by above-mentioned composition with toughener and additive
Material, is mixed；
3) by step 2) obtained by compound melt blending, extrusion wire drawing and pelletizing, obtain weather-proof PMMA-AS plastics and close
Gold.
The beneficial effects of the invention are as follows：
The present invention is using HI high impact PMMA resins and the general PMMA trees of esters of acrylic acid toughener toughness reinforcing for not containing double bond
Fat, has prominent weatherability concurrently again while shock resistance is significantly improved, and with fabulous gloss and hardness, fits
For automobile, household electrical appliances and other field.
It is specific as follows：
1. the general PMMA resins of esters of acrylic acid toughener toughness reinforcing for not containing double bond are used, and the refractive power of the toughener
Index is close or consistent with PMMA resins, while general PMMA resins shock resistance is greatly improved, it is ensured that the modeling of preparation
Expect that alloy has prominent weatherability, there is fabulous glossiness again.
2. using the HI high impact PMMA resins collaboration general PMMA resins of esters of acrylic acid toughener toughness reinforcing, on the one hand reduce
The consumption of esters of acrylic acid toughener, reduces cost, is on the other hand also beneficial to the raising of plastic alloy glossiness.
3. a certain amount of AS resins of addition, not only reduce the cost of plastic alloy, it is often more important that greatly improve modeling
Expect the processing fluidity of alloy, the plastic alloy can be used to prepare larger plastic part.
4. the need for difference, adding the pigment of different proportion, the plastic alloy can be dyed to different colours (especially
It is the black effect of bloom), it can be widely applied for the fields such as automobile exterior trimming parts (such as air-inlet grille), appliance shell, engineering works.
In addition, the preparation method that the present invention is provided is very simple, raw material is easy to get, suitable large-scale industrial production.
Embodiment
The present inventor passes through systematic research, finds using HI high impact PMMA resins and not double bond containing esters of acrylic acid increases
Tough dose is carried out the general PMMA resins of toughness reinforcing, and while general PMMA resins shock resistance is improved, PMMA resins can be retained again
Original weatherability, this has just greatly widened the application of PMMA resins, while adjusting HI high impact PMMA resins and propylene
The consumption of esters of gallic acid toughener can obtain the plastic alloy that various performances are balanced very much.
In the application of PMMA resins, in addition to needing emphasis and considering its shock resistance, in addition it is also necessary to emphasis consider be
Use cost, the performance such as the transparency, the hardness of AS resins is close to PMMA resins, and cost is far below PMMA resins, flowing
Property be far above PMMA resins, therefore be usually added into a certain amount of AS resins in actual applications instead of part PMMA resins so that
Use cost is greatly reduced, while improving processing fluidity.
A kind of weather-proof PMMA-AS plastic alloys, by weight including following components：40~60 parts of PMMA resins, 20~40
Part AS resins, 10~40 parts of toughener, 1~3 part of additive.
Described PMMA resins include 30~50 parts of general PMMA resins and 10~30 parts of HI high impact PMMA trees by weight
Fat.
It is preferred that, described general PMMA resin melts flow speed under 230 DEG C, 3.8Kg test conditions for (10~
30) g/10min, Izod notched impact strength is (1.8~4.0) KJ/m2, Rockwell hardness is more than 80.
It is preferred that, described HI high impact PMMA resin melts flow speed under 230 DEG C, 3.8Kg test conditions for (2~
6) g/10min, Izod notched impact strength is (5.0~10.0) KJ/m2, Rockwell hardness is more than 50.
Described AS resins are acrylonitrile AN and styrene St copolymer, it is preferred that AN content is many in AS resins
In 20%, its melt flow rate (MFR) is (20~60) g/10min under 220 DEG C, 10Kg test conditions, and Rockwell hardness is more than 80.
It is preferred that, described toughener is the esters of acrylic acid toughener of core shell structure；It is further preferred that the nucleocapsid
In the esters of acrylic acid toughener of structure, core is the polymer of acrylic ester monomer, and shell is (methyl) acrylics monomer
With styrene monomer or the homopolymer or copolymer of vinyl nitrile monomer.
It is preferred that, the refraction index of the esters of acrylic acid toughener of the core shell structure is 1.47~1.51, the toughener
Refraction index it is consistent with PMMA resins.
Described additive includes antioxidant, light stabilizer, lubricant and pigment.
It is preferred that, described antioxidant is at least one of Hinered phenols, phosphite ester kind antioxidant；Further preferably
, described antioxidant is irgasfos 168,264,1010,1076, at least one of 1098；Still further preferably, it is described
Antioxidant be antioxidant 1010 and irgasfos 168 with mass ratio 1:The compound antioxidant of 1 composition.
It is preferred that, described light stabilizer be in benzophenone, benzotriazole, hindered amine light stabilizer at least
It is a kind of；It is further preferred that described light stabilizer is at least one of UV-531, UV-9, UV-326, UV-P, UV-770；
Still further preferably, described light stabilizer is UV-P and UV-770 with mass ratio 1:The compounding light stabilizer of 1 composition.
It is preferred that, described lubricant is Tissuemat E, the double stearic acid of stearic acid, stearate, fatty acid amide, ethylene
At least one of acid amides；It is further preferred that described lubricant is Tissuemat E, zinc stearate, calcium stearate, stearic acid
At least one of magnesium, fatty acid amide；Still further preferably, described lubricant is Tissuemat E or calcium stearate.
Described pigment is the dyestuff that the art is commonly used, it is preferred that for transparent scarlet dye, 5B green dyes, purple orchid
At least one of dyestuff, transparent yellow dye and carbon black.But this is not limited only to, material can be dyed to different face as needed
Color, the black plastic alloy of bloom can be obtained by adding these pigment according to different ratios.
A kind of preparation method of weather-proof PMMA-AS plastic alloys, comprises the following steps：
1) PMMA resins and AS resins are dried；
2) step 1) obtained by PMMA resins and AS resins, weigh original by above-mentioned composition with toughener and additive
Material, is mixed；
3) by step 2) obtained by compound melt blending, extrusion wire drawing and pelletizing, obtain weather-proof PMMA-AS plastics and close
Gold.
It is preferred that, step 1) described in drying temperature be 80~100 DEG C, 2~5h of drying time.
It is preferred that, step 3) described in compound in an extruder melt blending, extrude wire drawing, wherein extruder screw rod
Rotating speed is (100~600) r/min, and extrusion temperature is 200~260 DEG C, and vacuum during extrusion is -0.06~-0.1MPa.
In the present invention, the purpose of addition HI high impact PMMA resins is the collaboration general PMMA trees of esters of acrylic acid toughener toughness reinforcing
Fat, it is possible to reduce the consumption of esters of acrylic acid toughener, this is conducive to the glossiness of plastic alloy, can prepare the black plastics of bloom
Alloy.The main purpose of addition AS resins is to improve the melt flow rate (MFR) of plastic alloy, beneficial to processing, while also functioning to reduction
The use cost of PMMA resins.From refraction index and PMMA resin identical esters of acrylic acid toughener, it is ensured that plastics
The glossiness of alloy, this black effect of bloom for being also beneficial to plastic alloy, while the esters of acrylic acid toughener does not contain carbon carbon
Double bond, therefore the plastic alloy finally given has prominent weatherability.
Present disclosure is described in further detail below by way of specific embodiment.
According to a kind of weather-proof PMMA-AS plastic alloys of the present invention, the consumption of PMMA resins is 40~60 parts.Wherein
General PMMA resin demands are 30~50 parts, can select PMMA CM207, the PMMA CM211 of Qi Mei companies or other are commercially available
General PMMA products；HI high impact PMMA resin demands are 10~30 parts, can select LG chemistry PMMA HI855H, French Ah
The PMMA DR101 of Kerma (unit of kinetic energy) or other commercially available HI high impact PMMA products.
According to a kind of weather-proof PMMA-AS plastic alloys of the present invention, the consumption of AS resins is 20~40 parts.Described
AS resins can select the AS PN-108L125 or other commercially available AS products of AS 80HF, Qi Mei companies of Tianjin Dagu chemical industry.
According to a kind of weather-proof PMMA-AS plastic alloys of the present invention, the consumption of esters of acrylic acid toughener for 10~
40 parts, preferably 15~30 parts, when the consumption of esters of acrylic acid toughener is less than 15 parts, the shock resistance of plastic alloy is not
It can meet and require, when the consumption of esters of acrylic acid toughener is higher than 30 parts, the shock resistance change of plastic alloy is little, but
Hardness, gloss etc. can be a greater impact, while cost increase.Esters of acrylic acid toughener used is the acrylic acid of core shell structure
In esters toughener, the esters of acrylic acid toughener of the core shell structure, core is the polymer of acrylic ester monomer, and shell is
(methyl) acrylics monomer and styrene monomer or the homopolymer or copolymer of vinyl nitrile monomer.Described propylene
Esters of gallic acid toughener can select the M210 or other commercially available similar products of the deep chemical industry of Japanese clock.
According to a kind of weather-proof PMMA-AS plastic alloys of the present invention, antioxidant, light stabilizer, lubricant quantity are equal
For for 0.1~1 part, preferably 0.2~0.5 part, described antioxidant, light stabilizer and lubricant is commercially available prod；Pigment
Consumption be preferably 0.1~1 part, when amount of pigment be less than 0.1 part when, plastic alloy does not reach bloom effect, works as amount of pigment
During higher than 1 part, the surface pit of plastic alloy increases, influence bloom effect, described pigment can select transparent scarlet dye,
The one or more of the blue dyestuff of 5B green dyes, purple, transparent yellow dye and carbon black.
A kind of weather-proof PMMA-AS plastic alloys prepared are subjected to performance test, analysis method is as follows：
Obtained plastic alloy is molded into batten and colour table using injection machine, injection temperature is 230~260 DEG C.
The weather resistance of A plastic alloys
Obtained colour table will be molded and carry out light aging resisting test according to GB/T 16422.1-2006 experimental method.
The impact property of B plastic alloys
Obtained impact batten will be molded and carry out Chalpy impact experiment according to GB/T1842-2008 experimental method.It is real
Test instrument：Mei Site industrial systems (China) Co., Ltd Charpy impact machine tester.
The tensile property of C plastic alloys
Obtained tensile bars will be molded and carry out tension test according to GB/T1040.2-2006 experimental method.Experiment instrument
Device：Mei Site industrial systems (China) Co., Ltd microcomputer controlled electronic universal tester.
The bending property of D plastic alloys
Obtained bending batten will be molded and carry out bend test according to GB/T9341-2008 experimental method.Laboratory apparatus：
Mei Site industrial systems (China) Co., Ltd microcomputer controlled electronic universal tester.
The melt flow rate (MFR) of E plastic alloys
Experimental method by plastic alloy particle according to GB/3682-2000 carries out melt flow rate (MFR) experiment.Experiment instrument
Device：Mei Site industrial systems (China) Co., Ltd melt flow rate (MFR) testing machine.
The Rockwell hardness of F plastic alloys
Obtained colour table will be molded and carry out hardness test according to GB/T3398.2-2008 experimental method.Laboratory apparatus：On
Hai Lianer testing equipments Co., Ltd XHR-150 plastic Rockwell apparatuses.
The glossiness of G plastic alloys
Obtained colour table will be molded and carry out brilliance test according to GB/T8807-1988 experimental method.Laboratory apparatus：
KONICA MINOLTA companies vancometer.
The present invention is described in further detail for following embodiments and comparative example, but it is to be noted that these realities
Limitation of the scope of the invention should be counted as in no instance by applying example and comparative example.
Embodiment 1：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：60 parts of PMMA resins CM207,20 parts
AS resins PN-108L125,20 parts of toughener M210,0.1 part of lubricant PE wax, 0.2 part of antioxidant 1010,0.2 part of antioxidant
168,0.22 parts of light stabilizers UV-P, 0.22 part of light stabilizer UV-770,0.7 part of pigment.
Step one：By PMMA resins and AS resins be placed in baking oven dry, oven temperature be 80~100 DEG C, the time be 2~
5h。
Step 2：PMMA resins in step one, AS resins, toughener and various additives are pressed into certain parts by weight
Add high speed agitator to stir, mixing time is 5min.
Step 3：The material mixed in step 2 is subjected to melt blending, extrusion wire drawing and pelletizing by extruder
Described weather-proof PMMA-AS plastic alloys are obtained, the screw speed of extruder is 500 revs/min, vacuum during blending extrusion
For -0.08MPa.Extrusion temperature is：One area's temperature is 220 DEG C, and two area's temperature are 230 DEG C, and three area's temperature are 230 DEG C, four area's temperature
Spend for 240 DEG C, five area's temperature are 240 DEG C, six area's temperature are 240 DEG C, seven area's temperature are 240 DEG C, eight area's temperature are 250 DEG C, nine
Area's temperature is 250 DEG C, and ten area's temperature are 250 DEG C.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Embodiment 2：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：60 parts of PMMA resins CM207,20 parts
AS resins PN-108L125,20 parts of toughener MBS 2388 (DOW Chemical MBS classes toughener), 0.1 part of lubricant PE wax, 0.2
Part antioxidant 1010,0.2 part of irgasfos 168,0.22 part of light stabilizer UV-P, 0.22 part of light stabilizer UV-770,0.7 part of face
Material.
The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Embodiment 3：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：60 parts of PMMA resins CM207,20 parts
AS resins PN-108L125,20 parts of toughener S2001 (the beautiful positive esters of acrylic acid toughener of Mitsubishi), 0.1 part of lubricant PE wax,
0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.22 part of light stabilizer UV-P, 0.22 part of light stabilizer UV-770,0.7 part
Pigment.
The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Embodiment 4：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：50 parts of PMMA resins CM207,10 parts
PMMA resins HI855H, 20 parts of AS resins PN-108L125,20 parts of toughener M210,0.1 part of lubricant PE wax, 0.2 part of antioxygen
1010,0.2 part of irgasfos 168 of agent, 0.22 part of light stabilizer UV-P, 0.22 part of light stabilizer UV-770,0.7 part of pigment.
The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Embodiment 5：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：30 parts of PMMA resins CM207,30 parts
PMMA resins HI855H, 20 parts of AS resins PN-108L125,20 parts of toughener M210,0.1 part of lubricant PE wax, 0.2 part of antioxygen
1010,0.2 part of irgasfos 168 of agent, 0.22 part of light stabilizer UV-P, 0.22 part of light stabilizer UV-770,0.7 part of pigment.
The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Embodiment 6：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：70 parts of PMMA resins CM207,20 parts
AS resins PN-108L125,10 parts of toughener M210,0.1 part of lubricant PE wax, 0.2 part of antioxidant 1010,0.2 part of antioxidant
168,0.22 parts of light stabilizers UV-P, 0.22 part of light stabilizer UV-770,0.7 part of pigment.
The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Embodiment 7：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：40 parts of PMMA resins CM207,20 parts
AS resins PN-108L125,40 parts of toughener M210,0.1 part of lubricant PE wax, 0.2 part of antioxidant 1010,0.2 part of antioxidant
168,0.22 parts of light stabilizers UV-P, 0.22 part of light stabilizer UV-770,0.7 part of pigment.
The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Embodiment 8：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：40 parts of PMMA resins CM207,20 parts
PMMA resins HI855H, 20 parts of AS resins PN-108L125,20 parts of toughener M210,0.1 part of lubricant PE wax, 0.2 part of antioxygen
1010,0.2 part of irgasfos 168 of agent, 0.22 part of light stabilizer UV-P, 0.22 part of light stabilizer UV-770,0.7 part of pigment.
The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Comparative example 1：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：60 parts of PMMA resins CM207,20 parts
AS resins PN-108L125,20 parts of toughener M210,0.1 part of lubricant PE wax, 0.2 part of antioxidant 1010,0.2 part of antioxidant
168,0.7 parts of pigment.
The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Comparative example 2：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：60 parts of PMMA resins CM207,20 parts
AS resins 2388,0.1 part of lubricant PE wax of PN-108L125,20 parts of toughener MBS, 0.2 part of antioxidant 1010,0.2 part of antioxygen
168,0.7 part of pigment of agent.
The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Comparative example 3：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：60 parts of PMMA resins CM207,20 parts
AS resins PN-108L125,20 parts of toughener S2001,0.1 part of lubricant PE wax, 0.2 part of antioxidant 1010,0.2 part of antioxidant
168,0.7 parts of pigment.
The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Comparative example 4：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：80 parts of PMMA resins CM207,20 parts
Toughener M210,0.1 part of lubricant PE wax, 0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.22 part of light stabilizer UV-P,
0.22 part of light stabilizer UV-770,0.7 part of pigment.
The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Comparative example 5：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：20 parts of PMMA resins CM207,60 parts
AS resins PN-108L125,20 parts of toughener M210,0.1 part of lubricant PE wax, 0.2 part of antioxidant 1010,0.2 part of antioxidant
168,0.22 parts of light stabilizers UV-P, 0.22 part of light stabilizer UV-770,0.7 part of pigment.
The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
Comparative example 6：
A kind of weather-proof PMMA-AS plastic alloys, are made up of the component of following parts by weight：60 parts of PMMA resins CM207,40 parts
PMMA resins HI855H, 0.1 part of lubricant PE wax, 0.2 part of antioxidant 1010,0.2 part of irgasfos 168,0.22 part of light stabilizer
UV-P, 0.22 part of light stabilizer UV-770,0.7 part of pigment.The preparation method of plastic alloy is same as Example 1.
Obtained plastic alloy is carried out to weather-proof, stretching, bending, impact, melt flow respectively according to above-mentioned method of testing
Dynamic speed, Rockwell hardness, glossiness test, measured physical property result such as Tables 1 and 2.
The plastic alloy xenon lamp aging test result (1300h) of table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| ΔL | -0.21 | -0.27 | -0.25 | -0.72 | -1.98 | -0.74 |
| Δa | -0.05 | -0.03 | -0.03 | -0.02 | -0.75 | -0.05 |
| Δb | 0.08 | -0.53 | 0.08 | 0.15 | -4.64 | 0.21 |
| ΔE | 0.25 | 0.60 | 0.26 | 0.74 | 5.10 | 0.77 |
The embodiment 1~3 in table 1, has using the obtained plastic alloys of esters of acrylic acid toughener toughened polymethyl methacrylate (PMMA)-AS
There is more prominent weatherability.It is can be seen that simultaneously from comparative example 1~3 when being added without light stabilizer, by esters of acrylic acid toughness reinforcing
Resulting plastic alloy still has excellent weatherability, and weather-proof by the plastic alloy obtained by MBS class toughener toughness reinforcings
Impatient acute decline.
Every physical property measurement result of the plastic alloy of table 2
The embodiment 1~3 in table 2, utilizes the modeling obtained by esters of acrylic acid toughener and MBS class toughener toughness reinforcings
The every mechanical properties of material alloy have no essential distinction, but have higher glossiness as the plastic alloy obtained by M210 toughness reinforcings,
This be due to M210 toughener refraction index it is consistent with PMMA resins.It can be seen by embodiment 1, embodiment 4 and embodiment 5
Go out, after HI high impact PMMA resins are added, the shock resistance of plastic alloy is substantially improved, but excessive add can cause plastics
Intensity, the hardness of alloy are strongly reduced, while mobility can also decline.
Embodiment 1, embodiment 6 and embodiment 7 in table 2, the anti-impact when M210 toughener consumptions are reduced to 10 parts
Hit performance degradation, and shock resistance is simply somewhat lifted when consumption increases to 40 parts, but rigidity and hardness but by
To extreme influence.
Embodiment 1, comparative example 4 and comparative example 5 in table 2, the resulting plastic alloy when being added without AS resins
Mechanical property and indifference, but mobility is slightly worse, when adding substantial amounts of AS resins, although the mobility of plastic alloy is very
It is good, but glossiness meeting degradation, therefore, consider from performance and use cost, appropriate AS resins should be added.From
Comparative example 6 is understood, only uses the general PMMA resins of HI high impact PMMA resin toughenings, and toughening effect is not very good, is flowed simultaneously
Property and hardness decline to a great extent, and other performances can also decline therewith.
The embodiment 8 in table 2 by adding a certain amount of HI high impact PMMA resins and refraction index is 1.49 ±
0.02 esters of acrylic acid toughener, adding appropriate AS resins improves mobility, and the plastic alloy finally given has prominent
Weatherability, excellent impact resistance, fabulous gloss, good hardness and other mechanical performances gone out, while processing fluidity
It is very good, therefore the various aspects of performance of the plastic alloy has obtained good balance.
For above-mentioned the disclosed embodiments and comparative example, purpose enables professional and technical personnel in the field to realize or use
The present invention.A variety of modifications to these above-mentioned embodiments and comparative example will be aobvious and easy for those skilled in the art
See, generic principles defined herein can without departing from the spirit or scope of the present invention, in other embodiments
It is middle to realize.Therefore, the present invention is not intended to be limited to the embodiments shown herein and comparative example, and is to fit to and this paper
The disclosed principle most wide scope consistent with features of novelty.
Claims (10)
1. a kind of weather-proof PMMA-AS plastic alloys, it is characterised in that：Include following components by weight：40~60 parts of PMMA trees
Fat, 20~40 parts of AS resins, 10~40 parts of toughener, 1~3 part of additive.
2. a kind of weather-proof PMMA-AS plastic alloys according to claim 1, it is characterised in that：PMMA resins are by weight
Including 30~50 parts of general PMMA resins and 10~30 parts of HI high impact PMMA resins.
3. a kind of weather-proof PMMA-AS plastic alloys according to claim 2, it is characterised in that：General PMMA resin melts
Flow rate under 230 DEG C, 3.8Kg test conditions be (10~30) g/10min, Izod notched impact strength for (1.8~
4.0)KJ/m2。
4. a kind of weather-proof PMMA-AS plastic alloys according to claim 2, it is characterised in that：HI high impact PMMA resins melt
Body flow rate under 230 DEG C, 3.8Kg test conditions be (2~6) g/10min, Izod notched impact strength for (5.0~
10.0)KJ/m2。
5. a kind of weather-proof PMMA-AS plastic alloys according to claim 1, it is characterised in that：The melt flows of AS resins
Speed is (20~60) g/10min under 220 DEG C, 10Kg test conditions.
6. a kind of weather-proof PMMA-AS plastic alloys according to claim 1, it is characterised in that：Toughener is core shell structure
Esters of acrylic acid toughener.
7. a kind of weather-proof PMMA-AS plastic alloys according to claim 6, it is characterised in that：The acrylic acid of core shell structure
In esters toughener, core is the polymer of acrylic ester monomer, and shell is (methyl) acrylics monomer and phenylethylene list
The homopolymer or copolymer of body or vinyl nitrile monomer.
8. a kind of weather-proof PMMA-AS plastic alloys according to claim 7, it is characterised in that：The acrylic acid of core shell structure
The refraction index of esters toughener is 1.47~1.51.
9. a kind of weather-proof PMMA-AS plastic alloys according to claim 1, it is characterised in that：Additive include antioxidant,
Light stabilizer, lubricant and pigment.
10. a kind of preparation method of weather-proof PMMA-AS plastic alloys, it is characterised in that：Comprise the following steps：
1) PMMA resins and AS resins are dried；
2) step 1) obtained by PMMA resins and AS resins, with toughener and additive as described in any one of claim 1~9
Composition weigh raw material, mix；
3) by step 2) obtained by compound melt blending, extrusion wire drawing and pelletizing, obtain weather-proof PMMA-AS plastic alloys.
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| CN111574798A (en) * | 2019-12-25 | 2020-08-25 | 重庆会通科技有限公司 | Modified PMMA-AS alloy material and preparation method thereof |
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| CN115572449A (en) * | 2022-09-30 | 2023-01-06 | 成都金发科技新材料有限公司 | Ultraviolet-resistant and high-toughness PMMA (polymethyl methacrylate) composition as well as preparation method and application thereof |
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Address after: 528322 Guangdong City, Shunde District Leliu street even Du Tian Ren Ren Industrial Park (self) plant No. 10 Applicant after: Guangdong harmony new materials Co. Ltd. Address before: 528322 No. 10 factory building of Tian Ren Industrial Park (DU Gang) in Leliu village, Leliu Town, Foshan City, Guangdong Province Applicant before: Guangdong harmony new materials Co. Ltd. |
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| CB02 | Change of applicant information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Canyao Inventor after: Zhu Fupeng Inventor after: Yu Haiou Inventor after: Yi Qingfeng Inventor after: Fang Anping Inventor before: Wang Canyao Inventor before: Zhu Fupeng Inventor before: Yu Haiou Inventor before: Yi Qingfeng Inventor before: He Jihui Inventor before: Fang Anping |
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| CB03 | Change of inventor or designer information | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
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Address after: 528300 Longchuang Road, Malong Village Committee, Beijiao Town, Shunde District, Foshan City, Guangdong Province Applicant after: Guangdong harmony new materials Co. Ltd. Address before: 528322 No. 10 Factory Building of Tianren Industrial Park, Liandu Village, Leliu Street, Shunde District, Foshan City, Guangdong Province Applicant before: Guangdong harmony new materials Co. Ltd. |
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| CB02 | Change of applicant information | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhu Fupeng Inventor after: Fang Anping Inventor before: Wang Canyao Inventor before: Zhu Fupeng Inventor before: Yu Haiou Inventor before: Yi Qingfeng Inventor before: Fang Anping |
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| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20191220 |
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| AD01 | Patent right deemed abandoned |