CN116535794A - High-impact-strength glass fiber reinforced PMMA/ABS resin and preparation method and application thereof - Google Patents
High-impact-strength glass fiber reinforced PMMA/ABS resin and preparation method and application thereof Download PDFInfo
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- CN116535794A CN116535794A CN202310451942.0A CN202310451942A CN116535794A CN 116535794 A CN116535794 A CN 116535794A CN 202310451942 A CN202310451942 A CN 202310451942A CN 116535794 A CN116535794 A CN 116535794A
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 55
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 54
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 54
- 239000003365 glass fiber Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 57
- 239000012745 toughening agent Substances 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 238000012360 testing method Methods 0.000 claims description 11
- 150000002148 esters Chemical group 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 abstract description 37
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 abstract description 37
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- -1 pentaerythritol ester Chemical class 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 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 3
- DEAKWVKQKRNPHF-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 DEAKWVKQKRNPHF-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- DMHHYBUEZRZGDK-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanamide Chemical compound NC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DMHHYBUEZRZGDK-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- GYOZZWNPRKAISG-UHFFFAOYSA-N P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(O)(C(CO)(CO)CO)C1=CC(=C(C(=C1)C(C)(C)C)C)C(C)(C)C)C(C)(C)C)C Chemical compound P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(O)(C(CO)(CO)CO)C1=CC(=C(C(=C1)C(C)(C)C)C)C(C)(C)C)C(C)(C)C)C GYOZZWNPRKAISG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical group C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical compound C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- QYVZEPLDLPYECM-XUTLUUPISA-N octadecyl (e)-3-(3,4-dihydroxyphenyl)prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)\C=C\C1=CC=C(O)C(O)=C1 QYVZEPLDLPYECM-XUTLUUPISA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use 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; Derivatives of such polymers
- C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-impact-strength glass fiber reinforced PMMA/ABS composite material, and a preparation method and application thereof. The high-impact-strength glass fiber reinforced PMMA/ABS composite material comprises the following components in parts by weight: 30-70 parts of polymethyl methacrylate PMMA; 10-40 parts of acrylonitrile-butadiene-styrene terpolymer ABS; 10-45 parts of toughening agent; 10-30 parts of glass fiber; 0.1 to 4.0 parts of lubricant; 0.1 to 0.5 part of antioxidant; 1.0 to 5.0 portions of dispersing agent; the dispersing agent is an ethylene-propylene copolymer and/or a carboxyl-containing ethylene-propylene copolymer. According to the invention, the toughness of the glass fiber reinforced PMMA/ABS composite material is improved by adding a specific dispersing agent and a toughening agent in a synergistic manner. The toughness of the high impact strength glass fiber reinforced PMMA/ABS composite material is higher than that of composite materials prepared by other toughening agent systems, and the high impact strength glass fiber reinforced PMMA/ABS composite material is more suitable for preparing household appliance shells and ornaments.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a high-impact-strength glass fiber reinforced PMMA/ABS composite material, and a preparation method and application thereof.
Background
The chemical synthesized polymer material has greatly changed the life of people since the birth. The polymer material has the advantages of good physical properties, low density, easy molding, most recycling, and the like, and is widely applied to various fields of furniture, household appliances, stationery, automobiles, buildings and the like, and is closely related to life of people. Meanwhile, in order to compensate for some performance short plates of the high polymer materials, composite materials have been developed. The composite material is a multicomponent material obtained by physically or chemically mixing two or more kinds of polymer materials or polymer materials with a metal or an inorganic material and then molding the mixture. By compounding different materials, the defects of certain performances of the original materials can be overcome, and the performances of the materials are improved. Glass fiber reinforced modified plastics are an important direction in many composite research areas. Glass fiber reinforced plastic has been widely used in various fields such as televisions, washing machines, electric tools, fan blades, etc. due to its excellent strength, lower density, excellent dimensional stability and low cost. However, because of the high glass fiber content, the notched Izod impact strength of glass fiber reinforced plastics is generally poor.
PMMA material has excellent weather resistance and light transmittance, and has excellent surface performance: the ABS is a plastic easy to process, and the product prepared by blending PMMA and ABS has good luster and lower production cost. However, the existing PMMA/ABS composite material has the problem of insufficient toughness and needs to be further improved. In the prior art, the toughness of the PMMA/ABS composite material is usually improved through glass fibers and a toughening agent, but from the practical use condition, the toughness of the material is improved to a certain extent by the existing scheme, but with the upgrading of the product, the market has higher requirements on the toughness of the composite material, and the toughness of the PMMA/ABS composite material needs to be further improved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the glass fiber reinforced PMMA/ABS composite material with better toughness, and the composite material has higher glossiness.
The invention further aims at providing a preparation method of the glass fiber reinforced PMMA/ABS composite material.
Another object of the invention is to provide the use of the glass fiber reinforced PMMA/ABS composite.
The above object of the present invention is achieved by the following technical scheme:
the high impact strength glass fiber reinforced PMMA/ABS composite material comprises the following components in parts by weight:
the dispersing agent is an ethylene-propylene copolymer and/or a carboxyl-containing ethylene-propylene copolymer.
The inventor has unexpectedly found that the adoption of the small amount of ethylene-propylene copolymer as the dispersing agent to be added into the glass fiber reinforced PMMA/ABS can better facilitate the dispersibility of the glass fiber in the PMMA/ABS composite material and further improve the toughness of the PMMA/ABS composite material. Particularly, the functional groups on the surface of the carboxyl-containing ethylene-propylene copolymer can be combined with hydroxyl groups on the surface of glass fibers through Van der Waals force, so that the dispersing agent can be well coated on the surfaces of the glass fibers, the binding force between the glass fibers and PMMA/ABS base materials is enhanced, the effect of an interfacial compatilizer is achieved, the impact strength of a composite material system is greatly improved, the surface fiber floating condition of the composite material is improved, and the overall glossiness of the material is also improved.
Preferably, in the high impact strength glass fiber reinforced PMMA/ABS composite material, the component of the dispersing agent is 3.0-4.5 parts.
Preferably, in the high impact strength glass fiber reinforced PMMA/ABS composite material, the weight of the toughening agent is 20-25 parts.
Preferably, the high impact strength glass fiber reinforced PMMA/ABS composite material comprises the following components in parts by weight:
preferably, the toughening agent is a methyl methacrylate type toughening agent.
The inventors found that when the amount of PMMA is low, the toughness of the composite material is high, but the glossiness is low, and when the amount of PMMA is too high, the glossiness of the composite material is high, but the toughness is remarkably reduced,
more toughening agent is selected in PMMA/ABS system, and the inventor finds that the methyl methacrylate toughening agent has better effect in the system of the invention.
More preferably, the toughening agent is methyl methacrylate-butadiene-styrene (MBS) and/or methyl methacrylate-acrylonitrile-styrene terpolymer (MAS).
Most preferably, the toughening agent is methyl methacrylate-acrylonitrile-styrene terpolymer (MAS), and when the toughening agent is methyl methacrylate-acrylonitrile-styrene terpolymer, the toughness of the obtained composite material is optimal.
Preferably, the glass fibers have an average diameter of 10 to 30 μm. Too small a diameter of the glass fiber does not significantly enhance the composite material, and too large a diameter of the glass fiber does not have a good bonding interface with the composite material.
Preferably, the mass flow rate of the melt of the ABS resin is 30-50 g/10min, the test standard is ISO1133-1-2011, and the test condition is 220 ℃ and 10kg. ABS in this melt mass flow rate range has better flowability, which is beneficial for better coating of glass fiber with polymer.
Preferably, the PMMA resin has a melt mass flow rate of 15-30 g/10min, and the test standard is ISO1133-1-2011, and the test condition is 220 ℃ and 10kg.
Preferably, the lubricant may be an amide-based lubricant, a stearate-based lubricant, a silicone-based lubricant, or an ester-based lubricant. Preferably, the lubricant is an ester lubricant. Preferably, the ester lubricant is an aliphatic stearate, such as an oleic aliphatic polyester or an erucic aliphatic polyester.
The antioxidant is one or a mixture of more of hindered amine, hindered phenol or phosphite or thioester.
The hindered amine antioxidant can be UV-3808, LA-402XP, LA-402AF and the like.
The hindered phenol antioxidant can be N, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-phenyl-propionamide (Irganox 1098), tetra [1093,5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (Irganox 1010), triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Iragnox 259), beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate N-octadecyl ester (Iragno 1076) or spiroglycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] (ADK AO-80) and the like.
The phosphite antioxidant can be 2, 4-di-tert-butylphenol (Irganox 168), bis (2, 6-di-tert-butyl-4-tolyl) pentaerythritol phosphite (PEP-36) or 627A, etc.
The thio-ester antioxidant can be distearyl thiodipropionate, dilauryl thiodipropionate, pentaerythritol dodecyl thiopropyl ester and the like.
The preparation method of the high impact strength glass fiber reinforced PMMA/ABS composite material comprises the steps of uniformly mixing all the components, carrying out melt extrusion and granulation at 160-240 ℃ by a double screw extruder, and drying to obtain the high impact strength glass fiber reinforced PMMA/ABS composite material.
The high impact strength glass fiber reinforced PMMA/ABS composite material is applied to the preparation of household appliance shells and ornaments. More specifically, the PMMA/ABS composite material has better luster, lower shrinkage after glass fiber is added, and is commonly used for preparing long-strip-shaped decorative pieces of household appliance shells, such as large-size (more than 50 inches) LED television decorative pieces.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the toughness and the glossiness of the glass fiber reinforced PMMA/ABS composite material are further improved by adding the specific dispersing agent to perform synergistic effect with the toughening agent under the premise of better other mechanical properties. The high-impact-strength glass fiber reinforced PMMA/ABS composite material is more suitable for being applied to preparing household appliance shells and ornaments.
Detailed Description
Technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional reagents, methods and apparatus commercially available in the art.
The following examples and comparative examples were prepared from the following raw materials:
polymethyl methacrylate PMMA LG chemical Co., ltd., trade name PMMA LG2, melt flow rate 20g/min
Acrylonitrile-butadiene-styrene terpolymer ABS 1 Basoff, brand ABS GP-35, melt flow rate 34g/10min;
acrylonitrile-butadiene-styrene terpolymer ABS 2LG chemical Co., ltd, trade mark ABS HP181, melt flow rate of 43g/min;
toughening agent 1MBS LG chemical Co., ltd, EM500
Toughening agent 2MAS Anchu east China sea plastics Co., ltd., Q500
Toughening agent 3 Gao Gu powder Jinhu petrochemistry Co., ltd., HR181
ECS13-03-534C, average diameter 13 μm, of glass fiber boulder group Co., ltd
The lubricant is an ester lubricant, commercially available and the same is used for all examples and comparative examples;
the antioxidant is an antioxidant 1010 and an antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:1, commercially available and all examples and comparative examples are the same;
dispersant 1 ethylene-propylene copolymer bath smelting Material technology (Shanghai) Co., ltd., 9010-79-1
Dispersant 2 carboxyl-containing ethylene-propylene copolymer Mitsui chemistry, 1105A
Dispersing agent 3 ethylene bis stearamide Hebei chemical engineering Co., ltd, EBS diffusion powder
The glass fiber reinforced PMMA/ABS composite materials of the examples and the comparative examples are prepared by the following method:
the components are dried and uniformly mixed according to the dosage of the table 1 and the table 2, and then the mixture is put into a double-screw machine, the length-diameter ratio of the screw is 40:1, the diameter is 35mm, the rotating speed of the extruder is controlled to be 300 revolutions per minute, the processing temperature is 160-240 ℃, and the high impact strength glass fiber reinforced PMMA/ABS composite material is obtained through extrusion cooling granulation.
Performance test of composite material:
impact strength: the test standard of the notch impact strength of the cantilever beam is ISO 180-2019, the test condition is normal temperature, and the unit is KJ/m 2 ；
Gloss level: the polypropylene composition was injection molded into a test panel and reflectance data at an angle of 60℃was measured using a gloss meter according to GB/T8807-1988 test method for specular gloss of plastics.
TABLE 1
TABLE 2
TABLE 3 Table 3
As can be seen from a comparison of comparative example 1 with example 1, the notched impact strength of the composite material is only 4.6KJ/m when no dispersant is added, even if a toughening agent is added 2 As can be seen from a comparison of comparative example 2 with example 1, if a non-methyl methacrylate-based toughening agent is used, the notched impact strength of the composite is only 4.9KJ/m even with the dispersant of the present application 2 As can be seen from a comparison of comparative example 3 with example 1, the notched impact strength of the composite material does not reach the level of the present invention if other conventional dispersants are used. Similarly, it can be seen from a comparison of comparative example 4 with example 6 that the notched impact strength of the composite material does not reach the level of the present invention if other conventional dispersants are used.
As can be seen from a comparison of example 1 with example 3, the use of MAS as a toughening agent provides a better toughening effect in the system of the present invention than MBS as a toughening agent. As can be seen from a comparison of example 1 and example 4, the dispersing effect of the carboxyl group-containing ethylene-propylene copolymer as a dispersing agent is superior to that of the ethylene-propylene copolymer dispersing agent, and thus the toughness of the obtained composite material is higher. As can be seen from the comparison of example 1 and example 10, when the number of dispersant parts is small, the effect of improving toughness is not as remarkable as that of the preferable embodiment (3 parts).
As can be seen from the comparison of example 1 and example 6, the gloss increases with increasing PMMA content of the system, but the toughness of the material deteriorates and the notched Izod impact strength decreases more.
As can be seen from the comparison of example 1, example 12 and example 17, the gloss tends to be lowered when the glass fiber content is high.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The high impact strength glass fiber reinforced PMMA/ABS composite material is characterized by comprising the following components in parts by weight:
the dispersing agent is an ethylene-propylene copolymer and/or a modified ethylene-propylene copolymer, and the modified ethylene-propylene copolymer is a carboxyl-containing ethylene-propylene copolymer.
2. The high impact strength glass fiber reinforced PMMA/ABS composite material according to claim 1, which is characterized by comprising the following components in parts by weight:
3. the high impact strength glass fiber reinforced PMMA/ABS composite of claim 1 or 2 wherein the toughening agent is a methyl methacrylate type toughening agent.
4. The high impact glass fiber reinforced PMMA/ABS composite of claim 1 or 2 wherein the toughening agent is MBS and/or MAS.
5. The high impact glass fiber reinforced PMMA/ABS composite of claim 1 or 2 wherein the glass fiber has an average diameter of 10 to 30 μm.
6. The high impact strength glass fiber reinforced PMMA/ABS composite material according to claim 1 or 2, wherein the mass flow rate of the melt of the ABS resin is 30-50 g/10min, the test standard is ISO1133-1-2011, and the test condition is 220 ℃ and 10kg.
7. The high impact strength glass fiber reinforced PMMA/ABS composite material according to claim 1 or 2, wherein the PMMA resin has a melt mass flow rate of 15-30 g/10min, and the test standard is ISO1133-1-2011, and the test condition is 220 ℃ and 10kg.
8. The high impact strength glass fiber reinforced PMMA/ABS composite of claim 1 or 2 wherein the lubricant is an ester lubricant; the antioxidant is one or a mixture of more of hindered amine, hindered phenol or phosphite or thioester.
9. The preparation method of the high impact strength glass fiber reinforced PMMA/ABS composite material according to any one of claims 1 to 8, which is characterized in that the components are uniformly mixed, and the high impact strength glass fiber reinforced PMMA/ABS composite material is obtained after the components are subjected to melt extrusion, granulation and drying at 160-240 ℃ by a double screw extruder.
10. The application of the high impact strength glass fiber reinforced PMMA/ABS composite material in preparing home appliance shells and ornaments according to any one of claims 1 to 8.
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| US5384353A (en) * | 1993-05-12 | 1995-01-24 | General Electric Company | Glass reinforced PC/ABS blend with toughness |
| CN106009476A (en) * | 2016-07-25 | 2016-10-12 | 金田集团（桐城）塑业有限公司 | High-hardness and anti-impact PMMA/ABS (Polymethyl Methacrylate/Acrylonitrile Butadiene Styrene) composite sheet material |
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| CN106009476A (en) * | 2016-07-25 | 2016-10-12 | 金田集团（桐城）塑业有限公司 | High-hardness and anti-impact PMMA/ABS (Polymethyl Methacrylate/Acrylonitrile Butadiene Styrene) composite sheet material |
| CN109181205A (en) * | 2018-07-16 | 2019-01-11 | 太仓市意欣塑胶有限公司 | High-strength abrasion-proof type moulding based on ABS alloy modified material |
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