CN114031888A - High-brightness PMMA (polymethyl methacrylate) and ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof - Google Patents
High-brightness PMMA (polymethyl methacrylate) and ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 106
- 239000002131 composite material Substances 0.000 title claims abstract description 90
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 68
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 51
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 51
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 title claims description 54
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 title description 34
- 239000000945 filler Substances 0.000 claims abstract description 203
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000002270 dispersing agent Substances 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 230000000051 modifying effect Effects 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims abstract description 14
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 14
- 235000012207 sodium gluconate Nutrition 0.000 claims abstract description 14
- 239000000176 sodium gluconate Substances 0.000 claims abstract description 14
- 229940005574 sodium gluconate Drugs 0.000 claims abstract description 14
- 239000000600 sorbitol Substances 0.000 claims abstract description 14
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 4
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims description 37
- 238000012986 modification Methods 0.000 claims description 37
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 19
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims description 11
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 11
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229940037312 stearamide Drugs 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- 239000012752 auxiliary agent Substances 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
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims 2
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 32
- 239000000243 solution Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 19
- 238000005259 measurement Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 239000002103 nanocoating Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000002310 reflectometry Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011895 specific detection Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000258971 Brachiopoda Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 229920001897 terpolymer Polymers 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The application relates to a high-brightness PMMA and ABS composite material and a preparation method thereof, and the high-brightness PMMA and ABS composite material comprises the following components in parts by weight: 200 portions and 300 portions of ABS resin; PMMA resin 160 and 240 parts; 6-8 parts of a compatilizer; 3-5 parts of an antioxidant; 30-60 parts of modified nano filler; the preparation steps of the modified nano filler are as follows: preheating the nano filler, placing the nano filler in aqueous hydrogen peroxide, carrying out ultrasonic heating and stirring on the nano filler, then heating and mixing the nano filler, the dispersing agent and the modifying liquid, and finally carrying out vacuum drying to obtain the modified nano filler; the modifying liquid is composed of one or more of sodium gluconate, sorbitol and N, N-dimethylformamide. According to the preparation method, the surface performance of the composite material is improved by adding the modified nano filler, and then the composite system is endowed with excellent glossiness.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a high-brightness PMMA and ABS composite material and a preparation method thereof.
Background
ABS resin is a terpolymer composed of acrylonitrile, butadiene and styrene, and has the common properties of three components, namely the advantages of corrosion resistance, high toughness and easy processing, so that the ABS resin is widely applied to various fields, but the ABS resin has low hardness and poor scratch resistance, and the application of the ABS resin in certain fields, such as liquid crystal television shells, automobile LED lamp shells and the like, is limited, so that other components are often added to achieve blending modification, wherein PMMA and ABS composite materials added with polymethyl methacrylate PMMA are taken as examples.
The PMMA and ABS composite material in the related technology is a composite material formed by mixing polymethyl methacrylate (PMMA) and acrylonitrile-butadiene-styrene copolymer (ABS) through a screw extruder, and has the advantages of corrosion resistance, scraping resistance and excellent mechanical property, so that the PMMA and ABS composite material is widely applied.
Disclosure of Invention
In order to enable the PMMA and ABS composite material to have excellent glossiness, the application provides a high-brightness PMMA and ABS composite material and a preparation method thereof.
In a first aspect, the present application provides a high-brightness PMMA and ABS composite material, which adopts the following technical scheme:
the high-brightness PMMA and ABS composite material comprises the following components in parts by weight:
200 portions and 300 portions of ABS resin;
PMMA resin 160 and 240 parts;
6-8 parts of a compatilizer;
3-5 parts of an antioxidant;
60-80 parts of modified nano filler;
the preparation steps of the modified nano filler are as follows:
a. pretreatment: preheating the nano filler, placing the preheated nano filler in aqueous hydrogen peroxide, and carrying out ultrasonic heating and stirring on the preheated nano filler to obtain a pretreated filler;
b. modification treatment: heating and mixing the pretreated filler, the dispersant and the modification liquid, and filtering and drying to obtain a modified nano filler;
the modifying liquid is composed of one or more of sodium gluconate, sorbitol and N, N-dimethylformamide.
By adopting the technical scheme, the ABS resin and the PMMA resin can be stably mixed with each other under the action of the compatilizer, rubber particles in the ABS can be uniformly dispersed in a matrix formed by the PMMA, the addition of the modified nano filler can form a skeleton and binding sites in the composite system, and a nano coating is formed on the surface layer of the composite system together with the resin, so that the hardness and the glossiness of the surface layer of the composite system are obviously improved, the composite system is scratch-resistant, and the glossiness is not easy to reduce due to scratch.
After the nano filler is subjected to ultrasonic treatment in hydrogen oxide solution, the surface affinity and the dispersion effect of the nano filler are improved, then the nano filler can be fully mixed with the modification liquid under the action of the dispersing agent, and through the synergistic action of sodium gluconate, sorbitol and N, N-dimethylformamide in the modification liquid,
the binding property and the gloss improvement effect of the nano filler are remarkably improved, and the reason for analyzing the effect is probably that the modification liquid can endow a mixed system with better fluidity and lubrication effect, and can also coat the surface of the nano filler to form a film, so that the binding force of the nano filler and a polar group is improved, and simultaneously, a steric hindrance repulsion force is generated, so that the agglomeration phenomenon of the nano filler is reduced, and the modified nano filler can stably and efficiently endow the composite system with better surface hardness and gloss.
Preferably, the specific preparation steps of the modified nano filler are as follows:
a. pretreatment: preheating the nano filler to 60-80 ℃, then placing the nano filler into 30-50% aqueous hydrogen peroxide solution by mass percent, and carrying out ultrasonic heating and stirring for 10-15min, wherein the ultrasonic frequency is 20-25KHz, so as to obtain the pretreated filler; b. Modification treatment: heating the pretreated filler, the dispersant and the modification liquid to 80-100 ℃, mixing the pretreated filler, the dispersant and the modification liquid at the rotating speed of 500-800r/min for 30-45min, and filtering and drying the mixture for 3-5min to obtain the modified nano filler.
By adopting the technical scheme, the surface affinity and the dispersion effect of the nano filler treated by the preparation steps are obviously improved, and the reason for analyzing the nano filler is probably that in the ultrasonic treatment process in a hydrogen peroxide solution, the polarity of the surface of the nano filler is enhanced, the nano filler is not easy to agglomerate, and meanwhile, the nano filler has stronger binding force with an active group, and is beneficial to the subsequent mixing of the nano filler and a modification solution.
Preferably, the nano filler in the step a is prepared from nano barium sulfate, nano aluminum silicate and nano silicon carbide in a weight ratio of 1: (1.5-2.5): (0.3-0.5).
By adopting the technical scheme, the nano-fillers with the components and the proportion can endow a composite system with better hardness and gloss, and the analysis probably results in that the nano-fillers have better compounding effect, different nano-fillers can be coated with modified films, the bonding force and the dispersion effect of the nano-fillers are greatly improved through unequal steric hindrance repulsive force on each nano-filler, and thus the nano-coating formed by the dispersed combination of the nano-fillers is endowed with higher diffuse reflectivity.
Preferably, the weight ratio of the pretreated filler to the dispersant to the modifying liquid is 1: (0.1-0.2): (3-7) mixing.
By adopting the technical scheme, the modifying effect of the pretreated filler, the dispersant and the modifying liquid in the proportion is optimal, and the reason for analyzing the effect is probably that the pretreated filler in the proportion can be fully combined with the modifying liquid under the action of the dispersant, and the coating film forming effect is good.
Preferably, the modifying solution is prepared from sodium gluconate, sorbitol and N, N-dimethylformamide according to a weight ratio of 1: (2-3): (0.5-0.8).
By adopting the technical scheme, the coating film forming effect of the modified liquid prepared according to the proportion is excellent, the three have a synergistic effect, the bonding performance and the bonding force of the nano filler can be remarkably improved through the coating formed modified film, and then the diffusion reflectivity of the formed nano coating is improved.
Preferably, the dispersant is one or more of polyethylene glycol, methylpentanol, polyacrylamide and sodium tripolyphosphate.
By adopting the technical scheme, the components and the proportioned dispersant have better adaptation and lubrication effects with the nano filler, so that the whole mixed system has stronger fluidity, and the modified nano filler can be rapidly and uniformly dispersed into the mixed system to complete modification operation.
Preferably, the composition also comprises the following components in parts by weight:
40-80 parts of SBS resin;
30-50 parts of PB resin.
By adopting the technical scheme, the SBS resin and the PB resin are added to enhance the binding power and stability between the composite system of the ABS resin and the PMMA resin, can be used as a binding agent and a modifier, further enhances the combination effect of the mixed system and the modified nano filler, and has excellent compatibility with the composite system.
Preferably, the compatibilizer consists of maleic anhydride, ethyl bis stearamide, and triethanolamine.
By adopting the technical scheme, the compatilizer of the components can obviously improve the mixing effect of the ABS resin and the PMMA resin, and the reason for analyzing the compatibility is probably that the compatilizer can graft styrene in the ABS through a maleic anhydride group and can also be fully mixed under the lubricating and compounding action of ethyl bis stearamide and triethanolamine, so that the aim of improving the dispersibility of a composite system is fulfilled, and the ethyl bis stearamide has a certain brightening effect.
In a second aspect, the application provides a preparation method of a high-brightness PMMA and ABS composite material, which adopts the following technical scheme:
a preparation method of a high-brightness PMMA and ABS composite material comprises the following steps:
s1, melt mixing: drying each component at 80 +/-5 ℃, heating and mixing each component and an auxiliary agent according to the corresponding weight part, and controlling the heating temperature to be 160-180 ℃ to prepare a mixture;
s2, extrusion granulation: adding the mixture into an extruder, extruding at 220-260 ℃, preferably 240 ℃, and cooling to room temperature by air to obtain the PMMA-ABS composite master batch.
By adopting the technical scheme, the preparation steps are convenient, and the parameters of each step are easy to control, so that the method is suitable for large-scale industrial production, and the prepared PMMA and ABS composite material master batch has stable and uniform performance, excellent surface hardness and glossiness, and meets the application conditions of the master batch in special fields.
Preferably, the air cooling step is as follows:
and introducing nitrogen, cooling the master batch to 80-100 ℃ at the speed of 5 ℃/s, preserving the heat for 10-25s, preferably reducing the temperature to 90 ℃, preserving the heat for 20s, pressurizing and introducing the nitrogen, cooling the master batch to room temperature at the speed of 15-20 ℃/s, preferably 15 ℃/s, and finishing cooling.
By adopting the technical scheme, the internal stress generated in the forming process of the PMMA and ABS composite material master batch prepared by the air cooling treatment is lower, the damage to a PMMA and ABS composite system is smaller, and the surface performance of the prepared product is better.
In summary, the present application has the following beneficial effects:
1. according to the application, the nano coating is formed on the surface layer of the composite system together with resin by adding the modified nano filler, the composite system is endowed with excellent surface hardness and glossiness by the structure of the nano coating, the purpose of high brightness can be achieved by diffusion reflection of illumination, and the nano coating is stable in structural performance, is acid and alkali resistant and is not easy to oxidize;
2. according to the application, the modified nano filler, the dispersing agent and the modifying liquid with specific components and proportions are endowed with excellent surface bonding performance and dispersibility, and the surface of the nano filler is coated with the film to form the film, so that the bonding force between the nano filler and a polar group is improved, the steric hindrance repulsion force is generated, and the occurrence of the agglomeration phenomenon of the nano filler is reduced;
3. the preparation method is simple, various parameters and conditions are easy to control and achieve, and the prepared composite material is stable and uniform in performance, has excellent surface hardness and glossiness, can meet application conditions in special fields, and is suitable for industrial mass production.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in the examples and comparative examples of the present application are commercially available except for the specific description below.
Preparation example
Preparation example 1
A modified nano filler is prepared by the following steps:
a. pretreatment: preheating 100kg of nano filler to 70 ℃, putting the nano filler into 40% hydrogen peroxide water solution by mass percent, carrying out ultrasonic heating and stirring for 12.5min, wherein the ultrasonic frequency is 20KHz, and then filtering and drying for 4min to obtain the pretreated filler;
the nano filler is prepared from nano barium sulfate, nano aluminum silicate and nano silicon carbide according to the weight ratio of 1: 2: 0.4;
b. modification treatment: mixing the pretreated filler, a dispersing agent and a modifying solution according to the weight ratio of 1: 0.15: 5, mixing and heating for 37.5min, controlling the heating temperature to 90 ℃ and the rotating speed to 650r/min, and filtering and drying for 4min to obtain the modified nano filler; the dispersant is polyethylene glycol;
the modifying liquid is prepared from sodium gluconate, sorbitol and N, N-dimethylformamide according to the weight ratio of 1: 2.5: 0.65.
Preparation example 2
A modified nano filler is different from the preparation example 1 in that the preparation steps are as follows:
a. pretreatment: preheating 100kg of nano filler to 40 ℃, putting the nano filler into 20% hydrogen peroxide water solution by mass percent, carrying out ultrasonic heating and stirring for 5min, wherein the ultrasonic frequency is 20KHz, and then filtering and drying for 3min to obtain the pretreated filler;
b. modification treatment: and mixing the pretreated filler with a dispersant and a modifying solution, heating for 15min at 60 ℃ and at the rotating speed of 300r/min, filtering and drying for 3min, wherein the rest are the same as those in preparation example 1, and thus obtaining the modified nano filler.
Preparation example 3
A modified nano filler is different from the preparation example 1 in that the preparation steps are as follows:
a. pretreatment: preheating 100kg of nano filler to 60 ℃, putting the nano filler into 30% hydrogen peroxide water solution by mass percent, carrying out ultrasonic heating and stirring for 10min, wherein the ultrasonic frequency is 20KHz, and then filtering and drying for 3min to obtain the pretreated filler;
b. modification treatment: and mixing the pretreated filler with a dispersant and a modifying solution, heating for 30min at 80 ℃ and at 500r/min, filtering and drying for 3min, wherein the rest are the same as those in preparation example 1, and thus obtaining the modified nano filler.
Preparation example 4
A modified nano filler is different from the preparation example 1 in that the preparation steps are as follows:
a. pretreatment: preheating 100kg of nano filler to 80 ℃, putting the nano filler into 50% hydrogen peroxide water solution by mass percent, carrying out ultrasonic heating and stirring for 15min, wherein the ultrasonic frequency is 25KHz, and then filtering and drying for 5min to obtain the pretreated filler;
b. modification treatment: and mixing the pretreated filler with a dispersant and a modifying solution, heating for 45min at 100 ℃ and at 800r/min, filtering and drying for 5min, wherein the rest are the same as those in preparation example 1, and thus obtaining the modified nano filler.
Preparation example 5
A modified nano filler is different from the preparation example 1 in that the preparation steps are as follows:
a. pretreatment: preheating 100kg of nano filler to 100 ℃, putting the nano filler into 60% hydrogen peroxide water solution by mass percent, carrying out ultrasonic heating and stirring for 20min, wherein the ultrasonic frequency is 25KHz, and then filtering and drying for 5min to obtain the pretreated filler;
b. modification treatment: and mixing the pretreated filler with a dispersant and a modifying solution, heating for 60min at the temperature of 120 ℃ and at the rotating speed of 1000r/min, filtering and drying for 5min, wherein the rest are the same as those in preparation example 1, and thus obtaining the modified nano filler.
Preparation example 6
A modified nano filler is different from the nano filler in preparation example 1 in that the nano filler is prepared from nano barium sulfate, nano aluminum silicate and nano silicon carbide in a weight ratio of 1: 1:0.2 composition, otherwise the same as in preparation example 1
Preparation example 7
A modified nano filler is different from the nano filler in preparation example 1 in that the nano filler is prepared from nano barium sulfate, nano aluminum silicate and nano silicon carbide in a weight ratio of 1: 1.5: 0.3, and the rest is the same as in preparation example 1.
Preparation example 8
A modified nano filler is different from the nano filler in preparation example 1 in that the nano filler is prepared from nano barium sulfate, nano aluminum silicate and nano silicon carbide in a weight ratio of 1: 2.5: 0.5, and the rest is the same as in preparation example 1.
Preparation example 9
A modified nano filler is different from the nano filler in preparation example 1 in that the nano filler is prepared from nano barium sulfate, nano aluminum silicate and nano silicon carbide in a weight ratio of 1: 3: 0.6, and the rest is the same as in preparation example 1.
Preparation example 10
The modified nano filler is different from the modified nano filler in the preparation example 1 in that the weight ratio of the pretreated filler to the dispersant to the modifying solution in the step b is 1: 0.05: 1, and the rest was the same as in preparation example 1.
Preparation example 11
The modified nano filler is different from the modified nano filler in the preparation example 1 in that the weight ratio of the pretreated filler to the dispersant to the modifying solution in the step b is 1: 0.1: 3 and the mixture was mixed, and the rest was the same as in preparation example 1.
Preparation example 12
The modified nano filler is different from the modified nano filler in the preparation example 1 in that the weight ratio of the pretreated filler to the dispersant to the modifying solution in the step b is 1:0.2: 7 was mixed, and the rest was the same as in preparation example 1.
Preparation example 13
The modified nano filler is different from the modified nano filler in the preparation example 1 in that the weight ratio of the pretreated filler to the dispersant to the modifying solution in the step b is 1: 0.25: 9, and the remainder was the same as in preparation example 1.
Preparation example 14
The modified nano filler is different from the modified nano filler prepared in preparation example 1 in that the modification liquid in the step b is prepared from sodium gluconate, sorbitol and N, N-dimethylformamide in a weight ratio of 1: 1: 0.3, and the rest is the same as in preparation example 1.
Preparation example 15
The modified nano filler is different from the modified nano filler prepared in preparation example 1 in that the modification liquid in the step b is prepared from sodium gluconate, sorbitol and N, N-dimethylformamide in a weight ratio of 1: 2: 0.5, and the rest is the same as in preparation example 1.
Preparation example 16
The modified nano filler is different from the modified nano filler prepared in preparation example 1 in that the modification liquid in the step b is prepared from sodium gluconate, sorbitol and N, N-dimethylformamide in a weight ratio of 1: 3: 0.8, and the rest is the same as in preparation example 1.
Preparation example 17
The modified nano filler is different from the modified nano filler prepared in preparation example 1 in that the modification liquid in the step b is prepared from sodium gluconate, sorbitol and N, N-dimethylformamide in a weight ratio of 1: 4: 1, the rest of the composition was the same as in preparation example 1.
Preparation example 18
A modified nanofiller differing from preparation example 1 in that the dispersant was composed of polyethylene glycol and methylpentanol in a weight ratio of 1:1, the remainder being the same as in preparation example 1.
Preparation example 19
A modified nano filler is different from the modified nano filler in preparation example 1 in that a dispersing agent is composed of polyethylene glycol and polyacrylamide according to a weight ratio of 1:1, and the rest is the same as that of the modified nano filler in preparation example 1.
Preparation example 20
A modified nano filler is different from the modified nano filler in preparation example 1 in that a dispersing agent is prepared from polyethylene glycol, polyacrylamide and sodium tripolyphosphate according to a weight ratio of 1:0.2, and the rest is the same as in preparation example 1.
Performance test
In each group of examples and comparative examples, five groups of master batches are respectively extracted and put into an injection machine to be injection-molded into a test sheet with the thickness of 1mm at the temperature of 220 +/-5 ℃, and then the test sheet is cold-pressed and cut into sample plates with the thickness of 5cm multiplied by 12cm, and the pencil hardness and the glossiness of the sample plates are respectively tested, wherein the test steps and the test standards are as follows:
(1) and (3) testing pencil hardness: the sample plate is placed on a placing table of a testing machine, the test can be carried out, the specific detection steps and the detection standard are tested according to GB/T6739-1996, the weight is 500g, and the test results are recorded in the following table and used for evaluating the scratch resistance of the material;
(2) and (3) testing the glossiness: the geometrical conditions of 20 degrees are selected for testing, the specific detection steps and the detection standard refer to ASTM D523-2014 Standard test method for specular gloss, and the average value of the test results (%) is recorded in the following table.
Examples
Example 1
The high-brightness PMMA and ABS composite material is prepared by the following preparation method, wherein the components and the corresponding weight are shown in Table 1:
s1, melt mixing: drying the components at 80 +/-5 ℃ for 4h, heating and mixing the components and the auxiliary agent in corresponding parts by weight for 20min, controlling the heating temperature to be 170 ℃ and the rotating speed to be 650r/min, and preparing a mixture;
the antioxidant is p-phenylenediamine;
the compatilizer consists of maleic anhydride, ethyl bis stearamide and triethanolamine according to the weight ratio of 1:0.2: 0.3;
s2, extrusion granulation: adding the mixture into an extruder, extruding at 240 ℃, introducing nitrogen, cooling the master batch to 90 ℃ at 5 ℃/s, preserving the temperature for 20s, pressurizing and introducing nitrogen, cooling the master batch to room temperature at 15 ℃/s, and cooling to obtain the PMMA-ABS composite master batch.
Examples 2 to 6
A high-brightness PMMA-ABS composite material is different from that of the embodiment 1 in that each component and the corresponding weight are shown in the table 1.
Table 1: each component and the corresponding weight (kg) in examples 1-6
Comparative example 1
The difference between the high-brightness PMMA-ABS composite material and the embodiment 1 is that the raw materials do not contain modified nano-filler, and the rest is the same as the embodiment 1.
Comparative example 2
A high-brightness PMMA and ABS composite material is different from that of the embodiment 1 in that the other parts are the same as the embodiment 1 except that the nano filler is not modified.
Five groups of the sample plates prepared in the above examples 1 to 6 and comparative examples 1 to 2 were extracted, pencil hardness and gloss thereof were measured according to the above measurement procedures and measurement standards, and the test results were recorded in the following table;
as can be seen from the above table, the pencil hardness of examples 1-6 is F-H, and the gloss is 95-98%, and it can be seen that the examples with the above components and the compounding ratio range all have better scratch resistance and gloss.
In particular, the sample plate prepared in example 3 has pencil hardness of H and glossiness of up to 98%, and it can be seen that example 3 is the best example, and the modified nano filler with the components and the proportion has the best effect of improving the glossiness and scratch resistance of the composite material.
As can also be seen from the above table, in comparative example 1, with respect to example 1, since the nano filler is not added, the scratch resistance and the glossiness are both greatly reduced, and the pencil hardness is only 2B; the gloss was only 80%, which is a 16% reduction over example 1.
As can also be seen from the above table, in comparative example 2, with respect to example 1, since the added nanofiller was not modified, the scratch resistance and gloss were both reduced to a small extent, and the pencil hardness was reduced to HB; the gloss was only 86%, which is a 9% reduction over example 1.
In summary, the nano-filler in the above ratio can be fully mixed with the ABS resin and the PMMA resin by the compatibilizer after being modified, wherein the modified nano-filler can form a skeleton and binding sites in the composite system, and can also form a nano-coating on the surface layer of the composite system together with the resin, and the formed nano-coating has a high diffuse reflectance, and can reflect relatively uniform and soft light under the illumination condition, thereby significantly improving the hardness and gloss of the surface layer of the composite system.
Examples 7 to 10
The difference between the high-brightness PMMA and ABS composite material and the embodiment 1 is that the used conditions of the modified nano-filler are different, and the specific corresponding relationship is shown in the table below.
Table: comparative tables for use of modified nanofillers in examples 7-10
| Group of | Modified nano filler |
| Example 7 | Prepared from preparation example 2 |
| Example 8 | Prepared from preparation example 3 |
| Example 9 | Prepared from preparation example 4 |
| Example 10 | Prepared from preparation example 5 |
Five groups of the sample plates prepared in the above examples 7 to 10 were extracted, pencil hardness and gloss thereof were measured according to the above measurement procedures and measurement standards, and the test results were recorded in the following table;
as can be seen from the table above, the pencil hardness of the modified nano-filler prepared by the preparation process is HB-F, and the glossiness of the modified nano-filler is 91-95%, so that the scratch resistance and the glossiness of the composite system can be improved better.
In particular, the sample plate prepared in example 1 has pencil hardness of F and gloss of up to 95%, and it can be seen that example 1 is the most preferred example, and the modified nano-filler prepared by the conditions of the parameters in preparation example 1 has the most preferred effect on improving the composite system, and gives the composite material excellent scratch resistance and gloss.
In conclusion, the surface affinity and the dispersion effect of the nano filler treated by the preparation steps are remarkably improved, and the reason for analyzing the nano filler is that the polarity of the surface of the nano filler is enhanced in the ultrasonic treatment process in a hydrogen peroxide solution, the nano filler is not easy to agglomerate, and meanwhile, the nano filler has stronger binding force with an active group, so that the nano filler is beneficial to the subsequent mixing of the nano filler and a modification liquid, and the scratch resistance and the glossiness of the composite material are further ensured.
Examples 11 to 14
The difference between the high-brightness PMMA and ABS composite material and the embodiment 1 is that the used conditions of the modified nano-filler are different, and the specific corresponding relationship is shown in the table below.
Table: comparative tables for use of modified nanofillers in examples 11-14
| Group of | Modified nano filler |
| Example 11 | Prepared from preparation example 6 |
| Example 12 | Prepared from preparation example 7 |
| Example 13 | Prepared from preparation example 8 |
| Example 14 | Prepared from preparation example 9 |
Comparative example 3
The difference between the high-brightness PMMA-ABS composite material and the embodiment 1 is that in the preparation process of the modified nano filler, the nano filler is only nano barium sulfate, and the rest is the same as the embodiment 1.
Comparative example 4
The difference between the high-brightness PMMA and ABS composite material and the embodiment 1 is that in the preparation process of the modified nano filler, the nano filler is prepared by mixing nano barium sulfate and nano aluminum silicate according to the weight ratio of 1: 2, the rest was the same as in example 1.
Comparative example 5
The difference between the high-brightness PMMA-ABS composite material and the embodiment 1 is that in the preparation process of the modified nano filler, the nano filler is prepared from nano barium sulfate and nano silicon carbide according to the weight ratio of 1: 0.4, and the rest is the same as example 1.
Five groups of the sample plates prepared in the above examples 11 to 14 and comparative examples 3 to 5 were extracted, pencil hardness and gloss thereof were measured according to the above measurement procedures and measurement standards, and the test results were recorded in the following table;
as can be seen from the table above, the pencil hardness of the modified nano-filler prepared by the nano-filler mixture is HB-F, and the glossiness of the modified nano-filler is 91-95% in the examples 1 and 11-14, so that the scratch resistance and the glossiness of the composite system can be improved better.
In particular, the sample plate prepared in example 1 has pencil hardness of F and glossiness of up to 95%, and it can be seen that example 1 is the best example, and the modified nano filler with the components and the proportion has the best effect of improving the glossiness and scratch resistance of the composite material.
As can also be seen from the above table, in comparative example 3, compared with example 1, since only nano barium sulfate is used as the filler, the scratch resistance and the glossiness are both greatly reduced, and the pencil hardness is only B; the gloss was only 88%, which is a 7% reduction over example 1.
As can also be seen from the above table, in comparative example 4, with respect to example 1, since the nanofiller lacks the nano silicon carbide, the scratch resistance and the gloss are both reduced, and the pencil hardness is reduced to HB; the gloss was only 91%, which is a 4% reduction over example 1.
As can also be seen from the above table, in comparative example 5, compared with example 1, the scratch resistance is greatly reduced and the pencil hardness is reduced to B due to the lack of nano aluminum silicate in the nano filler; the gloss was reduced by 90% in a small amount, which is 5% lower than that of example 1.
The reason for analyzing the effect probably is that the nano fillers have better compound effect, different nano fillers can be coated with modified films, and the binding force and the dispersion effect of the nano fillers are greatly improved through unequal steric hindrance repulsive force on each nano filler, so that the nano coating formed by the dispersed combination of the nano fillers has higher diffusion reflectivity.
In conclusion, the three nano-fillers have a compounding effect, when the nano-fillers are nano-barium sulfate, nano-aluminum silicate and nano-silicon carbide, the nano-fillers are prepared from the nano-barium sulfate, the nano-aluminum silicate and the nano-silicon carbide according to the weight ratio of 1: (1.5-2.5): (0.3-0.5), the composite material can endow the composite system with better glossiness and scratch resistance.
Examples 15 to 18
The difference between the high-brightness PMMA and ABS composite material and the embodiment 1 is that the used conditions of the modified nano-filler are different, and the specific corresponding relationship is shown in the table below.
Table: comparative tables for use of modified nanofillers in examples 15-18
| Group of | Modified nano filler |
| Example 15 | Prepared from preparation example 10 |
| Example 16 | Prepared from preparation example 11 |
| Example 17 | Prepared from preparation example 12 |
| Example 18 | Prepared from preparation example 13 |
Five groups of the sample plates prepared in the above examples 15 to 18 were extracted, pencil hardness and gloss thereof were measured according to the above measurement procedures and measurement standards, and the test results were recorded in the following table;
as can be seen from the table above, the pencil hardness in examples 1 and 15-18 is HB-F, and the glossiness is 90-95%, so that the modified nano-filler prepared by the pretreatment filler, the dispersant and the modifying solution can better improve the scratch resistance and the glossiness of the composite system.
In particular, the sample plate prepared in example 1 has pencil hardness of F and glossiness of up to 95%, and it can be seen that example 1 is the best example, and the modified nano filler with the above ratio has the best effect of improving the glossiness and scratch resistance of the composite material.
In summary, when the weight ratio of the pretreated filler, the dispersant and the modifying solution is 1: (0.1-0.2): and (3) when the components are mixed, the modification effect is optimal, and the analysis probably results in that the pretreatment filler in the proportion can be fully combined with the modification liquid under the action of the dispersing agent, the coating film forming effect is good, and the glossiness and the scratch resistance of the composite material are further guaranteed.
Examples 19 to 22
The difference between the high-brightness PMMA and ABS composite material and the embodiment 1 is that the used conditions of the modified nano-filler are different, and the specific corresponding relationship is shown in the table below.
Table: modified nanofiller use in examples 19-22
| Group of | Modified nano filler |
| Example 19 | Prepared from preparation 14 |
| Example 20 | Prepared from preparation example 15 |
| Example 21 | Prepared from preparation example 16 |
| Example 22 | Prepared from preparation example 17 |
Comparative example 6
The difference between the high-brightness PMMA-ABS composite material and the embodiment 1 is that the modification liquid does not contain sodium gluconate, and the other parts are the same as the embodiment 1.
Comparative example 7
The high-brightness PMMA-ABS composite material is different from that of the embodiment 1 in that the modification liquid does not contain sorbitol, and the other parts are the same as those of the embodiment 1.
Comparative example 8
The high-brightness PMMA-ABS composite material is different from that of the embodiment 1 in that the modification liquid does not contain N, N-dimethylformamide, and the rest is the same as that of the embodiment 1.
Five groups of the sample plates prepared in the above examples 19 to 22 and comparative examples 6 to 8 were extracted, pencil hardness and gloss thereof were measured according to the above measurement procedures and measurement standards, and the test results were recorded in the following table;
as can be seen from the table above, the pencil hardness in example 1 and examples 19-22 is F, and the glossiness is 88-95%, and it can be seen that the modified nano-filler prepared by the above-mentioned modifying solution can better improve the scratch resistance and glossiness of the composite system.
In particular, the sample plate prepared in example 1 has pencil hardness of F and glossiness of up to 95%, and example 1 is the best example, and the modified nano filler prepared from the modified liquid prepared from the components and the proportion has the best effect on improving the glossiness and scratch resistance of the composite material.
As can be seen from the table above, in comparative example 6, compared with example 1, the scratch resistance is greatly reduced due to the lack of sodium gluconate in the modifying solution, and the pencil hardness is only HB; the gloss was reduced to a small extent, with only 93% gloss, which was reduced by 2% relative to example 1.
As can be seen from the above table, in comparative example 7, the pencil hardness is F but the gloss is greatly reduced, and the gloss is only 88% and is reduced by 7% compared with example 1, because sorbitol is absent in the modification liquid, compared with example 1.
As can be seen from the above table, in comparative example 8, compared with example 1, the pencil hardness is still F due to the lack of N, N-dimethylformamide in the modifying solution, but the glossiness is greatly reduced, and is only 91%, which is reduced by 4% compared with example 1.
The reason for analyzing the above may be that the coating film forming effect of the modified liquid with the above ratio is excellent, and the three have synergistic effect, so that the binding performance and binding force of the nano filler can be remarkably improved through the coating formed modified film, and then the diffusion reflectivity of the formed nano coating is improved.
In conclusion, the three components in the modification liquid have a synergistic effect, when the modification liquid simultaneously selects sodium gluconate, sorbitol and N, N-dimethylformamide, the modification liquid is prepared from the following components in a weight ratio of 1: (2-3): (0.5-0.8), the composite material can endow the composite system with better glossiness and scratch resistance.
Examples 23 to 25
The difference between the high-brightness PMMA and ABS composite material and the embodiment 1 is that the used conditions of the modified nano-filler are different, and the specific corresponding relationship is shown in the table below.
Table: comparative tables for use of modified nanofillers in examples 23-25
| Group of | Modified nano filler |
| Example 23 | Prepared from preparation 18 |
| Example 24 | Prepared from preparation example 19 |
| Example 25 | Prepared from preparation example 20 |
Five groups of the sample plates prepared in the above examples 23 to 25 were extracted, pencil hardness and gloss thereof were measured according to the above measurement procedures and measurement standards, and the test results were recorded in the following table;
as can be seen from the table above, the pencil hardness in the examples 1 and 23-25 is F, and the glossiness is 95-97%, and it can be seen that the modified nano-filler prepared by selecting the components and the dispersant in proportion can better improve the scratch resistance and the glossiness of the composite system.
In particular, the sample plate prepared in example 25 has pencil hardness of F and glossiness of 97%, and it can be seen that example 25 is the best example, and the dispersing effect of the component and the dispersant in the proportion is better.
In summary, when the dispersant is prepared from polyethylene glycol, polyacrylamide and sodium tripolyphosphate according to the weight ratio of 1: when the nano filler is 0.2, the dispersion effect is optimal, and the reason for analyzing the nano filler is probably that the nano filler and the nano filler have optimal adaptation and lubrication effects, so that the overall fluidity of a mixed system can be improved, and the dispersion effect of the modified nano filler is further ensured.
Examples 26 to 28
A high-brightness PMMA and ABS composite material is different from that of the embodiment 1 in that the components and the using amount are shown in the table 2.
Table 2: EXAMPLES 26-28 the respective Components and the respective amounts (kg)
Five groups of the sample plates prepared in the above examples 26 to 28 were extracted, and the pencil hardness and the gloss thereof were measured according to the above measurement procedures and measurement standards, and the test results were recorded in the following table;
as can be seen from the table above, the pencil hardness in examples 1 and 26-28 is F-H, and the glossiness is 95-97%, so that the scratch resistance and the glossiness of the composite system can be better improved after the SBS resin and the PB resin are added.
In particular, the sample plate prepared in example 27 has pencil hardness H and gloss up to 97%, and example 27 is the best example, and the scratch resistance and gloss of the composite system prepared from the components and the ratio are the best.
In summary, the reason why the scratch resistance and the gloss of the composite system can be further improved by adding the SBS resin and the PB resin according to the corresponding weights in examples 26 to 28 is analyzed that the components can be used as a binder and a modifier, thereby enhancing the bonding effect between the mixed system and the modified nano filler, improving the bonding force and stability between the composite systems, and further ensuring the scratch resistance and the gloss of the composite system.
Comparative example 9
A high-brightness PMMA and ABS composite material is different from that of the embodiment 1 in that maleic anhydride is not included in a compatilizer, and the rest is the same as that of the embodiment 1.
Comparative example 10
A high-brightness PMMA and ABS composite material is different from that of the embodiment 1 in that maleic anhydride and ethyl bis stearamide are not included in a compatilizer, and the rest is the same as that of the embodiment 1.
Comparative example 11
A high-brightness PMMA and ABS composite material is different from that of the embodiment 1 in that maleic anhydride and triethanolamine are not included in a compatilizer, and the rest is the same as that of the embodiment 1.
The five groups of the sample plates prepared in the above comparative examples 9 to 11 were extracted, the pencil hardness and the gloss thereof were measured according to the above measurement procedures and measurement standards, and the test results were recorded in the following table;
as can also be seen from the above table, in comparative example 9, compared with example 1, the scratch resistance is greatly reduced due to the lack of maleic anhydride in the compatibilizer, and the pencil hardness is only HB; the gloss was reduced to a small extent, with only 91% gloss, which was reduced by 4% relative to example 1.
As can also be seen from the above table, in comparative example 10, compared with example 1, the scratch resistance is greatly reduced due to the lack of maleic anhydride and ethyl bis stearamide in the compatilizer, and the pencil hardness is only HB; the gloss was greatly reduced, and the gloss was only 87%, which was 8% lower than that of example 1.
As can also be seen from the above table, in comparative example 11, compared with example 1, the scratch resistance is greatly reduced due to the lack of maleic anhydride and triethanolamine in the compatilizer, and the pencil hardness is only HB; the gloss was greatly reduced, and the gloss was only 90%, which was 5% lower than that of example 1.
In conclusion, when the compatilizer consists of three components, the mixing effect of the ABS resin and the PMMA resin can be obviously improved, and the reason for analyzing the compatilizer is probably that the compatilizer can be fully mixed under the lubricating and compounding action of ethyl bis stearamide and triethanolamine besides the maleic anhydride group grafted styrene in the ABS, so that the aim of improving the dispersibility of a composite system is fulfilled, and the ethyl bis stearamide has a certain brightening effect.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The high-brightness PMMA and ABS composite material is characterized by comprising the following components in parts by weight:
200 portions and 300 portions of ABS resin;
PMMA resin 160 and 240 parts;
6-8 parts of a compatilizer;
3-5 parts of an antioxidant;
60-80 parts of modified nano filler;
the preparation steps of the modified nano filler are as follows:
a. pretreatment: preheating the nano filler, placing the preheated nano filler in aqueous hydrogen peroxide, carrying out ultrasonic heating and stirring on the nano filler, and filtering and drying the mixture to obtain a pretreated filler;
b. modification treatment: heating and mixing the pretreated filler, the dispersant and the modification liquid, and filtering and drying to obtain a modified nano filler;
the modifying liquid is composed of one or more of sodium gluconate, sorbitol and N, N-dimethylformamide.
2. The high-brightness PMMA-ABS composite material of claim 1, which is characterized in that the modified nano filler is prepared by the following specific steps:
a. pretreatment: preheating the nano filler to 60-80 ℃, putting the nano filler into 30-50% hydrogen peroxide water solution by mass percent, carrying out ultrasonic heating and stirring for 10-15min, wherein the ultrasonic frequency is 20-25KHz, and filtering and drying for 3-5min to obtain the pretreated filler;
b. modification treatment: heating the pretreated filler, the dispersant and the modification liquid to 80-100 ℃, mixing the pretreated filler, the dispersant and the modification liquid at the rotating speed of 500-800r/min for 30-45min, and filtering and drying the mixture for 3-5min to obtain the modified nano filler.
3. The high brightness PMMA, ABS composite material of claim 2, characterized in that the nano filler in a is prepared by mixing nano barium sulfate, nano aluminum silicate and nano silicon carbide according to the weight ratio of 1: (1.5-2.5): (0.3-0.5).
4. The high-brightness PMMA and ABS composite material as claimed in claim 2, wherein the weight ratio of the pretreated filler to the dispersant and the modifying liquid is 1: (0.1-0.2): (3-7) mixing.
5. The high-brightness PMMA and ABS composite material as claimed in claim 4, wherein the modification liquid is prepared from sodium gluconate, sorbitol and N, N-dimethylformamide according to a weight ratio of 1: (2-3): (0.5-0.8).
6. The high brightness PMMA, ABS composite material of claim 4, wherein the dispersant is one or more of polyethylene glycol, methyl amyl alcohol, polyacrylamide and sodium tripolyphosphate.
7. The high-brightness PMMA and ABS composite material of claim 1, which is characterized by further comprising the following components in parts by weight:
40-60 parts of SBS resin;
30-50 parts of PB resin.
8. The high gloss PMMA and ABS composite of claim 1, wherein the compatibilizer is comprised of maleic anhydride, ethyl bis stearamide, and triethanolamine.
9. The preparation method of the high-brightness PMMA-ABS composite material of any one of claims 1-8, which is characterized by comprising the following steps:
s1, melt mixing: drying each component at 80 +/-5 ℃, heating and mixing each component and an auxiliary agent according to the corresponding weight part, and controlling the heating temperature to be 160-180 ℃ to prepare a mixture;
s2, extrusion granulation: adding the mixture into an extruder, extruding at the temperature of 220-260 ℃, and air-cooling to room temperature to obtain the PMMA-ABS composite master batch.
10. The preparation method of the high-brightness PMMA-ABS composite material of claim 9, which is characterized by comprising the following air cooling steps:
and introducing nitrogen, cooling the master batch to 80-100 ℃ at the speed of 5 ℃/s, preserving the temperature for 10-25s, pressurizing and introducing the nitrogen, and cooling the master batch to the room temperature at the speed of 15-20 ℃/s to finish cooling.
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