CN114031888B - Highlight PMMA (polymethyl methacrylate) and ABS (Acrylonitrile butadiene styrene) composite material and preparation method thereof - Google Patents

Highlight PMMA (polymethyl methacrylate) and ABS (Acrylonitrile butadiene styrene) composite material and preparation method thereof Download PDF

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Publication number
CN114031888B
CN114031888B CN202111556509.0A CN202111556509A CN114031888B CN 114031888 B CN114031888 B CN 114031888B CN 202111556509 A CN202111556509 A CN 202111556509A CN 114031888 B CN114031888 B CN 114031888B
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filler
nano
pmma
parts
modified
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CN114031888A (en
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岑忠于
董利春
王波
孙潇
卢金金
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Ningbo Ruilong New Mstar Technology Ltd
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Ningbo Ruilong New Mstar Technology Ltd
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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

Abstract

The application relates to a highlight PMMA (polymethyl methacrylate) and ABS (acrylonitrile butadiene styrene) composite material and a preparation method thereof, wherein the highlight PMMA and ABS composite material comprises the following components in parts by weight: 200-300 parts of ABS resin; 160-240 parts of PMMA resin; 6-8 parts of compatilizer; 3-5 parts of an antioxidant; 30-60 parts of modified nano filler; the preparation method of the modified nano filler comprises the following steps: firstly preheating nano filler, then placing the nano filler in hydrogen peroxide aqueous solution, carrying out ultrasonic heating and stirring on the nano filler, then heating and mixing the nano filler with dispersing agent and modifying liquid, and finally carrying out vacuum drying to obtain modified nano filler; the modified liquid consists of one or more of sodium gluconate, sorbitol and N, N-dimethylformamide. The application improves the surface property of the composite material by adding the modified nano filler, and then endows the composite system with excellent glossiness.

Description

Highlight PMMA (polymethyl methacrylate) and ABS (Acrylonitrile butadiene styrene) composite material and preparation method thereof
Technical Field
The application relates to the technical field of high polymer materials, in particular to a highlight PMMA (polymethyl methacrylate) and ABS (acrylonitrile butadiene styrene) composite material and a preparation method thereof.
Background
ABS resin is a terpolymer composed of acrylonitrile, butadiene and styrene, has the common properties of three components, namely the advantages of corrosion resistance, high toughness and easy processing, and is widely applied to various fields, but ABS has lower hardness and poorer scratch resistance, so that the ABS resin is limited in application in certain fields, such as a liquid crystal television shell, an automobile LED lamp shell and the like, and other components are often added to achieve blending modification, wherein PMMA and ABS composite materials added with polymethyl methacrylate PMMA are taken as an example.
The PMMA and ABS composite materials in the related art are composite materials formed by mixing polymethyl methacrylate PMMA and acrylonitrile-butadiene-styrene copolymer ABS through a screw extruder, and have the advantages of corrosion resistance, scratch resistance and excellent mechanical properties, so that the PMMA and ABS composite materials are widely applied, but the PMMA and ABS composite materials are formed by simply mixing, so that the product surface properties are poor, and the product cannot have excellent glossiness.
Disclosure of Invention
The application provides a highlight PMMA and ABS composite material and a preparation method thereof, in order to ensure that the PMMA and ABS composite material has better glossiness.
In a first aspect, the application provides a highlight PMMA and ABS composite material, which adopts the following technical scheme:
the highlight PMMA and ABS composite material comprises the following components in parts by weight:
200-300 parts of ABS resin;
160-240 parts of PMMA resin;
6-8 parts of compatilizer;
3-5 parts of an antioxidant;
60-80 parts of modified nano filler;
the preparation method of the modified nano filler comprises the following steps:
a. pretreatment: preheating nano filler, placing the nano filler in hydrogen peroxide water solution, and carrying out ultrasonic heating and stirring on the nano filler to obtain pretreated filler;
b. modification treatment: heating and mixing the pretreated filler, a dispersing agent and a modifying liquid, and then filtering and drying to obtain a modified nano filler;
the modified liquid consists 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 mutually and stably mixed under the action of the compatilizer, rubber particles in the ABS can be uniformly dispersed in a matrix formed by PMMA, wherein the addition of the modified nano filler can form a skeleton and a binding site in a composite system, and can form a nano coating together with the resin on the surface layer of the composite system, 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 difficult to reduce the glossiness due to scratch, and the analysis is probably due to the fact that the formed nano coating has higher reflectivity and can reflect relatively uniform light under the illumination condition.
After ultrasonic treatment in hydrogen peroxide solution, the surface affinity and dispersion effect of the nano filler are improved, then the nano filler can be fully mixed with the modified liquid under the action of the dispersing agent, and the synergistic effect of sodium gluconate, sorbitol and N, N-dimethylformamide in the modified liquid is achieved,
the combination property and the glossiness improvement effect of the nano-filler are remarkably improved, and the reasons for the combination property and the glossiness improvement effect are probably that the modified liquid can endow the mixed system with better fluidity and lubricating effect, can also coat the surface of the nano-filler into a film, and can generate steric hindrance repulsive force while improving the combination force of the nano-filler and the polar group, so that the occurrence of 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 glossiness.
Preferably, the specific preparation steps of the modified nano-filler are as follows:
a. pretreatment: preheating nano filler to 60-80 ℃, placing the nano filler in 30-50% hydrogen peroxide aqueous solution by mass percent, and carrying out ultrasonic heating and stirring for 10-15min at an ultrasonic frequency of 20-25KHz to obtain pretreated filler; b. modification treatment: heating the pretreated filler, the dispersing agent and the modifying liquid to 80-100 ℃, mixing for 30-45min at the rotating speed of 500-800r/min, and filtering and drying 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 analysis is probably due to the fact that the polarity of the surface of the nano-filler is enhanced, agglomeration is not easy to occur, the binding force with active groups is stronger, and the subsequent mixing of the nano-filler and the modified liquid is facilitated.
Preferably, the nano filler in the a is prepared from 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).
By adopting the technical scheme, the nano-filler with the components and the proportion can endow the composite system with better hardness and glossiness, and the analysis is probably due to the fact that the nano-fillers have better compounding effect, the different nano-fillers can be coated with the modified film, and the binding force and the dispersing effect of the nano-filler 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 is endowed with higher diffuse reflectivity.
Preferably, the pretreatment filler, the dispersant and the modifying liquid are mixed according to the weight ratio of 1: (0.1-0.2): (3-7) mixing.
By adopting the technical scheme, the pretreatment filler, the dispersing agent and the modifying liquid with the proportion have optimal modifying effect, and the analysis of the reason is probably that the pretreatment filler with the proportion can be fully combined with the modifying liquid under the action of the dispersing agent, so that the effect of coating the pretreated filler into a film is better.
Preferably, the modifying solution is prepared from sodium gluconate, sorbitol and N, N-dimethylformamide according to the weight ratio of 1: (2-3): (0.5-0.8).
By adopting the technical scheme, the coating film effect of the modified liquid with the proportion is better, and the three have a synergistic effect, and the bonding performance and the bonding force of the nano filler are obviously improved through the coated modified film, so that the diffuse reflectivity of the formed nano coating is improved.
Preferably, the dispersing agent is one or more of polyethylene glycol, methyl amyl alcohol, polyacrylamide and sodium tripolyphosphate.
By adopting the technical scheme, the dispersing agent with the components and the proportion has 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, and the modification operation is completed.
Preferably, the composition further 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 force and stability between the composite system of the ABS resin and the PMMA resin, and can be used as a modifier while being used as a binder, so that the combination effect of the mixed system and the modified nano filler is enhanced, and the SBS resin, the PB resin and the composite system have better compatibility.
Preferably, the compatibilizing agent consists of maleic anhydride, ethyldistearamide 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 analysis of the reasons is probably that the compatilizer can be fully mixed under the lubrication compounding effect of the ethyl distearamide and the triethanolamine besides grafting the styrene in the ABS through the maleic anhydride group, so that the aim of improving the dispersibility of a composite system is fulfilled, and the ethyl distearamide has a certain brightening effect.
In a second aspect, the application provides a preparation method of a highlight PMMA and ABS composite material, which adopts the following technical scheme:
a preparation method of a highlight PMMA-ABS composite material comprises the following steps:
s1, melting and mixing: drying each component at 80+/-5 ℃, heating and mixing each component and an auxiliary agent according to corresponding parts by weight, 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 air-cooling to room temperature to obtain PMMA and ABS composite master batch.
By adopting the technical scheme, the preparation steps are more convenient, and the parameters of each step are easy to control, so that the preparation method is suitable for mass industrialized production, and the prepared PMMA and ABS composite master batch has stable and uniform performance, has better surface hardness and glossiness, and meets the application conditions in the special field.
Preferably, the air cooling step is as follows:
introducing nitrogen, cooling the master batch to 80-100 ℃ at 5 ℃/s, firstly preserving heat for 10-25s, preferably 90 ℃, preserving heat for 20s, and then pressurizing and introducing nitrogen to cool the master batch to room temperature at 15-20 ℃/s, preferably 15 ℃/s, thus completing cooling.
By adopting the technical scheme, the PMMA and ABS composite master batch prepared by the air cooling treatment is low in internal stress generated in the forming process, and then the PMMA and ABS composite system is less damaged, so that the surface performance of the prepared product is excellent.
In summary, the 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 the resin by adding the modified nano filler, and the composite system is endowed with excellent surface hardness and glossiness by virtue of the structure of the nano coating, so that the aim of highlighting can be achieved by diffuse reflection of illumination, and the nano coating has stable structural performance, acid and alkali resistance and is not easy to oxidize;
2. according to the application, through the modified nano filler, the dispersing agent and the modifying liquid with specific components and proportions, the modified nano filler is endowed with excellent surface binding property and dispersibility, and through coating the surface of the nano filler into a film, the binding force between the nano filler and the polar group is improved, and meanwhile, the steric hindrance repulsive force is generated, so that 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 has stable and uniform performance, excellent surface hardness and glossiness, can meet the application conditions in the special field, and is suitable for industrialized mass production.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in each of examples and comparative examples of the present application are commercially available except for the following specific descriptions.
Preparation example
Preparation example 1
A modified nano filler is prepared by the following steps:
a. pretreatment: preheating 100kg of nano filler to 70 ℃, placing the nano filler in 40% hydrogen peroxide aqueous solution by mass percent, carrying out ultrasonic heating and stirring for 12.5min, carrying out ultrasonic frequency of 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: the pretreatment filler, the dispersing agent and the modifying liquid are mixed according to the weight ratio of 1:0.15:5, mixing and heating for 37.5min, controlling the heating temperature to 90 ℃, controlling the rotating speed to 650r/min, filtering and drying for 4min, and obtaining the modified nano filler; the dispersing agent is polyethylene glycol;
the modified 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
The modified nanofiller differs from preparation example 1 in that the preparation steps are as follows:
a. pretreatment: preheating 100kg of nano filler to 40 ℃, placing the nano filler in a hydrogen peroxide aqueous solution with the mass percentage of 20%, carrying out ultrasonic heating and stirring for 5min, carrying out ultrasonic frequency of 20KHz, and then filtering and drying for 3min to obtain the pretreated filler;
b. modification treatment: and mixing and heating the pretreated filler, the dispersing agent and the modifying liquid for 15min, controlling the heating temperature to 60 ℃, controlling the rotating speed to 300r/min, filtering and drying for 3min, and preparing the modified nano filler by the same method as in preparation example 1.
Preparation example 3
The modified nanofiller differs from preparation example 1 in that the preparation steps are as follows:
a. pretreatment: preheating 100kg of nano filler to 60 ℃, placing the nano filler in 30% hydrogen peroxide aqueous solution by mass percent, carrying out ultrasonic heating and stirring for 10min, carrying out ultrasonic frequency of 20KHz, and then filtering and drying for 3min to obtain the pretreated filler;
b. modification treatment: and mixing and heating the pretreated filler, the dispersing agent and the modifying liquid for 30min, controlling the heating temperature to 80 ℃, controlling the rotating speed to 500r/min, filtering and drying for 3min, and preparing the modified nano filler by the same method as in preparation example 1.
Preparation example 4
The modified nanofiller differs from preparation example 1 in that the preparation steps are as follows:
a. pretreatment: preheating 100kg of nano filler to 80 ℃, placing the nano filler in a hydrogen peroxide aqueous solution with the mass percentage of 50%, carrying out ultrasonic heating and stirring for 15min, carrying out ultrasonic frequency of 25KHz, and then filtering and drying for 5min to obtain the pretreated filler;
b. modification treatment: and mixing and heating the pretreated filler, the dispersing agent and the modifying liquid for 45min, controlling the heating temperature to 100 ℃, controlling the rotating speed to 800r/min, filtering and drying for 5min, and preparing the modified nano filler by the same method as in preparation example 1.
Preparation example 5
The modified nanofiller differs from preparation example 1 in that the preparation steps are as follows:
a. pretreatment: preheating 100kg of nano filler to 100 ℃, placing the nano filler in a 60% hydrogen peroxide aqueous solution by mass percent, carrying out ultrasonic heating and stirring for 20min, carrying out ultrasonic frequency of 25KHz, and then filtering and drying for 5min to obtain the pretreated filler;
b. modification treatment: and mixing and heating the pretreated filler, the dispersing agent and the modifying liquid for 60min, controlling the heating temperature to 120 ℃, controlling the rotating speed to 1000r/min, filtering and drying for 5min, and preparing the modified nano filler by the same method as in preparation example 1.
Preparation example 6
The modified nanofiller is different from the preparation example 1 in that the nanofiller comprises nano barium sulfate, nano aluminum silicate and nano silicon carbide according to the weight ratio of 1:1:0.2, all other components being identical to those of preparation 1
Preparation example 7
The modified nanofiller is different from the preparation example 1 in that the nanofiller comprises nano barium sulfate, nano aluminum silicate and nano silicon carbide according to the weight ratio of 1:1.5:0.3, and the other components were the same as in preparation example 1.
Preparation example 8
The modified nanofiller is different from the preparation example 1 in that the nanofiller comprises nano barium sulfate, nano aluminum silicate and nano silicon carbide according to the weight ratio of 1:2.5:0.5, and the other components were the same as in preparation example 1.
Preparation example 9
The modified nanofiller is different from the preparation example 1 in that the nanofiller comprises nano barium sulfate, nano aluminum silicate and nano silicon carbide according to the weight ratio of 1:3:0.6, and the other components were the same as in preparation example 1.
Preparation example 10
The modified nano filler is different from the preparation example 1 in that the pretreatment filler, the dispersing agent and the modifying liquid in the weight ratio of 1:0.05:1, and the other components were the same as in preparation example 1.
PREPARATION EXAMPLE 11
The modified nano filler is different from the preparation example 1 in that the pretreatment filler, the dispersing agent and the modifying liquid in the weight ratio of 1:0.1:3, and the other components were the same as in preparation example 1.
Preparation example 12
The modified nano filler is different from the preparation example 1 in that the pretreatment filler, the dispersing agent and the modifying liquid in the weight ratio of 1:0.2:7, and the other components were the same as in preparation example 1.
Preparation example 13
The modified nano filler is different from the preparation example 1 in that the pretreatment filler, the dispersing agent and the modifying liquid in the weight ratio of 1:0.25:9, and the other components were the same as in preparation example 1.
PREPARATION EXAMPLE 14
The modified nano-filler is different from the preparation example 1 in that the modified liquid in the step b comprises sodium gluconate, sorbitol and N, N-dimethylformamide according to the weight ratio of 1:1:0.3, and the other components were the same as in preparation example 1.
Preparation example 15
The modified nano-filler is different from the preparation example 1 in that the modified liquid in the step b comprises sodium gluconate, sorbitol and N, N-dimethylformamide according to the weight ratio of 1:2:0.5, and the other components were the same as in preparation example 1.
PREPARATION EXAMPLE 16
The modified nano-filler is different from the preparation example 1 in that the modified liquid in the step b comprises sodium gluconate, sorbitol and N, N-dimethylformamide according to the weight ratio of 1:3:0.8, and the other components were the same as in preparation example 1.
Preparation example 17
The modified nano-filler is different from the preparation example 1 in that the modified liquid in the step b comprises sodium gluconate, sorbitol and N, N-dimethylformamide according to the weight ratio of 1:4:1, and the other components were the same as in preparation example 1.
PREPARATION EXAMPLE 18
The modified nanofiller is different from preparation example 1 in that the dispersing agent consists of polyethylene glycol and methylpentanol according to the weight ratio of 1:1, and the other components are the same as preparation example 1.
Preparation example 19
The modified nanofiller is different from preparation example 1 in that the dispersing agent consists of polyethylene glycol and polyacrylamide in a weight ratio of 1:1, and the other components are the same as in preparation example 1.
Preparation example 20
The modified nano filler is different from the preparation example 1 in that the dispersing agent comprises polyethylene glycol, polyacrylamide and sodium tripolyphosphate according to the weight ratio of 1:1:0.2, and the other components were the same as in preparation example 1.
Performance test
Five groups of master batches in each group of examples and comparative examples are respectively extracted and put into an injection machine to be injected at 220+/-5 ℃ to form a test sheet with the thickness of 1mm, and then the test sheet is subjected to cold pressing and cutting to form a sample plate with the thickness of 5cm multiplied by 12cm, and then pencil hardness and glossiness of the sample plate are respectively tested, wherein the test steps and the test standards are as follows:
(1) Pencil hardness test: after the sample plate is placed on a placing table of a testing machine, testing can be carried out, specific detection steps and detection standards are tested according to GB/T6739-1996, weight is 500g, and test results are recorded in the following table and are used for evaluating scratch resistance of materials;
(2) Gloss test: the test was performed using a 20 ° geometry, and specific test procedures and test standards were referred to ASTM D523-2014 "standard test method for specular gloss", and the test results (%) were averaged and reported in the following table.
Examples
Example 1
The highlight PMMA and ABS composite material comprises the following components in parts by weight as shown in table 1, and is prepared by the following preparation method:
s1, melting and mixing: drying the components at 80+/-5 ℃ for 4 hours, heating and mixing the components and the auxiliary agent according to the corresponding parts by weight for 20 minutes, controlling the heating temperature to 170 ℃ and the rotating speed to 650r/min, and preparing a mixture;
the antioxidant is p-phenylenediamine;
the compatilizer consists of maleic anhydride, ethyl distearamide 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 ℃, then introducing nitrogen, cooling the master batch to 90 ℃ at 5 ℃/s, preserving heat for 20s, pressurizing and introducing nitrogen, cooling the master batch to room temperature at 15 ℃/s, and finally cooling to obtain the PMMA and ABS composite master batch.
Examples 2 to 6
A highlighted PMMA, ABS composite, differing from example 1 in that the components and their respective weights are shown in table 1.
Table 1: each component and the corresponding weight (kg) in examples 1 to 6
Comparative example 1
The highlight PMMA and ABS composite material is different from example 1 in that the raw materials do not contain modified nanofiller, and all the other materials are the same as in example 1.
Comparative example 2
A highlighted PMMA, ABS composite was different from example 1 in that the nanofiller was not modified, but was the same as example 1.
Five groups of sample plates were prepared in the above examples 1 to 6 and comparative examples 1 to 2, and the pencil hardness and gloss were measured according to the above measurement procedures and measurement criteria, and the test results were recorded in the following table;
as can be seen from the above table, the pencil hardness is F-H and the gloss is 95-98% in examples 1-6, and it is seen that the above components and examples within the compounding ratio range have excellent scratch resistance and gloss.
In particular, the sample plate prepared in example 3 has a pencil hardness of H and a glossiness of 98%, and example 3 is a best example, and the modified nanofiller prepared by the components and the proportions has the best improvement effect on the glossiness and scratch resistance of the composite material.
It can also be seen from the above table that comparative example 1 has a significant reduction in scratch resistance and gloss, with pencil hardness of only 2B, compared to example 1, due to the absence of nanofiller; the gloss was only 80% reduced by 16% relative to example 1.
As can also be seen from the above table, comparative example 2 has little decrease in scratch resistance and gloss and has reduced pencil hardness to HB, since the added nanofiller is not modified, compared to example 1; the gloss was only 86% and 9% lower than in example 1.
In summary, after the nano-filler with the proportion is modified, the nano-filler can be fully mixed with the ABS resin and the PMMA resin through the compatilizer, wherein the modified nano-filler can form a skeleton and a bonding site in a composite system, and can also form a nano-coating on the surface layer of the composite system together with the resin, so that the formed nano-coating has higher diffuse reflectivity, and can reflect relatively uniform and soft light under the illumination condition, thereby obviously improving the hardness and the glossiness of the surface layer of the composite system.
Examples 7 to 10
The difference between the highlighted PMMA and ABS composite material and the embodiment 1 is that the modified nano filler is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: comparison Table of usage of modified nanofillers in examples 7-10
Group of Modified nanofiller
Example 7 Is made ofPreparation example 2
Example 8 Prepared from preparation example 3
Example 9 Prepared from preparation 4
Example 10 Prepared from preparation 5
Five groups of sample plates were obtained in examples 7 to 10, and the pencil hardness and gloss were measured according to the above measurement procedures and measurement standards, and the test results were recorded in the following table;
from the above table, the pencil hardness of example 1 and examples 7-10 is HB-F and the glossiness is 91-95%, and the modified nano-filler prepared by the preparation process can better improve the scratch resistance and glossiness of the composite system.
In particular, the sample plate prepared in example 1 has a pencil hardness of F and a glossiness of up to 95%, and it can be seen that example 1 is an optimal example, and the modified nanofiller prepared according to the parameters in preparation example 1 has an optimal modifying effect on the composite system, and imparts excellent scratch resistance and glossiness to the composite material.
In summary, the surface affinity and the dispersion effect of the nano-filler treated by the preparation steps are obviously improved, and the analysis is probably due to the fact that in the process of ultrasonic treatment in hydrogen peroxide solution, the polarity of the surface of the nano-filler is enhanced, agglomeration is not easy to occur, the binding force with active groups is stronger, the subsequent mixing of the nano-filler and the modifying liquid is facilitated, and the scratch resistance and the glossiness of the composite material are guaranteed.
Examples 11 to 14
The difference between the highlighted PMMA and ABS composite material and the embodiment 1 is that the modified nano filler is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: comparison of usage of modified nanofillers in examples 11-14
Group of Modified nanofiller
Example 11 From preparation 6
Example 12 Prepared from preparation 7
Example 13 Prepared from preparation 8
Example 14 Prepared in preparation example 9
Comparative example 3
The highlight PMMA and ABS composite material is different from the modified nanofiller in the preparation process of the embodiment 1, wherein the nanofiller is only nano barium sulfate, and the other materials are the same as the embodiment 1.
Comparative example 4
The highlight PMMA and ABS composite material is different from the embodiment 1 in the preparation process of the modified nano filler, wherein the nano filler comprises nano barium sulfate and nano aluminum silicate according to the weight ratio of 1:2, the other components are the same as in example 1.
Comparative example 5
The highlight PMMA and ABS composite material is different from the embodiment 1 in the preparation process of the modified nano filler, wherein the nano filler comprises nano barium sulfate and nano silicon carbide according to the weight ratio of 1:0.4, and the other components are the same as in example 1.
Five groups of sample plates prepared in the above examples 11 to 14 and comparative examples 3 to 5 were drawn, and the pencil hardness and gloss thereof were measured according to the above measurement procedures and measurement criteria, and the test results were recorded in the following table;
from the above table, the pencil hardness of example 1 and examples 11-14 is HB-F and the gloss is 91-95%, and it can be seen that the modified nanofiller prepared by the above-mentioned nanofiller proportion can better improve the scratch resistance and gloss of the composite system.
In particular, the sample plate prepared in example 1 has a pencil hardness of F and a glossiness of 95%, and example 1 is a best example, and the modified nanofiller prepared by the components and the proportions has the best improvement effect on the glossiness and scratch resistance of the composite material.
As can also be seen from the above table, compared with example 1, comparative example 3 has substantially reduced scratch resistance and gloss due to the use of only nano barium sulfate as filler, and has pencil hardness of only B; the gloss was only 88% reduced by 7% relative to example 1.
As can also be seen from the above table, comparative example 4 has reduced scratch resistance and gloss due to the absence of nano silicon carbide as compared to example 1, and reduced pencil hardness to HB; the gloss was only 91% reduced by 4% relative to example 1.
As can also be seen from the above table, comparative example 5 has a significant reduction in scratch resistance and a pencil hardness of B compared to example 1 due to the absence of nano aluminum silicate as the nano filler; the gloss was reduced by a small amount of 90% and 5% compared to example 1.
The reason for analysis is probably that the nano fillers have better compounding effect, different nano fillers can be coated with modified films, and the binding force and dispersing 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 dispersing and combining the nano fillers is endowed with higher diffuse reflectivity.
In summary, the three nano fillers have a compound effect, when the nano fillers are simultaneously selected from three of 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) can endow the composite system with better glossiness and scratch resistance.
Examples 15 to 18
The difference between the highlighted PMMA and ABS composite material and the embodiment 1 is that the modified nano filler is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: comparison Table of usage of modified nanofillers in examples 15-18
Group of Modified nanofiller
Example 15 Prepared from preparation 10
Example 16 Prepared from preparation 11
Example 17 From preparation 12
Example 18 Prepared in preparation example 13
Five groups of sample plates were prepared in examples 15 to 18 above, and the pencil hardness and gloss were measured according to the above measurement procedures and measurement criteria, and the test results were recorded in the following table;
from the above table, the pencil hardness of example 1 and examples 15-18 is HB-F, and the glossiness is 90-95%, and it can be seen that the modified nano-filler prepared by the pretreatment filler, the dispersant and the modifying liquid can better improve the scratch resistance and glossiness of the composite system.
In particular, the sample plate prepared in example 1 has a pencil hardness of F and a glossiness of up to 95%, and it can be seen that example 1 is an optimal example, and the modified nanofiller in the ratio has an optimal effect on improving the glossiness and scratch resistance of the composite material.
In summary, when the pretreatment filler, the dispersant and the modifying liquid are mixed according to the weight ratio of 1: (0.1-0.2): (3-7), and the reason for analysis is probably that the pretreated filler with the proportion can be fully combined with the modifying liquid under the action of the dispersing agent, so that the effect of coating the pretreated filler into a film is better, and the glossiness and scratch resistance of the composite material are further ensured.
Examples 19 to 22
The difference between the highlighted PMMA and ABS composite material and the embodiment 1 is that the modified nano filler is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: comparison Table of usage of modified nanofillers in examples 19-22
Group of Modified nanofiller
Example 19 From preparation 14
Example 20 Prepared in preparation 15
Example 21 From preparation 16
Example 22 Prepared in preparation example 17
Comparative example 6
The difference between the highlighted PMMA and ABS composite material and the modified liquid in example 1 is that sodium gluconate is not contained in the modified liquid, and the modified liquid is the same as the modified liquid in example 1.
Comparative example 7
The difference between the highlighted PMMA and ABS composite material and the modified liquid in example 1 is that sorbitol is not contained in the modified liquid, and the modified liquid is the same as the modified liquid in example 1.
Comparative example 8
A highlight PMMA/ABS composite material was different from example 1 in that N, N-dimethylformamide was not contained in the modified liquid, and the other was the same as in example 1.
Five groups of sample plates prepared in the above examples 19 to 22 and comparative examples 6 to 8 were extracted, and the pencil hardness and gloss thereof were measured according to the above measurement steps and measurement criteria, and the test results were recorded in the following table;
from the above table, 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 proportion can better promote the scratch resistance and glossiness of the composite system.
In particular, the sample plate prepared in example 1 has a pencil hardness of F and a glossiness of 95%, and example 1 is a best example, and the modified nanofiller prepared from the component and the modifying liquid in 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, comparative example 6 has a significantly reduced scratch resistance due to the lack of sodium gluconate in the modified liquid, and has a pencil hardness of only HB, relative to example 1; the gloss was reduced by a small amount, with a gloss of only 93%, 2% compared to example 1.
As can also be seen from the above table, comparative example 7 has a pencil hardness of F, but a gloss level of 88% and a gloss level of 7% lower than example 1, due to the absence of sorbitol in the modified liquid.
As can also be seen from the above table, in comparative example 8, the pencil hardness was still F but the gloss was greatly reduced by 91% and 4% compared to example 1, due to the lack of N, N-dimethylformamide in the modified liquid.
The reason for analysis is probably that the modified liquid with the proportion has better coating film effect, and the three have synergistic effect, and the bonding performance and the bonding force of the nano filler can be obviously improved through the coated modified film, so that the diffuse reflectance of the formed nano coating is improved.
In summary, the three components in the modified liquid have synergistic effect, when the modified liquid is simultaneously selected from sodium gluconate, sorbitol and N, N-dimethylformamide, the modified liquid is prepared from sodium gluconate, sorbitol and N, N-dimethylformamide according to the weight ratio of 1: (2-3): (0.5-0.8) can endow the composite system with better glossiness and scratch resistance.
Examples 23 to 25
The difference between the highlighted PMMA and ABS composite material and the embodiment 1 is that the modified nano filler is used in different conditions, and the specific corresponding relation is shown in the table below.
Table: comparison of usage of modified nanofillers in examples 23-25
Group of Modified nanofiller
Example 23 From preparation 18
Example 24 From preparation 19
Example 25 From preparation example 20
Five groups of sample plates were prepared in examples 23 to 25, and the pencil hardness and gloss were measured according to the above measurement procedures and measurement standards, and the test results were shown in the following table;
from the above table, the pencil hardness in example 1 and examples 23-25 is F, and the glossiness is 95-97%, and it can be seen that the modified nano filler prepared by selecting the above components and proportioning the dispersing agent can better improve the scratch resistance and glossiness of the composite system.
In particular, the sample plate prepared in example 25 has a pencil hardness of F and a gloss of 97%, and it is found that example 25 is an optimal example, and the dispersing agent prepared by the components and the proportions has a good dispersing effect.
In summary, when the dispersant is prepared from polyethylene glycol, polyacrylamide and sodium tripolyphosphate in a weight ratio of 1:1: when the nano-filler is formed by 0.2, the dispersion effect is optimal, and the analysis is probably due to the fact that the nano-filler and the nano-filler have optimal adaptation and lubrication effects, so that the fluidity of the whole mixed system can be improved, and the dispersion effect of the modified nano-filler is guaranteed.
Examples 26 to 28
A highlighted PMMA, ABS composite material differs from example 1 in that the components and amounts are shown in Table 2.
Table 2: each component and corresponding amount (kg) in examples 26 to 28
Five groups of sample plates were prepared in examples 26 to 28, and the pencil hardness and gloss were measured according to the above measurement procedures and measurement criteria, and the test results were shown in the following table;
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as can be seen from the above table, the pencil hardness in the examples 1 and 26-28 is F-H and the glossiness is 95-97%, and it can be seen that the scratch resistance and glossiness of the composite system can be better improved after SBS resin and PB resin are added.
In particular, the sample plate prepared in example 27 has a pencil hardness of H and a gloss of up to 97%, and it can be seen that example 27 is an optimal example, and the scratch resistance and gloss of the composite system under the composition and the proportion are optimal.
In summary, after the SBS resin and PB resin are added according to the corresponding weights in examples 26-28, the scratch resistance and glossiness of the composite system can be further improved, and the reason for analyzing the scratch resistance and glossiness of the composite system is probably that the components can be used as a binder and a modifier, so that the bonding effect of the mixed system and the modified nano-filler is enhanced, the bonding force and stability between the composite systems are improved, and the scratch resistance and glossiness of the composite system are further ensured.
Comparative example 9
A highlighted PMMA, ABS composite material differs from example 1 in that the compatibilizer does not include maleic anhydride, and is otherwise the same as example 1.
Comparative example 10
A highlighted PMMA, ABS composite material differs from example 1 in that the compatibilizing agent does not include maleic anhydride and ethyl bis-stearamide, all of which are the same as example 1.
Comparative example 11
A highlighted PMMA, ABS composite, differing from example 1 in that the compatibilizing agent did not include maleic anhydride and triethanolamine, all of which were the same as in example 1.
Five groups of sample plates were obtained in the above comparative examples 9 to 11, and the pencil hardness and gloss were measured according to the above measurement procedures and measurement criteria, and the test results were recorded in the following table;
as can also be seen from the above table, comparative example 9 has a significantly reduced scratch resistance and pencil hardness of only HB, relative to example 1, due to the lack of maleic anhydride in the compatibilizer; the gloss was reduced by a small amount, with a gloss of only 91% and a 4% reduction over example 1.
As can also be seen from the above table, comparative example 10 has a significantly reduced scratch resistance and pencil hardness of only HB, relative to example 1, due to the lack of maleic anhydride and ethyl bis-stearamide in the compatibilizer; the gloss was greatly reduced, with a gloss of only 87%, 8% reduction over example 1.
It can also be seen from the above table that comparative example 11 has a significantly reduced scratch resistance and pencil hardness of only HB, relative to example 1, due to the lack of maleic anhydride and triethanolamine in the compatibilizer; the gloss was greatly reduced, with a gloss of only 90% and a 5% reduction over example 1.
In summary, when the compatibilizer is composed of three components, the mixing effect of the ABS resin and the PMMA resin can be remarkably improved, and the reason for analyzing the mixing effect is probably that the compatibilizer can be fully mixed under the lubrication compounding effect of the ethyl distearamide and the triethanolamine besides grafting the styrene in the ABS through the maleic anhydride group, so that the aim of improving the dispersibility of a composite system is fulfilled, and the ethyl distearamide has a certain brightening effect.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (4)

1. The highlight PMMA-ABS composite material is characterized by comprising the following components in parts by weight:
200-300 parts of ABS resin;
160-240 parts of PMMA resin;
6-8 parts of compatilizer;
the compatilizer consists of maleic anhydride, ethyl distearamide and triethanolamine;
3-5 parts of an antioxidant;
60-80 parts of modified nano filler;
the preparation method of the modified nano filler comprises the following steps:
a. pretreatment: preheating nano filler to 60-80 ℃, placing the nano filler in 30-50% hydrogen peroxide aqueous solution by mass percent, carrying out ultrasonic heating and stirring for 10-15min, and carrying out filtration and drying for 3-5min at the ultrasonic frequency of 20-25KHz to obtain the pretreated filler;
the nano filler in the a is prepared from 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);
b. modification treatment: the pretreatment filler, the dispersing agent and the modifying liquid are mixed according to the weight ratio of 1: (0.1-0.2): (3-7) mixing and heating to 80-100 ℃, mixing for 30-45min at a rotating speed of 500-800r/min, and then filtering and drying for 3-5min to obtain the modified nano filler;
the modified liquid is prepared from sodium gluconate, sorbitol and N, N-dimethylformamide according to the weight ratio of 1: (2-3): (0.5-0.8); the dispersing agent is polyethylene glycol or one or more of polyethylene glycol, methyl amyl alcohol, polyacrylamide and sodium tripolyphosphate.
2. The highlight PMMA/ABS composite material according to claim 1, further comprising the following components in parts by weight:
40-60 parts of SBS resin;
30-50 parts of PB resin.
3. The preparation method of the highlight PMMA and ABS composite material as claimed in any one of claims 1 to 2, which is characterized by comprising the following steps:
s1, melting and mixing: drying each component at 80+/-5 ℃, heating and mixing each component and an auxiliary agent according to corresponding parts by weight, 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 ℃, and air-cooling to room temperature to obtain PMMA and ABS composite master batch.
4. The method for preparing the highlight PMMA and ABS composite material according to claim 3, wherein the air cooling step is as follows:
introducing nitrogen, cooling the master batch to 80-100 ℃ at 5 ℃/s, preserving heat for 10-25s, pressurizing and introducing nitrogen, cooling the master batch to room temperature at 15-20 ℃/s, and thus completing cooling.
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