CN113072789A - PMMA/MBS/AS polymer composite material AMS and preparation method thereof - Google Patents

PMMA/MBS/AS polymer composite material AMS and preparation method thereof Download PDF

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CN113072789A
CN113072789A CN202110527827.8A CN202110527827A CN113072789A CN 113072789 A CN113072789 A CN 113072789A CN 202110527827 A CN202110527827 A CN 202110527827A CN 113072789 A CN113072789 A CN 113072789A
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pmma
mbs
zones
ams
polymer composite
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王浦
王晨
魏喜顺
袁秀雷
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Zhejiang Kaixin Optoelectronics Tech Co 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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention relates to the technical field of high molecular materials, in particular to a PMMA/MBS/AS polymer composite material AMS and a preparation method thereof, wherein the PMMA/MBS/AS polymer composite material AMS comprises the following raw materials in percentage by weight: PMMA: 48-84%, MBS: 10-30%, AS: 5-18%, compatibilizer: 0.1-1%, weather-resistant agent: 0.1-0.3%, flame retardant: 0.2-0.5%, antioxidant: 0.2-0.5%, heat stabilizer: 0.2-0.5%, dispersing agent: 0.1 to 0.2%, light stabilizer: 0.1 to 0.2 percent; weighing the materials according to the formula, and fully stirring and uniformly mixing; and putting the obtained material into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product AMS. The invention can prepare a composite material with high transparency, low haze, high weather resistance and impact resistance, and broadens the application field of the material.

Description

PMMA/MBS/AS polymer composite material AMS and preparation method thereof
Technical Field
The invention relates to the technical field of high molecular materials, in particular to a PMMA/MBS/AS polymer composite material AMS and a preparation method thereof.
Background
Polymethyl methacrylate (PMMA) is a high molecular polymer, also called as acrylic, has high transparency, light transmittance of 90-92%, good chemical property, insulation property, weather resistance and processability, low density, high mechanical strength, low price and the like, and is applied to various fields, such as display panels, household appliance parts, automobile parts, ornaments and the like. However, PMMA is low in toughness, poor in ductility, prone to brittle fracture and brittle, and limits its further applications.
In the prior art, PMMA impact resistance can be improved by compounding PMMA and MBS, but MBS belongs to low-temperature rubber, high weather resistance is poor, the compounded output material of PMMA and MBS in a high-temperature state presents a fogging and whitening condition, the toughness of the output material is improved, but light transmittance is low, haze is high, optical performance is poor, and the application field is limited.
In the prior art, compared with the PMMA and AS composite output material and PMMA and MBS composite output material, PMMA and AS composite improves the weather resistance of the output material, but the PMMA and AS composite output material has poor impact resistance, poor toughness and limited application field.
Because high light transmittance, low haze, high toughness, impact resistance and high weather resistance can not be achieved at the same time, the PMMA modified material which is really put on the market is few, and the problem which needs to be solved at present is urgent.
PMMA/MBS has the phenomenon of whiting and fogging of products under high-temperature operation, has low temperature range,
disclosure of Invention
1. Technical problem to be solved
The purpose of the invention is: aims to provide a PMMA/MBS/AS polymer composite material AMS and a preparation method thereof, which can realize a composite material with high transparency, low haze, high weather resistance and impact resistance, and solve the problems in the prior art.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
The PMMA/MBS/AS polymer composite material AMS comprises the following raw materials in percentage by weight: PMMA: 48-84%, MBS: 10-30%, AS: 5-18%, compatibilizer: 0.1-1%, weather-resistant agent: 0.1-0.3%, flame retardant: 0.2-0.5%, antioxidant: 0.2-0.5%, heat stabilizer: 0.2-0.5%, dispersing agent: 0.1 to 0.2%, light stabilizer: 0.1 to 0.2 percent;
the PMMA is polymethyl methacrylate with the content of more than 98 percent, the average molecular weight of the PMMA is 25-30 ten thousand, the MBS is a terpolymer of methyl methacrylate, butadiene and styrene with the content of more than 98 percent, the number average molecular weight of the MBS is 30-35 ten thousand, the AS is a graft copolymer of acrylonitrile and styrene with the content of more than 98 percent, and the molecular weight of the AS is 25-35 ten thousand.
Further, the compatilizer is one or more of styrene-methacrylic acid, styrene-maleic anhydride copolymer and styrene-maleic anhydride copolymer. The modified composite material is used for improving the compatibility of PMMA, MBS and AS, thereby improving the impact strength of the modified composite material AMS.
Further, the weather resisting agent is one or a mixture of more of 2-hydroxy-4-n-octoxy benzophenone, salicylate, benzophenone, triazine and hindered amine free radical trapping agent. The modified composite material AMS is used for improving the high temperature resistance of the modified composite material AMS, so that the high temperature resistance of the modified composite material AMS is more stable.
Further, the flame retardant is one or more of bis- (2,4, 6-tribromophenoxy) ethane, ethane bisphenol A-bis (diphenyl phosphate) and tolyl diphenyl phosphate. The modified composite material AMS is used for improving the flame retardance of the modified composite material AMS.
Furthermore, the antioxidant is prepared by mixing a phenol antioxidant, a phosphate antioxidant and a thioester antioxidant according to the mass ratio of 1:1: 1. For reducing the probability of PMMA, MBS and AS being oxidized in the molten state. Wherein the phenolic antioxidant may be pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), the phosphate antioxidant may be tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), and the thioester antioxidant may be pentaerythritol tetrakis (3-laurylthiopropionate) (antioxidant 412S).
Furthermore, the heat stabilizer is an octyl tin stabilizer, and the octyl tin stabilizer has a good heat stabilizing effect.
Further, the heat stabilizer is isooctyl dithioglycolate di-n-octyl tin. The method is used for improving the thermal stability of the modified composite material AMS.
Further, the dispersing agent is mainly prepared by mixing C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether according to the mass ratio of 1: 3. The mixture for improving PMMA, MBS and AS is more uniform and dispersed when being stirred.
Further, the light stabilizer is methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer. The number average molecular weight of the modified composite material is 10-15 ten thousand, and the modified composite material is used for improving the aging resistance of the modified composite material AMS.
Further, the UV-400 ultraviolet absorbent is also included, and the weight percentage of the ultraviolet absorbent is as follows: 0.3 to 0.5 percent. The modified composite material AMS is used for improving the ultraviolet resistance of the modified composite material AMS.
Further, AS is a transparent material.
Further, the method for preparing the PMMA/MBS/AS composite material AMS comprises the following steps:
step a: drying and dehydrating granular PMMA, granular MBS, granular AS, a compatilizer, a weather resistant agent, a flame retardant, an antioxidant, a heat stabilizer, a diffusant and a light stabilizer, weighing the materials according to the formula, and fully stirring and uniformly mixing;
step b: and (b) putting the material obtained in the step a into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product AMS.
Further, in step a: the stirring speed is 300-500rpm, and the stirring time is 2-4 minutes; in the step b: the twin-screw extruder is divided into 11 sections, and the temperature setting range of each section is as follows: a first area: 170-185 ℃, and a second zone: 185-200 ℃, and three zones: 200-210 ℃, four zones: 210-220 ℃, five zones: 220-225 ℃, six zones: 225-230 ℃, seven areas: 230-235 ℃ and eight zones: 235-240 ℃, 220-235 ℃ in the nine zones, and ten zones: 210-220 ℃, eleven regions: 195-200 ℃, the retention time is controlled to be 1-2 minutes, and the vacuum degree is controlled to be 0.6-0.8 MPa.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
firstly, the MBS contains unsaturated butadiene and is easy to age under the action of oxygen and ultraviolet rays, so the weather resistance is poor, the AS has a coating effect on the MBS under the high-temperature operation, the AS can protect the MBS, the weather resistance of the high-yield discharge material is improved, the transmittance of the high-yield discharge material is improved under the high-temperature operation, the heat conduction capability is delayed, and the application field of the output material is widened.
The high light transmittance and the low haze of the composite material AMS are considered, the toughness of the composite material AMS is improved, and the weather resistance of the composite material AMS is improved. The application field of the composite material AMS is enlarged.
Detailed Description
Example 1:
a method for preparing PMMA/MBS/AS polymer composite material AMS comprises the following steps:
step a: mixing granular PMMA, granular MBS, granular AS, styrene-methacrylic acid, 2-hydroxy-4-n-octyloxy benzophenone, bis- (2,4, 6-tribromophenoxy), an antioxidant, isooctyl dithioglycolate di-n-octyltin, C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether according to the mass ratio of 1:3, drying and dehydrating methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer, weighing the materials according to the following formula, and mixing the materials to obtain the PMMA: 61.9%, MBS: 18%, AS: 18%, styrene-methacrylic acid: 0.5%, 2-hydroxy-4-n-octyloxy benzophenone: 0.1%, bis- (2,4, 6-tribromophenoxy): 0.2%, antioxidant: 0.3%, isooctyl dithioglycolate di-n-octyl tin: 0.2 percent of C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether are mixed according to the mass ratio of 1: 3: 0.1%, methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer: 0.2%, UV400 UV absorber: 0.5 percent; stirring and mixing for 3 minutes at 300rpm to obtain a mixed material;
step b: and (b) putting the material obtained in the step a into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product of the polymer composite material AMS. Wherein: a first zone of the double-screw extruder: 170 ℃, zone two: 185 ℃, three zones: 200 ℃, four zones: 210 ℃, five zones: 220 ℃, six zones: 225 ℃, seven zones: 230 ℃, eight zones: 235 ℃, nine zones 220 ℃, ten zones: 210 ℃, eleven zones: the retention time is controlled at 1 minute at 195 ℃, and the vacuum degree is controlled at 0.6 MPa.
Example 2:
a method for preparing PMMA/MBS/AS polymer composite material AMS comprises the following steps:
step a: mixing granular PMMA, granular MBS, granular AS, styrene-methacrylic acid, 2-hydroxy-4-n-octyloxy benzophenone, bis- (2,4, 6-tribromophenoxy), an antioxidant, isooctyl dithioglycolate di-n-octyltin, C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether according to the mass ratio of 1:3, drying and dehydrating methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer, weighing the materials according to the following formula, and mixing the materials to obtain the PMMA: 73.9%, MBS: 18%, AS: 6%, styrene-methacrylic acid: 0.5%, 2-hydroxy-4-n-octyloxy benzophenone: 0.1%, bis- (2,4, 6-tribromophenoxy): 0.2%, antioxidant: 0.3%, isooctyl dithioglycolate di-n-octyl tin: 0.2 percent of C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether are mixed according to the mass ratio of 1: 3: 0.1%, methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer: 0.2%, UV400 UV absorber: 0.5 percent; stirring and mixing the mixture for 2.5 minutes at 350rpm to obtain a mixed material;
step b: and (b) putting the material obtained in the step a into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product of the polymer composite material AMS. Wherein: a first zone of the double-screw extruder: 170 ℃, zone two: 185 ℃, three zones: 200 ℃, four zones: 210 ℃, five zones: 220 ℃, six zones: 225 ℃, seven zones: 230 ℃, eight zones: 235 ℃, nine zones 220 ℃, ten zones: 210 ℃, eleven zones: the retention time is controlled at 1 minute at 195 ℃, and the vacuum degree is controlled at 0.6 MPa.
Example 3:
a method for preparing PMMA/MBS/AS polymer composite material AMS comprises the following steps:
step a: mixing granular PMMA, granular MBS, granular AS, styrene-methacrylic acid, 2-hydroxy-4-n-octyloxy benzophenone, bis- (2,4, 6-tribromophenoxy), an antioxidant, isooctyl dithioglycolate di-n-octyltin, C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether according to the mass ratio of 1:3, drying and dehydrating methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer, weighing the materials according to the following formula, and mixing the materials to obtain the PMMA: 81.9%, MBS: 10%, AS: 6%, styrene-methacrylic acid: 0.5%, 2-hydroxy-4-n-octyloxy benzophenone: 0.1%, bis- (2,4, 6-tribromophenoxy): 0.2%, antioxidant: 0.3%, isooctyl dithioglycolate di-n-octyl tin: 0.2 percent of C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether are mixed according to the mass ratio of 1: 3: 0.1%, methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer: 0.2%, UV400 UV absorber: 0.5 percent; stirring and mixing the mixture for 2.5 minutes at 350rpm to obtain a mixed material;
step b: and (b) putting the material obtained in the step a into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product of the polymer composite material AMS. Wherein: a first zone of the double-screw extruder: 170 ℃, zone two: 185 ℃, three zones: 200 ℃, four zones: 210 ℃, five zones: 220 ℃, six zones: 225 ℃, seven zones: 230 ℃, eight zones: 235 ℃, nine zones 220 ℃, ten zones: 210 ℃, eleven zones: the retention time is controlled at 1 minute at 195 ℃, and the vacuum degree is controlled at 0.6 MPa.
Example 4:
a method for preparing PMMA/MBS/AS polymer composite material AMS comprises the following steps:
step a: mixing granular PMMA, granular MBS, granular AS, styrene-methacrylic acid, 2-hydroxy-4-n-octyloxy benzophenone, bis- (2,4, 6-tribromophenoxy), an antioxidant, isooctyl dithioglycolate di-n-octyltin, C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether according to the mass ratio of 1:3, drying and dehydrating methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer, weighing the materials according to the following formula, and mixing the materials to obtain the PMMA: 63.9%, MBS: 28%, AS: 6%, styrene-methacrylic acid: 0.5%, 2-hydroxy-4-n-octyloxy benzophenone: 0.1%, bis- (2,4, 6-tribromophenoxy): 0.2%, antioxidant: 0.3%, isooctyl dithioglycolate di-n-octyl tin: 0.2 percent of C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether are mixed according to the mass ratio of 1: 3: 0.1%, methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer: 0.2%, UV400 UV absorber: 0.5 percent; stirring and mixing the mixture for 2.5 minutes at 350rpm to obtain a mixed material;
step b: and (b) putting the material obtained in the step a into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product of the polymer composite material AMS. Wherein: a first zone of the double-screw extruder: 170 ℃, zone two: 185 ℃, three zones: 200 ℃, four zones: 210 ℃, five zones: 220 ℃, six zones: 225 ℃, seven zones: 230 ℃, eight zones: 235 ℃, nine zones 220 ℃, ten zones: 210 ℃, eleven zones: the retention time is controlled at 1 minute at 195 ℃, and the vacuum degree is controlled at 0.6 MPa.
Example 5:
a method for preparing PMMA/MBS/AS polymer composite material AMS comprises the following steps:
step a: mixing granular PMMA, granular MBS, granular AS, styrene-methacrylic acid, 2-hydroxy-4-n-octyloxy benzophenone, bis- (2,4, 6-tribromophenoxy), an antioxidant, isooctyl dithioglycolate di-n-octyltin, C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether according to the mass ratio of 1:3, drying and dehydrating methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer, weighing the materials according to the following formula, and mixing the materials to obtain the PMMA: 53.9%, MBS: 28%, AS: 16%, styrene-methacrylic acid: 0.5%, 2-hydroxy-4-n-octyloxy benzophenone: 0.1%, bis- (2,4, 6-tribromophenoxy): 0.2%, antioxidant: 0.3%, isooctyl dithioglycolate di-n-octyl tin: 0.2 percent of C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether are mixed according to the mass ratio of 1: 3: 0.1%, methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer: 0.2%, UV400 UV absorber: 0.5 percent; stirring and mixing the mixture for 2.5 minutes at 350rpm to obtain a mixed material;
step b: and (b) putting the material obtained in the step a into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product of the polymer composite material AMS. Wherein: a first zone of the double-screw extruder: 170 ℃, zone two: 185 ℃, three zones: 200 ℃, four zones: 210 ℃, five zones: 220 ℃, six zones: 225 ℃, seven zones: 230 ℃, eight zones: 235 ℃, nine zones 220 ℃, ten zones: 210 ℃, eleven zones: the retention time is controlled at 1 minute at 195 ℃, and the vacuum degree is controlled at 0.6 MPa.
Example 6:
a method for preparing PMMA/MBS/AS polymer composite material AMS comprises the following steps:
step a: mixing granular PMMA, granular MBS, granular AS, styrene-methacrylic acid, 2-hydroxy-4-n-octyloxy benzophenone, bis- (2,4, 6-tribromophenoxy), an antioxidant, isooctyl dithioglycolate di-n-octyltin, C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether according to the mass ratio of 1:3, drying and dehydrating methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer, weighing the materials according to the following formula, and mixing the materials to obtain the PMMA: 65.9%, MBS: 20%, AS: 12%, styrene-methacrylic acid: 0.5%, 2-hydroxy-4-n-octyloxy benzophenone: 0.1%, bis- (2,4, 6-tribromophenoxy): 0.2%, antioxidant: 0.3%, isooctyl dithioglycolate di-n-octyl tin: 0.2 percent of C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether are mixed according to the mass ratio of 1: 3: 0.1%, methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer: 0.2%, UV400 UV absorber: 0.5 percent; stirring and mixing the mixture for 2.5 minutes at 350rpm to obtain a mixed material;
step b: and (b) putting the material obtained in the step a into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product of the polymer composite material AMS. Wherein: a first zone of the double-screw extruder: 170 ℃, zone two: 185 ℃, three zones: 200 ℃, four zones: 210 ℃, five zones: 220 ℃, six zones: 225 ℃, seven zones: 230 ℃, eight zones: 235 ℃, nine zones 220 ℃, ten zones: 210 ℃, eleven zones: the retention time is controlled at 1 minute at 195 ℃, and the vacuum degree is controlled at 0.6 MPa.
Example 7:
a method for preparing PMMA/MBS/AS polymer composite material AMS comprises the following steps:
step a: mixing granular PMMA, granular MBS, granular AS, styrene-methacrylic acid, 2-hydroxy-4-n-octyloxy benzophenone, bis- (2,4, 6-tribromophenoxy), an antioxidant, isooctyl dithioglycolate di-n-octyltin, C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether according to the mass ratio of 1:3, drying and dehydrating methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer, weighing the materials according to the following formula, and mixing the materials to obtain the PMMA: 66.4%, MBS: 20%, AS: 12%, styrene-methacrylic acid: 0.5%, 2-hydroxy-4-n-octyloxy benzophenone: 0.1%, bis- (2,4, 6-tribromophenoxy): 0.2%, antioxidant: 0.3%, isooctyl dithioglycolate di-n-octyl tin: 0.2 percent of C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether are mixed according to the mass ratio of 1: 3: 0.1%, methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer: 0.2 percent; stirring and mixing the mixture for 2.5 minutes at 350rpm to obtain a mixed material;
step b: and (b) putting the material obtained in the step a into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product of the polymer composite material AMS. Wherein: a first zone of the double-screw extruder: 170 ℃, zone two: 185 ℃, three zones: 200 ℃, four zones: 210 ℃, five zones: 220 ℃, six zones: 225 ℃, seven zones: 230 ℃, eight zones: 235 ℃, nine zones 220 ℃, ten zones: 210 ℃, eleven zones: the retention time is controlled at 1 minute at 195 ℃, and the vacuum degree is controlled at 0.6 MPa.
Example 8:
a method for preparing PMMA/MBS/AS polymer composite material AMS comprises the following steps:
step a: mixing granular PMMA, granular MBS, granular AS, styrene-methacrylic acid, 2-hydroxy-4-n-octyloxy benzophenone, bis- (2,4, 6-tribromophenoxy), an antioxidant, isooctyl dithioglycolate di-n-octyltin, C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether according to the mass ratio of 1:3, drying and dehydrating methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer, weighing the materials according to the following formula, and mixing the materials to obtain the PMMA: 65.4%, MBS: 20%, AS: 12%, styrene-methacrylic acid: 1%, 2-hydroxy-4-n-octyloxy benzophenone: 0.1%, bis- (2,4, 6-tribromophenoxy): 0.2%, antioxidant: 0.3%, isooctyl dithioglycolate di-n-octyl tin: 0.2 percent of C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether are mixed according to the mass ratio of 1: 3: 0.1%, methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer: 0.2%, UV400 UV absorber: 0.5 percent; stirring and mixing the mixture for 2.5 minutes at 350rpm to obtain a mixed material;
step b: and (b) putting the material obtained in the step a into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product of the polymer composite material AMS. Wherein: a first zone of the double-screw extruder: 170 ℃, zone two: 185 ℃, three zones: 200 ℃, four zones: 210 ℃, five zones: 220 ℃, six zones: 225 ℃, seven zones: 230 ℃, eight zones: 235 ℃, nine zones 220 ℃, ten zones: 210 ℃, eleven zones: the retention time is controlled at 1 minute at 195 ℃, and the vacuum degree is controlled at 0.6 MPa.
Example 9:
a method for preparing PMMA/MBS/AS polymer composite material AMS comprises the following steps:
step a: mixing granular PMMA, granular MBS, granular AS, styrene-methacrylic acid, 2-hydroxy-4-n-octyloxy benzophenone, bis- (2,4, 6-tribromophenoxy), an antioxidant, isooctyl dithioglycolate di-n-octyltin, C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether according to the mass ratio of 1:3, drying and dehydrating methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer, weighing the materials according to the following formula, and mixing the materials to obtain the PMMA: 65.7%, MBS: 20%, AS: 12%, styrene-methacrylic acid: 0.5%, 2-hydroxy-4-n-octyloxy benzophenone: 0.3%, bis- (2,4, 6-tribromophenoxy): 0.2%, antioxidant: 0.3%, isooctyl dithioglycolate di-n-octyl tin: 0.2 percent of C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether are mixed according to the mass ratio of 1: 3: 0.1%, methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer: 0.2%, UV400 UV absorber: 0.5 percent; stirring and mixing the mixture for 2.5 minutes at 350rpm to obtain a mixed material;
step b: and (b) putting the material obtained in the step a into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product of the polymer composite material AMS. Wherein: a first zone of the double-screw extruder: 170 ℃, zone two: 185 ℃, three zones: 200 ℃, four zones: 210 ℃, five zones: 220 ℃, six zones: 225 ℃, seven zones: 230 ℃, eight zones: 235 ℃, nine zones 220 ℃, ten zones: 210 ℃, eleven zones: the retention time is controlled at 1 minute at 195 ℃, and the vacuum degree is controlled at 0.6 MPa.
Example 10:
a method for preparing PMMA/MBS/AS polymer composite material AMS comprises the following steps:
step a: mixing granular PMMA, granular MBS, granular AS, styrene-methacrylic acid, 2-hydroxy-4-n-octyloxy benzophenone, bis- (2,4, 6-tribromophenoxy), an antioxidant, isooctyl dithioglycolate di-n-octyltin, C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether according to the mass ratio of 1:3, drying and dehydrating methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer, weighing the materials according to the following formula, and mixing the materials to obtain the PMMA: 65.6 percent and MBS: 20%, AS: 12%, styrene-methacrylic acid: 0.5%, 2-hydroxy-4-n-octyloxy benzophenone: 0.1%, bis- (2,4, 6-tribromophenoxy): 0.2%, antioxidant: 0.3%, isooctyl dithioglycolate di-n-octyl tin: 0.5 percent, C12 fatty alcohol polyoxypropylene polyoxyethylene ether phosphate and organic silicon polyoxyethylene ether are mixed according to the mass ratio of 1: 3: 0.1%, methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer: 0.2%, UV400 UV absorber: 0.5 percent; stirring and mixing the mixture for 2.5 minutes at 350rpm to obtain a mixed material;
step b: and (b) putting the material obtained in the step a into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product of the polymer composite material AMS. Wherein: a first zone of the double-screw extruder: 170 ℃, zone two: 185 ℃, three zones: 200 ℃, four zones: 210 ℃, five zones: 220 ℃, six zones: 225 ℃, seven zones: 230 ℃, eight zones: 235 ℃, nine zones 220 ℃, ten zones: 210 ℃, eleven zones: the retention time is controlled at 1 minute at 195 ℃, and the vacuum degree is controlled at 0.6 MPa.
Comparative example 1
A method for preparing AMS which is a PMMA/MBS/AS polymer composite material, under the same conditions AS example 6 except that MBS is not added in the step (a) and PMMA is added in an amount of 85.9%.
Comparative example 2
A method for preparing AMS which is a PMMA/MBS/AS polymer composite material, under the same conditions AS in example 6 except that AS is not added in the step (a) and the amount of PMMA added is 77.9%.
Comparative example 3
A method for preparing AMS which is a PMMA/MBS/AS polymer composite material, the preparation method is the same AS that of the example 6 except that MBS and AS are not added in the step (a) and the addition amount of PMMA is 97.9%.
Comparative example 4
A process for preparing an AMS PMMA/MBS/AS polymer composite, except for step (b), in a first zone of a twin-screw extruder: 175 ℃, zone two: 190 ℃, three zones: 205 ℃, four zones: 215 ℃, five zones: 225 ℃, six zones: 230 ℃, seven zones: 235 ℃, eight zones: 240 ℃, nine zones 225 ℃, ten zones: 215 ℃, eleven regions: the temperature was 200 ℃ and the other conditions were the same as in example 6.
Comparative example 5
A process for preparing an AMS PMMA/MBS/AS polymer composite, except for step (b), in a first zone of a twin-screw extruder: 180 ℃, zone two: 190 ℃, three zones: 210 ℃, four zones: 220 ℃, five zones: 225 ℃, six zones: 230 ℃, seven zones: 235 ℃, eight zones: 240 ℃, nine zones 230 ℃, ten zones: 220 ℃, eleven zones: 195 ℃ and the other conditions were the same as in example 6.
The specific gravities of examples 1 to 10 and comparative examples 1 to 5 were measured in accordance with ASTM D792/(GB/T1033), notched impact strength in accordance with ASTM D256/(GB/T1843), tensile properties in accordance with ASTM D638/(GB/T1040), flexural properties in accordance with ASTM D790/(GB/T9341), flame retardancy in accordance with UL-94/(GB/T2408), melt index in accordance with ASTM D1238/(GB/T3682), light transmittance in accordance with ASTM D1003/(GB 2410 to 80), light transmittance in accordance with ASTM 1003/(GB/2410 to 80, heat distortion temperature in accordance with ASTM D648(GB/T1643.1), the gloss measurement is carried out according to ASTM D2457 (GB/T8807) and the pencil hardness measurement is carried out according to ASTM D3363/(GB/T6739).
The performance test results are shown below:
watch 1
Item Condition/method Unit of Example 1 Example 2 Example 3 Example 4 Example 5
Refractive index nd - 1.49 1.49 1.49 1.49 1.49
Light transmittance 3.2mm ％ 91.0 91.0 91.5 91.0 90.0
Haze degree 3.2mm ％ 0.6 0.5 0.5 0.6 0.7
Fluidity of the resin 230℃/3.8kg g/10min 4.1 4.3 2.4 4.2 4.4
ViCAT softening Property B/50 ℃ 92.0 92.0 95.0 92.0 90.0
Heat distortion temperature 1.8MPa ℃ 84.3 83.5 93.3 84.5 83.3
Coefficient of linear expansion - 1×10-4/℃ 0.7 0.7 0.7 0.7 0.7
charpy impact strength nodched KJ/m2 3.0 3.2 2.7 3.0 3.4
Hardness of pencil 750g - 2H 2H 2H 2H 2H
Tensile strength 5mm/min MPa 46.0 47.0 45.0 47.0 45.0
Elongation percentage 5mm/min ％ 35 35 34 35 36
Tensile modulus 1mm/min GPa 1.78 2.3 2.1 1.8 1.9
Bending strength 2mm/min MPa 81 80 85 80 77
Flexural modulus 2mm/min GPa 2.1 2.2 2.4 2.0 2.1
Density of - g/cm3 1.18 1.17 1.17 1.17 1.17
Molding shrinkage ratio - ％ 0.6 0.5 0.4 0.5 0.4
Water absorption rate 23℃，24hr ％ 0.4 0.4 0.4 0.4 0.4
Flame retardant properties 1.5mm Class HB HB HB HB HB
Ultraviolet transmittance - ％ 1.6 1.7 1.8 1.5 1.6
Watch two
Item Condition/method Unit of Example 6 Example 7 Example 8 Example 9 Example 10
Refractive index nd - 1.49 1.49 1.49 1.49 1.49
Light transmittance 3.2mm ％ 91.0 91.0 90.8 90.7 90.8
Haze degree 3.2mm ％ 0.5 0.5 0.5 0.6 0.6
Fluidity of the resin 230℃/3.8kg g/10min 3.4 3.4 3.4 3.5 3.4
ViCAT softening Property B/50 ℃ 92.0 92.0 92.0 93.5 92.0
Heat distortion temperature 1.8MPa ℃ 83.3 83.3 80.3 82.9 83.3
Coefficient of linear expansion - 1×10-4/℃ 0.7 0.7 0.7 0.7 0.7
charpy impact strength nodched kJ/m2 3.3 3.3 3.3 3.3 3.6
Hardness of pencil 750g - 2H 2H 2H 2H 2H
Tensile strength 5mm/min MPa 42.0 42.0 42.0 42.0 42.0
Elongation percentage 5mm/min ％ 34 34 34 34 34
Tensile modulus 1mm/min GPa 1.99 1.99 1.99 1.99 1.99
Bending strength 2mm/min MPa 75 75 75 75 75
Flexural modulus 2mm/min GPa 2.0 2.0 2.0 2.0 2.0
Density of - g/cm3 1.17 1.17 1.17 1.17 1.17
Molding shrinkage ratio - ％ 0.4 0.4 0.4 0.4 0.4
Water absorption rate 23℃，24hr ％ 0.4 0.4 0.4 0.4 0.4
Flame retardant properties 1.5mm Class HB HB HB HB HB
Ultraviolet transmittance - ％ 1.6 14.8 1.6 1.6 1.6
Watch III
Item Condition/method Unit of Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
Refractive index nd - 1.49 1.49 1.49 1.49 1.49
Light transmittance 3.2mm ％ 91.6 91.7 92 91.2 91.3
Haze degree 3.2mm ％ 0.3 0.4 0.2 0.5 0.5
Fluidity of the resin 230℃/3.8kg g/10min 1.8 2.0 1.4 3.4 3.4
ViCAT softening Property B/50 ℃ 100 98 106 92.0 92.0
Heat distortion temperature 1.8MPa ℃ 95 94 100 83.3 83.3
Coefficient of linear expansion - 1×10-4/℃ 0.6 0.6 0.6 0.7 0.7
charpy impact strength nodched kJ/m2 1.7 1.9 1.5 3.3 3.3
Hardness of pencil 750g - 3H 3H 3H 2H 2H
Tensile strength 5mm/min MPa 61 57 71 42.0 42.0
Elongation percentage 5mm/min ％ 16 21 6 34 34
Tensile modulus 1mm/min GPa 2.9 2.9 2.9 1.99 1.99
Bending strength 2mm/min MPa 102 98 113 75 75
Flexural modulus 2mm/min GPa 3.0 3.0 3.0 2.0 2.0
Density of - g/cm3 1.19 1.19 1.19 1.17 1.17
Molding shrinkage ratio - ％ 0.9 0.8 1.19 0.4 0.4
Water absorption rate 23℃，24hr ％ 0.4 0.4 0.4 0.4 0.4
Flame retardant properties 1.5mm Class HB HB HB HB HB
Ultraviolet transmittance - ％ 1.7 1.7 1.8 1.6 1.6
As can be seen from examples 1 to 6 and comparative examples 1 to 3, the addition of MBS can effectively improve the impact strength of the material, but AMS has poor weather resistance, the addition of AS can effectively improve the weather resistance of the material and has small influence on light transmittance, but if AS and AMS are increased in the same ratio, the light transmittance of the material can be reduced, the haze of the material can be improved, and the influence on the optical performance of the material is large, AS can be seen from examples 6 and 7, the UV400 ultraviolet absorbent mainly improves the ultraviolet resistance of the material, and AS can be seen from examples 8 to 10, the compatilizer can effectively improve the heat distortion temperature of the material but has influence on light transmittance; the weather resisting agent can effectively improve the fluidity and the heat distortion temperature but has the influence on the haze and the light transmittance, and the heat stabilizing agent can effectively improve the impact capability of the material but has the influence on the light transmittance and the haze of the material. Example 6 and comparative examples 4-5 show that the temperature of the twin screw extruder has an effect on the optical properties of the material, but not much.
The above; but are merely preferred embodiments of the invention; the scope of the invention is not limited thereto; any person skilled in the art is within the technical scope of the present disclosure; the technical scheme and the improved concept of the invention are equally replaced or changed; are intended to be covered by the scope of the present invention.

Claims (10)

1. A PMMA/MBS/AS polymer composite AMS is characterized in that: comprises the following raw materials in percentage by weight: PMMA: 48-84%, MBS: 10-30%, AS: 5-18%, compatibilizer: 0.1-1%, weather-resistant agent: 0.1-0.3%, flame retardant: 0.2-0.5%, antioxidant: 0.2-0.5%, heat stabilizer: 0.2-0.5%, dispersing agent: 0.1 to 0.2%, light stabilizer: 0.1 to 0.2 percent;
the PMMA is polymethyl methacrylate, the MBS is a terpolymer of methyl methacrylate, butadiene and styrene, and the AS is a graft copolymer of acrylonitrile and styrene.
2. A PMMA/MBS/AS polymer composite AMS according to claim 1 wherein: the compatilizer is one or more of styrene-methacrylic acid, styrene-maleic anhydride copolymer and styrene-maleic anhydride copolymer.
3. A PMMA/MBS/AS polymer composite AMS according to claim 1 wherein: the weather resisting agent is one or a mixture of 2-hydroxy-4-n-octoxy benzophenone, salicylate, benzophenone, triazine and hindered amine free radical scavenger.
4. A PMMA/MBS/AS polymer composite AMS according to claim 1 wherein: the flame retardant is one or a mixture of more of bis- (2,4, 6-tribromophenoxy), ethane bisphenol A-bis (diphenyl phosphate) and tolyl diphenyl phosphate.
5. A PMMA/MBS/AS polymer composite AMS according to claim 1 wherein: the antioxidant is prepared by mixing a phenol antioxidant, a phosphate antioxidant and a thioester antioxidant according to the mass ratio of 1:1: 1.
6. A PMMA/MBS/AS polymer composite AMS according to claim 1 wherein: the heat stabilizer is octyl tin stabilizer.
7. A PMMA/MBS/AS polymer composite AMS according to claim 1 wherein: the light stabilizer is methacrylic acid (2,2,6, 6-tetramethyl) piperidine copolymer.
8. A PMMA/MBS/AS polymer composite AMS according to claim 1 wherein: also included are UV400 UV absorbers: 0.3 to 0.5 percent.
9. Method for preparing an AMS of PMMA/MBS/AS polymer composite AS defined in any one of claims 1 to 8, characterized in that: the method comprises the following steps:
step a: drying and dehydrating granular PMMA, granular MBS, granular AS, a compatilizer, a weather resistant agent, a flame retardant, an antioxidant, a heat stabilizer, a diffusant and a light stabilizer, weighing the materials according to the formula, and fully stirring and uniformly mixing;
step b: and (b) putting the material obtained in the step a into a double-screw extruder, and carrying out melting, blending, cooling and granulation in the double-screw extruder to obtain the product AMS.
10. The method for preparing the PMMA/MBS/AS polymer composite AMS AS claimed in claim 9, wherein the method comprises the following steps: in the step a: the stirring speed is 300-500rpm, and the stirring time is 2-4 minutes; in the step b: the twin-screw extruder is divided into 11 sections, and the temperature setting range of each section is as follows: a first area: 170-185 ℃, and a second zone: 185-200 ℃, and three zones: 200-210 ℃, four zones: 210-220 ℃, five zones: 220-225 ℃, six zones: 225-230 ℃, seven areas: 230-235 ℃ and eight zones: 235-240 ℃, 220-235 ℃ in the nine zones, and ten zones: 210-220 ℃, eleven regions: 195-200 ℃, the retention time is controlled to be 1-2 minutes, and the vacuum degree is controlled to be 0.6-0.8 MPa.
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