CN107841077A - A kind of heat resistant transparent PMMA/ASA alloy materials and preparation method thereof - Google Patents
A kind of heat resistant transparent PMMA/ASA alloy materials and preparation method thereof Download PDFInfo
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- CN107841077A CN107841077A CN201711097289.3A CN201711097289A CN107841077A CN 107841077 A CN107841077 A CN 107841077A CN 201711097289 A CN201711097289 A CN 201711097289A CN 107841077 A CN107841077 A CN 107841077A
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- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 91
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 239000000956 alloy Substances 0.000 title claims abstract description 47
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 51
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 43
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 33
- 238000005453 pelletization Methods 0.000 claims description 25
- 239000004611 light stabiliser Substances 0.000 claims description 20
- -1 sulphur ester Chemical class 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 16
- 239000005864 Sulphur Substances 0.000 claims description 15
- 239000002530 phenolic antioxidant Substances 0.000 claims description 15
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000008188 pellet Substances 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 1
- 239000008117 stearic acid Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 5
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 abstract description 3
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 15
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001565 benzotriazoles Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229920000800 acrylic rubber Polymers 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- 229920005479 Lucite® Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LEDRCCVNHBPBAG-UHFFFAOYSA-N benzene;prop-2-enenitrile Chemical compound C=CC#N.C1=CC=CC=C1 LEDRCCVNHBPBAG-UHFFFAOYSA-N 0.000 description 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention provides a kind of transparent PMMA/ASA alloy materials and preparation method, includes according to the composition of alloy material described in mass percent meter：PMMA 48~73.5%, ASA 15~30%, styrene methyl methacrylate anhydrous maleic acid anhydride polymer 10~30%, antioxidant 0.3~0.6% and auxiliary agent 0.8~1.5%.The alloy material has excellent heat resistance, mechanical performance, transparency, glossiness and ageing-resistant performance.
Description
Technical field
The invention belongs to polymeric material field, is related to a kind of transparent PMMA/ASA alloy materials and preparation method thereof.
Background technology
Polymethyl methacrylate (PMMA, is commonly called as lucite, acryl or acrylic), has crystal in general transparent
Degree, for light transmittance up to more than 92%, being stained with dyestuff has good color development effect.In addition, PMMA has splendid weatherability, higher
Case hardness and lustrous surface and preferable high-temperature behavior.PMMA in aviation, automobile, electronics, medical treatment, chemical industry, building materials, defend
The industry such as bath and Advertisement label is widely used.
The A of CN 101870794 disclose a kind of transparent toughened polymethyl methacrylate (PMMA) material and preparation method thereof.Transparent toughened polymethyl methacrylate (PMMA) material
Material, it is composed of the following components by weight percentage：Polymethyl methacrylate 70-80%；Toughener 20-30%；Lubricant
0.5-1%；Antioxidant 0.2-0.6%.The invention uses MBS toughness reinforcings, and it is strong that this toughened system can effectively improve PMMA impacts
Degree, and transparency is not influenceed, but MBS contains butadiene unsaturated double-bond in itself, weatherability is poor, seriously limits PMMA materials
Material uses out of doors.
The A of CN 106046643 disclose a kind of high high-compatibility PMMA/ASA alloy resin compositions and preparation method thereof,
The composition includes following components and content：Polymethyl methacrylate (PMMA) resin 65-80 parts by weight, acrylonitrile-benzene
Ethylene-butyl acrylate (ASA) resin 15-25 parts by weight, compatilizer 8-15 parts by weight, processing aid 0.51.5 parts by weight；Will
Above-mentioned raw material premix 3-10 minutes in high-speed mixer, and then premix obtains through double screw extruder extruding pelletization
PMMA/ASA alloy resin compositions.But its PMMA/ASA alloy provided is opaque, have impact on it in lighting advertisement board
Deng the application in field.
The content of the invention
To solve technical problem present in prior art, the present invention provide a kind of transparent PMMA/ASA alloy materials and its
Preparation method, the alloy material have excellent heat resistance, mechanical performance, transparency, glossiness and ageing-resistant performance.
To reach above-mentioned purpose, the present invention uses following technical scheme：
It is an object of the present invention to provide a kind of transparent PMMA/ASA alloy materials, according to conjunction described in mass percent meter
The composition of golden material includes：
Wherein, PMMA mass percent can be 48%, 50%, 55%, 60%, 65%, 70% or 73.5% etc.,
ASA mass percent can be 15%, 16%, 18%, 20%, 22%, 25%, 28% or 30% etc., styrene-methyl third
The mass percent of e pioic acid methyl ester-anhydrous maleic acid anhydride polymer be 10%, 12%, 15%, 18%, 20%, 22%, 25%,
28% or 30% etc., the mass percent of antioxidant can be 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55% or
0.6% etc., the mass parts of auxiliary agent can be 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4% or 1.5% etc.,
It is not limited to cited numerical value, other interior unrequited numerical value of above-mentioned each number range are equally applicable.
Acrylic rubber (ASA) toughened polymethyl methacrylate (PMMA) that the present invention is coated using SAN, acrylic rubber have excellent weather resistance
Can, just there are SAN claddings, can improve acrylic rubber and PMMA compatibility, and the dispersion effect in PMMA, but third
The addition of olefin(e) acid rubber, the HDT hydraulic performance declines of PMMA materials can be caused again, therefore introduce third component MSM, improved and improve PMMA
Heat resistance.
The number-average molecular weight for the PMMA that the present invention uses is 25~350,000, and the methyl methacrylate in the PMMA contains
Measure as 98~100%.Wherein PMMA number-average molecular weight can be 250,000,260,000,270,000,280,000,290,000,300,000,310,000,32
Ten thousandth, 330,000,340,000 or 350,000 etc., the content of the methyl methacrylate in PMMA can be 98%, 98.2%, 98.5%,
98.8%th, 99%, 99.2%, 99.5%, 99.8% or 100% etc., it is not limited to cited numerical value, above-mentioned each numerical value
In the range of other unrequited numerical value it is equally applicable.
The number-average molecular weight for the ASA that the present invention uses is 25~30W, such as 25W, 26W, 27W, 28W, 29W or 30W, but
It is not limited in cited numerical value, other unrequited numerical value are equally applicable in the number range.
The styrene methyl methacrylate that the present invention uses-anhydrous maleic acid anhydride polymer is by styrene-methyl third
E pioic acid methyl ester copolymer is added to reactive extrursion in double screw extruder and is prepared into after being mixed with anhydrous maleic acid acid anhydride and initiator
Arrive.Specific preparation method is prior art, is repeated no more in specification.
The styrene methyl methacrylate that the present invention uses-anhydrous maleic acid anhydride polymer number-average molecular weight be 10~
15W, such as 10W, 11W, 12W, 13W, 14W or 15W, it is not limited to cited numerical value, in the number range, other are not
The numerical value enumerated is equally applicable.
As currently preferred technical scheme, the antioxidant is phenolic antioxidant, phosphoric acid ester antioxidant and sulphur
The composition of esters antioxidant.
Wherein, the phenolic antioxidant can be four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites
Ester (antioxidant 1010) and/or β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester (antioxidant 1076), phosphoric acid
Esters antioxidant can be three (2,4- di-tert-butyl-phenyls) phosphite esters (irgasfos 168) and/or double (2,4- di-tert-butyls
Base) pentaerythritol diphosphites (antioxidant 6280), sulphur ester antioxidant can be (the 3- lauryls thio third of pentaerythrite four
Acid esters) (antioxidant 412S).The mass ratio of the phenolic antioxidant, phosphoric acid ester antioxidant and sulphur ester antioxidant can be
(1~2):(1~2):1, such as 1:2:1、1.1:1.8:1、1.2:1.5:1、1.5:1.2:1、1.8:1.1:1 or 2:1:1 etc., but simultaneously
Cited numerical value is not limited only to, other unrequited numerical value are equally applicable in the number range.
As currently preferred technical scheme, the mass percent of the phenolic antioxidant is 0.10~0.20%, such as
0.10%th, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19% or 0.20%
Deng it is not limited to cited numerical value, other unrequited numerical value are equally applicable in the number range.
Preferably, the mass percent of the phosphoric acid ester antioxidant be 0.10~0.20%, such as 0.10%, 0.11%,
0.12%th, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19% or 0.20% etc., but simultaneously not only limit
It is equally applicable in other unrequited numerical value in cited numerical value, the number range.
Preferably, the mass percent of the sulphur ester antioxidant be 0.10~0.20%, such as 0.10%, 0.11%,
0.12%th, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19% or 0.20% etc., but simultaneously not only limit
It is equally applicable in other unrequited numerical value in cited numerical value, the number range.
The present invention can effectively improve glossiness of the material after xenon lamp aging test using the antioxidant systems of compounding
Conservation rate, and ternary built synergy is optimal.
As currently preferred technical scheme, the auxiliary agent includes ultraviolet absorber, light stabilizer and lubricant.
As currently preferred technical scheme, the UV absorption machine is benzotriazole ultraviolet absorber.
Preferably, the mass percent of the ultraviolet absorber be 0.20~0.40%, such as 0.20%, 0.22%,
0.25%th, 0.28%, 0.30%, 0.32%, 0.35%, 0.38% or 0.40% etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the number range.
Preferably, the light stabilizer is hindered amine light stabilizer.
Preferably, the mass percent of the light stabilizer be 0.40~0.70%, such as 0.40%, 0.45%, 0.50%,
0.55%th, 0.60%, 0.65% or 0.70% etc., it is not limited to cited numerical value, interior other of the number range do not arrange
The numerical value of act is equally applicable.
As currently preferred technical scheme, the lubricant is pentaerythritol tetrastearate.
Preferably, the mass percent of the lubricant be 0.20~0.40%, such as 0.20%, 0.22%, 0.25%,
0.28%th, 0.30%, 0.32%, 0.35%, 0.38% or 0.40% etc., it is not limited to cited numerical value, the numerical value
In the range of other unrequited numerical value it is equally applicable.
The two of the object of the invention are to provide a kind of preparation method of above-mentioned PMMA/ASA alloy materials, the preparation method
Comprise the following steps：
(1) PMMA, ASA, styrene methyl methacrylate-anhydrous maleic acid anhydride polymer, antioxidant and auxiliary agent are existed
Stirring is lower to be mixed, and obtains compound；
(2) compound for obtaining step (1) is added in double screw extruder, and extruding pelletization obtains the PMMA/ASA and closed
Golden material.
As currently preferred technical scheme, the speed of step (1) described stirring is 100~500rpm, as 100rpm,
150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm or 500rpm etc., it is not limited to cited
Numerical value, other unrequited numerical value are equally applicable in the number range, preferably 200~300rpm.
Preferably, the time of the stirring is 2~4min, as 2min, 2.2min, 2.5min, 2.8min, 3min,
3.2min, 3.5min, 3.8min or 4min etc., it is not limited to cited numerical value, other are unrequited in the number range
Numerical value it is equally applicable.
As currently preferred technical scheme, the pellet feeding section extrusion temperature of step (2) described double screw extruder
For 170~190 DEG C, such as 170 DEG C, 172 DEG C, 175 DEG C, 178 DEG C, 180 DEG C, 182 DEG C, 185 DEG C, 188 DEG C or 190 DEG C, but simultaneously
Cited numerical value is not limited only to, other unrequited numerical value are equally applicable in the number range.
Preferably, the fluxing zone extrusion temperature of step (2) described double screw extruder is 200~220 DEG C, such as 200 DEG C,
202 DEG C, 205 DEG C, 208 DEG C, 210 DEG C, 212 DEG C, 215 DEG C, 218 DEG C or 220 DEG C etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the number range.
Preferably, the melt conveying zone extrusion temperature of step (2) described double screw extruder is 190~220 DEG C, such as 190
DEG C, 195 DEG C, 200 DEG C, 205 DEG C, 210 DEG C, 215 DEG C or 220 DEG C etc., it is not limited to cited numerical value, the number range
Other interior unrequited numerical value are equally applicable.
Preferably, the head temperature of step (2) described double screw extruder be 210~230 DEG C, such as 210 DEG C, 212 DEG C,
215 DEG C, 218 DEG C, 220 DEG C, 222 DEG C, 225 DEG C, 228 DEG C or 230 DEG C etc., it is not limited to cited numerical value, the numerical value
In the range of other unrequited numerical value it is equally applicable.
As currently preferred technical scheme, the vacuum of step (2) described extruding pelletization is 0.6~0.8MPa,
0.6MPa, 0.62MPa, 0.65MPa, 0.68MPa, 0.7MPa, 0.72MPa, 0.75MPa, 0.78MPa or 0.8MPa etc., but simultaneously
Cited numerical value is not limited only to, other unrequited numerical value are equally suitable in the number range.
Compared with prior art, the present invention at least has the advantages that：
(1) present invention provides a kind of transparent PMMA/ASA alloy materials, and the alloy material has excellent heat resistance,
Heat distortion temperature is up to 85.3~103.6 DEG C, and the glossiness of the alloy material is dropped by less than 10% after resistance to Thermal test；
(2) present invention provides a kind of transparent PMMA/ASA alloy materials, and the alloy material has excellent mechanical performance,
Notched Izod impact hit intensity is up to 96.3J/M, and tensile strength is up to 68.5MPa, and bending strength is up to 96.6MPa；
(3) present invention provides a kind of transparent PMMA/ASA alloy materials, and the alloy material has excellent transparency, light
Damp degree and ageing-resistant performance, transparency is up to 86.6%, and glossiness is up to 86.2；
(4) present invention provides a kind of preparation method of transparent PMMA/ASA alloy materials, and the preparation method technique is simple,
Suitable for industrialized production.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method comprise the following steps：
(1) by 73.3g PMMA, 15g ASA, 10g styrene methyl methacrylates-anhydrous maleic acid anhydride polymer,
0.2g phenolic antioxidants, 0.2g phosphoric acid esters antioxidant, 0.1g sulphur ester antioxidants, 0.3g benzotriazoles ultraviolet absorber,
0.6g hindered amine light stabilizers and 0.3g pentaerythritol tetrastearates are stirred 3min at 200 rpm, are mixed
Material；
(2) compound for obtaining step (1) is added in double screw extruder, and extruding pelletization obtains the PMMA/ASA and closed
Golden material.
Wherein, the pellet feeding section extrusion temperature of the double screw extruder is 180 DEG C, and fluxing zone extrusion temperature is 210
DEG C, melt conveying zone extrusion temperature is 205 DEG C, and head temperature is 220 DEG C, and the vacuum of extruding pelletization is 0.7MPa.
Embodiment 2
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method comprise the following steps：
(1) by 68.3g PMMA, 20g ASA, 10g styrene methyl methacrylates-anhydrous maleic acid anhydride polymer,
0.2g phenolic antioxidants, 0.2g phosphoric acid esters antioxidant, 0.1g sulphur ester antioxidants, 0.3g benzotriazoles ultraviolet absorber,
0.6g hindered amine light stabilizers and 0.3g pentaerythritol tetrastearates are stirred 1min at 500 rpm, are mixed
Material；
(2) compound for obtaining step (1) is added in double screw extruder, and extruding pelletization obtains the PMMA/ASA and closed
Golden material.
Wherein, the pellet feeding section extrusion temperature of the double screw extruder is 180 DEG C, and fluxing zone extrusion temperature is 210
DEG C, melt conveying zone extrusion temperature is 205 DEG C, and head temperature is 220 DEG C, and the vacuum of extruding pelletization is 0.7MPa.
Embodiment 3
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method comprise the following steps：
(1) by 63.3g PMMA, 25g ASA, 10g styrene methyl methacrylates-anhydrous maleic acid anhydride polymer,
0.2g phenolic antioxidants, 0.2g phosphoric acid esters antioxidant, 0.1g sulphur ester antioxidants, 0.3g benzotriazoles ultraviolet absorber,
0.6g hindered amine light stabilizers and 0.3g pentaerythritol tetrastearates are stirred 1min at 500 rpm, are mixed
Material；
(2) compound for obtaining step (1) is added in double screw extruder, and extruding pelletization obtains the PMMA/ASA and closed
Golden material.
Wherein, the pellet feeding section extrusion temperature of the double screw extruder is 180 DEG C, and fluxing zone extrusion temperature is 210
DEG C, melt conveying zone extrusion temperature is 205 DEG C, and head temperature is 220 DEG C, and the vacuum of extruding pelletization is 0.7MPa.
Embodiment 4
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method comprise the following steps：
(1) by 58.3g PMMA, 30g ASA, 10g styrene methyl methacrylates-anhydrous maleic acid anhydride polymer,
0.2g phenolic antioxidants, 0.2g phosphoric acid esters antioxidant, 0.1g sulphur ester antioxidants, 0.3g benzotriazoles ultraviolet absorber,
0.6g hindered amine light stabilizers and 0.3g pentaerythritol tetrastearates are stirred 1min at 500 rpm, are mixed
Material；
(2) compound for obtaining step (1) is added in double screw extruder, and extruding pelletization obtains the PMMA/ASA and closed
Golden material.
Wherein, the pellet feeding section extrusion temperature of the double screw extruder is 180 DEG C, and fluxing zone extrusion temperature is 210
DEG C, melt conveying zone extrusion temperature is 205 DEG C, and head temperature is 220 DEG C, and the vacuum of extruding pelletization is 0.7MPa.
Embodiment 5
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method comprise the following steps：
(1) by 63.3g PMMA, 20g ASA, 15g styrene methyl methacrylates-anhydrous maleic acid anhydride polymer,
0.2g phenolic antioxidants, 0.2g phosphoric acid esters antioxidant, 0.1g sulphur ester antioxidants, 0.3g benzotriazoles ultraviolet absorber,
0.6g hindered amine light stabilizers and 0.3g pentaerythritol tetrastearates are stirred 1min at 500 rpm, are mixed
Material；
(2) compound for obtaining step (1) is added in double screw extruder, and extruding pelletization obtains the PMMA/ASA and closed
Golden material.
Wherein, the pellet feeding section extrusion temperature of the double screw extruder is 180 DEG C, and fluxing zone extrusion temperature is 210
DEG C, melt conveying zone extrusion temperature is 205 DEG C, and head temperature is 220 DEG C, and the vacuum of extruding pelletization is 0.7MPa.
Embodiment 6
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method comprise the following steps：
(1) by 58.3g PMMA, 20g ASA, 20g styrene methyl methacrylates-anhydrous maleic acid anhydride polymer,
0.2g phenolic antioxidants, 0.2g phosphoric acid esters antioxidant, 0.1g sulphur ester antioxidants, 0.3g benzotriazoles ultraviolet absorber,
0.6g hindered amine light stabilizers and 0.3g pentaerythritol tetrastearates are stirred 1min at 500 rpm, are mixed
Material；
(2) compound for obtaining step (1) is added in double screw extruder, and extruding pelletization obtains the PMMA/ASA and closed
Golden material.
Wherein, the pellet feeding section extrusion temperature of the double screw extruder is 180 DEG C, and fluxing zone extrusion temperature is 210
DEG C, melt conveying zone extrusion temperature is 205 DEG C, and head temperature is 220 DEG C, and the vacuum of extruding pelletization is 0.7MPa.
Embodiment 7
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method comprise the following steps：
(1) by 53.3g PMMA, 20g ASA, 25g styrene methyl methacrylates-anhydrous maleic acid anhydride polymer,
0.2g phenolic antioxidants, 0.2g phosphoric acid esters antioxidant, 0.1g sulphur ester antioxidants, 0.3g benzotriazoles ultraviolet absorber,
0.6g hindered amine light stabilizers and 0.3g pentaerythritol tetrastearates are stirred 1min at 500 rpm, are mixed
Material；
(2) compound for obtaining step (1) is added in double screw extruder, and extruding pelletization obtains the PMMA/ASA and closed
Golden material.
Wherein, the pellet feeding section extrusion temperature of the double screw extruder is 180 DEG C, and fluxing zone extrusion temperature is 210
DEG C, melt conveying zone extrusion temperature is 205 DEG C, and head temperature is 220 DEG C, and the vacuum of extruding pelletization is 0.7MPa.
Embodiment 8
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method comprise the following steps：
(1) by 48.3g PMMA, 20g ASA, 30g styrene methyl methacrylates-anhydrous maleic acid anhydride polymer,
0.2g phenolic antioxidants, 0.2g phosphoric acid esters antioxidant, 0.1g sulphur ester antioxidants, 0.3g benzotriazoles ultraviolet absorber,
0.6g hindered amine light stabilizers and 0.3g pentaerythritol tetrastearates are stirred 1min at 500 rpm, are mixed
Material；
(2) compound for obtaining step (1) is added in double screw extruder, and extruding pelletization obtains the PMMA/ASA and closed
Golden material.
Wherein, the pellet feeding section extrusion temperature of the double screw extruder is 180 DEG C, and fluxing zone extrusion temperature is 210
DEG C, melt conveying zone extrusion temperature is 205 DEG C, and head temperature is 220 DEG C, and the vacuum of extruding pelletization is 0.7MPa.
Embodiment 9
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method comprise the following steps：
(1) by 63.7g PMMA, 20g ASA, 15g styrene methyl methacrylates-anhydrous maleic acid anhydride polymer,
0.1g antioxidant 1076s, 0.1g antioxidant 6280,0.2g antioxidant 412S, 0.2g ultraviolet absorber UV-P, 0.4g light stabilizers
1min is stirred with 777D and 0.2g pentaerythritol tetrastearates at 500 rpm, obtains compound；
(2) compound for obtaining step (1) is added in double screw extruder, and extruding pelletization obtains the PMMA/ASA and closed
Golden material.
Wherein, the pellet feeding section extrusion temperature of the double screw extruder is 170 DEG C, and fluxing zone extrusion temperature is 200
DEG C, melt conveying zone extrusion temperature is 190 DEG C, and head temperature is 210 DEG C, and the vacuum of extruding pelletization is 0.8MPa.
Embodiment 10
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method comprise the following steps：
(1) by 63g PMMA, 20g ASA, 15g styrene methyl methacrylates-anhydrous maleic acid anhydride polymer,
0.2g antioxidant 1076s, 0.2g antioxidant 6280,0.1g antioxidant 412S, 0.4g ultraviolet absorber UV-P, 0.7g light stabilizers
1min is stirred with 777D and 0.4g pentaerythritol tetrastearates at 500 rpm, obtains compound；
(2) compound for obtaining step (1) is added in double screw extruder, and extruding pelletization obtains the PMMA/ASA and closed
Golden material.
Wherein, the pellet feeding section extrusion temperature of the double screw extruder is 190 DEG C, and fluxing zone extrusion temperature is 220
DEG C, melt conveying zone extrusion temperature is 220 DEG C, and head temperature is 230 DEG C, and the vacuum of extruding pelletization is 0.6MPa.
Comparative example 1
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method do not add benzene second except step (1)
Alkene-methyl methacrylate-anhydrous maleic acid anhydride polymer and PMMA addition be 78.3g outside, other conditions with implementation
Example 6 is identical.
Comparative example 2
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method except step (1) do not add ASA and
PMMA addition is that other conditions are same as Example 6 outside 78.3g.
Comparative example 3
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method do not add benzene second except step (1)
Alkene-methyl methacrylate-anhydrous maleic acid anhydride polymer and ASA and PMMA addition be outside 98.3g, other conditions with
Embodiment 6 is identical.
Comparative example 4
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method do not add thioesters except step (1)
Kind antioxidant and PMMA addition are that other conditions are same as Example 6 outside 58.4g.
Comparative example 5
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method do not add phosphoric acid except step (1)
Esters antioxidant and PMMA addition are that other conditions are same as Example 6 outside 58.5g.
Comparative example 6
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method do not add phenols except step (1)
Antioxidant and PMMA addition are that other conditions are same as Example 6 outside 58.5g.
Comparative example 7
A kind of preparation method of transparent PMMA/ASA alloy materials, the preparation method do not add antioxygen except step (1)
Agent and PMMA addition are that other conditions are same as Example 6 outside 58.8g.
The PMMA used in embodiment 1-8 and comparative example 1-7 number-average molecular weight is 30W, wherein methyl methacrylate
The content of ester is 99.6%；The number-average molecular weight that ASA number-average molecular weight is 300,000, MSM is 200,000；Phenolic antioxidant is antioxygen
Agent 1010, phosphoric acid ester antioxidant are irgasfos 168, and sulphur ester antioxidant is antioxidant 412S；Benzotriazole UV absorption
Agent is ultraviolet absorber UV-P, and hindered amine light stabilizer is light stabilizer 777D.
Embodiment 1-10 and comparative example 1-7 proportion are tested by ASTM D792/ (GB/T1033) standard, lacked
Mouth impact strength is tested by ASTM D256/ (GB/T1843) standard, and ASTM D638/ (GB/ are pressed in tensile property test
T1040) standard is tested, and bending property test is tested by ASTM D790/ (GB/T9341) standard, and fire resistance is surveyed
Examination is tested by UL-94/ (GB/T2408) standard, and melt index test is carried out by ASTM D1238/ (GB/T3682) standard
Test, transparency are tested by test by ASTM D1003/ (GB/2410-80) standard, and transparency presses ASTM by test
D1003/ (GB/2410-80) standard is tested, and ASTM D648 (GB/T1643.1) standard testing is pressed in heat distortion temperature test,
ASTM D2457 (GB/T 8807) standard testing is pressed in glossiness test, and pencil hardness test presses ASTM D3363/ (GB/T6739)
Standard testing.
Table 1
Table 2
From embodiment 1 to embodiment 4 as can be seen that the addition of ASA rubber powders can effectively improve material impact intensity, at the same it is right
Transparency influence is smaller, but rubber powder addition influences substantially on material HDT, and rubber powder is more, and HDT is smaller；From embodiment 5 to 8
As can be seen that the addition of MSM resins can effectively improve the HDT of material, but transparency is had a great influence.Embodiment 6 with it is right
Ratio 4-7 can be seen that the antioxidant systems using compounding, can effectively improve gloss of the material after xenon lamp aging test
Conservation rate is spent, and ternary built is more preferable than the synergy of binary built.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of transparent PMMA/ASA alloy materials, it is characterised in that according to the composition of alloy material described in mass percent meter
Including：
2. alloy material according to claim 1, it is characterised in that the antioxidant is phenolic antioxidant, phosphoric acid ester
The composition of antioxidant and sulphur ester antioxidant.
3. alloy material according to claim 1 or 2, it is characterised in that the mass percent of the phenolic antioxidant is
0.1~0.2%；
Preferably, the mass percent of the phosphoric acid ester antioxidant is 0.1~0.2%；
Preferably, the mass percent of the sulphur ester antioxidant is 0.1~0.2%.
4. according to the alloy material described in claim any one of 1-3, it is characterised in that the auxiliary agent include ultraviolet absorber,
Light stabilizer and lubricant.
5. alloy material according to claim 4, it is characterised in that the UV absorption machine is the ultraviolet suction of benzotriazole
Receive agent；
Preferably, the mass percent of the ultraviolet absorber is 0.2~0.4%；
Preferably, the light stabilizer is hindered amine light stabilizer；
Preferably, the mass percent of the light stabilizer is 0.4~0.7%.
6. the alloy material according to claim 4 or 5, it is characterised in that the lubricant is the stearic acid of pentaerythrite four
Ester；
Preferably, the mass percent of the lubricant is 0.2~0.4%.
A kind of 7. preparation method of any one of claim 1-6 PMMA/ASA alloy materials, it is characterised in that the preparation
Method comprises the following steps：
(1) PMMA, ASA, styrene methyl methacrylate-anhydrous maleic acid anhydride polymer, antioxidant and auxiliary agent are being stirred
Lower mixing, obtains compound；
(2) compound for obtaining step (1) is added in double screw extruder, and extruding pelletization obtains the PMMA/ASA alloy materials
Material.
8. preparation method according to claim 7, it is characterised in that the speed of step (1) described stirring be 100~
500rpm, preferably 200~300rpm；
Preferably, the time of the stirring is 2~4min.
9. the preparation method according to claim 7 or 8, it is characterised in that the pellet of step (2) described double screw extruder
Feeding section extrusion temperature is 170~190 DEG C；
Preferably, the fluxing zone extrusion temperature of step (2) described double screw extruder is 200~220 DEG C；
Preferably, the melt conveying zone extrusion temperature of step (2) described double screw extruder is 190~220 DEG C；
Preferably, the head temperature of step (2) described double screw extruder is 210~230 DEG C.
10. according to the preparation method described in any one of claim 7~9, it is characterised in that step (2) described extruding pelletization
Vacuum is 0.6~0.8MPa.
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Denomination of invention: A heat-resistant transparent PMMA/ASA alloy material and its preparation method Granted publication date: 20200421 Pledgee: Dongguan Humen Branch of China Postal Savings Bank Co.,Ltd. Pledgor: SILVER AGE ENGINEERING PLASTIC (DONGGUAN) Co.,Ltd. Registration number: Y2024980023581 |