CN116218115B - PMMA alloy material and preparation method and application thereof - Google Patents
PMMA alloy material and preparation method and application thereof Download PDFInfo
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 62
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 62
- 239000000956 alloy Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012745 toughening agent Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 4
- 238000012360 testing method Methods 0.000 claims description 19
- 239000004611 light stabiliser Substances 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000012792 core layer Substances 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 150000002148 esters Chemical group 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920005573 silicon-containing polymer Polymers 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 24
- 238000002474 experimental method Methods 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229910052724 xenon Inorganic materials 0.000 abstract description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 9
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RZPFVRFSYMUDJO-UHFFFAOYSA-N 2h-naphthalen-1-one Chemical compound C1=CC=C2C(=O)CC=CC2=C1 RZPFVRFSYMUDJO-UHFFFAOYSA-N 0.000 description 1
- ZEHOVWPIGREOPO-UHFFFAOYSA-N 4,5,6,7-tetrachloro-2-[2-(4,5,6,7-tetrachloro-1,3-dioxoinden-2-yl)quinolin-8-yl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C(=O)N1C(C1=N2)=CC=CC1=CC=C2C1C(=O)C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C2C1=O ZEHOVWPIGREOPO-UHFFFAOYSA-N 0.000 description 1
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 238000005275 alloying Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- -1 pentaerythritol ester Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a PMMA alloy material and a preparation method and application thereof. The PMMA alloy material comprises the following components in parts by weight: 60-78 parts of PMMA resin, 20-35 parts of ASA toughening agent, 0.5-3 parts of graphene oxide, 0.5-3 parts of siloxane and 1.5-9 parts of auxiliary agent; the graphene oxide contains an epoxy group. The PMMA alloy material prepared by the method has higher glossiness, weather resistance and impact property, and simultaneously can realize good solvent resistance, and meets the requirements of ageing and cold-hot alternation experiments of a dry (PV 3929) and wet (PV 3930) xenon lamp of an automobile exterior trim.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a PMMA alloy material and a preparation method and application thereof.
Background
Polymethyl methacrylate (PMMA) has excellent weather resistance, higher hardness, good temperature resistance, excellent coloring performance and transparency, and is widely applied in industry. However, the common PMMA has poor toughness and is easy to crack, so that the further application of the PMMA is limited.
In order to improve the impact resistance properties, PMMA is usually alloyed, i.e. a second polymer matrix is added, which is one of the most desirable materials for its alloying due to the fact that the acrylonitrile-styrene-acrylate terpolymer (ASA) has a solubility parameter very consistent with PMMA, but the addition of ASA material inevitably brings a certain loss of surface scratch resistance to PMMA. The traditional modification can properly improve the scratch and blushing resistance of the surface by adding the lubricant, but cannot improve the linear wear resistance, and cannot meet the FAM test in chemical reagent resistance.
Disclosure of Invention
The invention aims to provide a PMMA alloy material, and a preparation method and application thereof. The solvent-resistant PMMA alloy material has higher glossiness, weather resistance, linear wear resistance and impact resistance, and can realize good solvent resistance.
In order to achieve the above purpose, the present invention adopts the following technical scheme: the PMMA alloy material comprises the following components in parts by weight:
the graphene oxide contains an epoxy group.
Preferably, the PMMA alloy material comprises the following components in parts by weight:
preferably, the PMMA resin has a melt index of 8-12g/10min under the test condition of 10kg at 220 ℃ according to GB/T3682-2018 standard. If the fluidity of PMMA resin is too low, the injection molding product is difficult, the surface is easy to generate gas wire defects, and if the fluidity is too high, the toughness of alloy materials is low, the surface density of the product is low, and the solvent resistance is poor.
Preferably, the ASA toughening agent is an organosilicon/acrylic copolymer toughening agent with a core-shell structure, wherein the core layer is silicon-containing acrylic resin, and the shell layer is one or two of epoxy modified methyl methacrylate copolymer or acrylonitrile-styrene copolymer.
Preferably, the PMMA alloy material further comprises 0.3-5 parts of high-gloss black powder component. The high-gloss black powder is a common component in the industry, such as a mixture of naphthalenone red, anthraquinone green and quinophthalone yellow.
Preferably, the PMMA alloy material at least comprises one of the following (1) - (3):
(1) The sheet diameter of the graphene oxide is 0.5-5 mu m, and the single-layer thickness is 0.8-1.2nm; the sheet diameter is too small, the thickness is less than 0.8nm, the specific surface energy of graphene oxide is too large, aggregation is easy to occur, pits are generated on the surface of a product, and the glossiness is affected; the graphene oxide with the sheet diameter being overlarge and the thickness being more than 1.2nm influences the reflective performance of the surface of the product, so that the glossiness of the surface of the product is reduced;
(2) The siloxane is polyester (pentaerythritol ester) modified silicone master batch (the siloxane content is about 50%), the melting point is 50-60 ℃, and the testing method is according to GB/T28724-2012; when the PMMA product is corroded by partial solvent, the solvent volatilizes to force the surface of the product to generate heat, the temperature can reach 50-60 ℃, at the moment, silicone master batch can be dissociated around scratches to form synergistic effect with graphene oxide, and further the solvent resistance is improved; the melting point is too low, the precipitation is easy, the melting point is too high, the lubricating performance in a PMMA system is poor, and the linear wear resistance is also poor;
(3) The auxiliary agent comprises at least one of an antioxidant, a lubricant and a light stabilizer.
More preferably, the PMMA alloy material at least comprises one of the following (1) to (3):
(1) The antioxidant is a mixture of phosphite antioxidants and hindered phenol antioxidants;
(2) The lubricant is an ester lubricant;
(3) The light stabilizer is at least one of benzotriazole light stabilizer, triazine light stabilizer and hindered amine light stabilizer.
The preparation method of the solvent-resistant PMMA alloy material comprises the following steps:
uniformly mixing 1/2 of the total weight of PMMA resin and other all components to obtain a premix, adding the premix into a double screw extruder, mixing with the rest of PMMA resin to obtain a mixture, and finally melting, plasticizing, extruding, drawing, cooling and granulating to obtain the solvent-resistant PMMA alloy material.
Preferably, the preparation method of the solvent-resistant PMMA alloy material at least comprises one of the following (1) to (2):
(1) The length-diameter ratio of the double-screw extruder is 40:1, a step of;
(2) The process conditions of the double-screw extruder are as follows: the temperature of the first area is 120-140 ℃, the temperature of the second area is 140-180 ℃, the temperature of the third area is 200-230 ℃, the temperature of the fourth area is 240-250 ℃, the temperature of the fifth area is 240-250 ℃, the temperature of the sixth area is 240-250 ℃, the temperature of the seventh area is 240-250 ℃, the temperature of the eighth area is 240-250 ℃, the temperature of the ninth area is 240-250 ℃, the temperature of the machine head is 240-250 ℃, the rotating speed of a host machine is 450 revolutions per minute, the current of the host machine is 60-70%, the vacuum negative pressure is-0.075 to-0.08 MPa, and the melt pressure is 8-10MPa.
The solvent-resistant PMMA alloy material is applied to the preparation of plastic products for automobile exterior trim, such as automobile door outer column trim panels, triangular plates, grid bright strips, bumper lower extension guard plates and the like.
According to the invention, PMMA resin and ASA toughening agent components are selected, graphene oxide and siloxane are added, the epoxy group of the graphene oxide provides compatibility with matrix resin, the graphene oxide forms a net structure on the surface of a product, the surface hardness of the product is improved, the siloxane reduces the surface friction coefficient of a material, and finally a net barrier layer with lower damping can be formed on the surface of the material by compounding the graphene oxide and the siloxane in a PMMA alloy system, so that the wear resistance (linear wear resistance) and the solvent resistance (chemical reagent resistance FAM A) of the material are improved while the highlight black effect is ensured.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, PMMA resin and ASA toughening agent are selected, and graphene oxide and siloxane are compounded, so that the glossiness of the PMMA alloy material can be effectively improved, the solvent resistance is improved, and meanwhile, the requirements of an automobile exterior trim dry state (PV 3929), a wet state (PV 3930) xenon lamp aging, a cold-hot alternating experiment, an impact performance experiment and a linear wear-resisting experiment are met.
Drawings
Fig. 1 is a schematic diagram of the solvent resistance principle of the PMMA alloy material of the invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples, antioxidants, lubricants, light stabilizers, and high gloss black powders were all obtained commercially and used in the same manner in parallel experiments unless otherwise specified.
The raw materials used in the examples and comparative examples are described in Table 1.
TABLE 1
Examples 1 to 14 and comparative examples 1 to 5
PMMA alloy materials of examples 1 to 14 and comparative examples 1 to 5 were prepared as shown in tables 2 and 3.
The preparation method of PMMA alloy materials of examples 1 to 14 and comparative examples 1 to 5 comprises the following steps:
uniformly mixing 1/2 of the total weight of PMMA resin and other all components to obtain a premix, adding the premix into a double screw extruder, mixing with the rest of PMMA resin to obtain a mixture, and finally melting, plasticizing, extruding, drawing, cooling and granulating to obtain the solvent-resistant PMMA alloy material.
Wherein the aspect ratio of the twin-screw extruder is 40:1, the technological conditions of the double-screw extruder are as follows: the temperature of the first area is 130 ℃, the temperature of the second area is 160 ℃, the temperature of the third area is 220 ℃, the temperature of the fourth area is 240 ℃, the temperature of the fifth area is 240 ℃, the temperature of the sixth area is 240 ℃, the temperature of the seventh area is 240 ℃, the temperature of the eighth area is 240 ℃, the temperature of the ninth area is 240 ℃, the temperature of a machine head is 240 ℃, the rotating speed of a host machine is 450 revolutions per minute, the current of the host machine is 65%, the vacuum negative pressure is-0.075 MPa, and the melt pressure is 9MPa.
Table 2 the amounts (parts by weight) of the components in the examples
Table 3 amounts of the components (parts by weight) in the comparative examples
Performance testing
The solvent-resistant PMMA alloy materials prepared in examples 1 to 14 and comparative examples 1 to 5 were subjected to performance test, and the specific test method and conditions are as follows:
1. and (3) testing mechanical properties of the material:
the impact strength of the simply supported beam (comprising the impact of the simply supported beam without a notch and the impact of the simply supported beam notch) is tested according to the ISO 179-2010 standard, the length is 80mm, the width is 10mm, the thickness is 4mm, for the impact test of the notch of the simply supported beam, the notch type A is tested, and the test environment is 23 ℃ and 50 percent of humidity is tested;
2. linear abrasion resistance test:
and (3) preparing a sample by using a highlight die or a part actual die with the polishing degree of 8000+/-100 meshes. The surface of the template is clean and has no appearance defect, and the size of the template is equal to or more than 110mm, 110mm and 2mm. The test was performed using a Taber linear abrader, with at least 3 samples tested, as follows:
1) A friction head (Taber accessory number 131434) with the diameter of 3/4 inch is stuck on a friction disk (Taber accessory number 130572) with the diameter of 1 inch by using circular double-sided adhesive, and then the assembled friction disk is assembled on a weight frame, and the weight frame is leveled by using a balance weight;
2) Setting equipment parameters and loading loads: the friction speed is 25cycles/min, the friction stroke is 75mm, the friction cycle is 10 times, and the load is 8N;
3) The gloss (20 ° reflectance angle) of the friction area before and after friction was measured using a BYK or Konica Minolta triangle gloss tester, and the gloss retention (gloss retention=post-test gloss/pre-test gloss×100%) was calculated, and the quality of the linear abrasion resistance was judged from the level of the gloss retention, with the gloss retention being lower when the linear abrasion resistance was poor and higher when the linear abrasion resistance was good.
Note that: each time a test is carried out, the friction head needs to be ground to ensure the effectiveness of the test, and the surface of the sample plate needs to be cleaned up after the glossiness test after friction.
3. Weather resistance test:
tests were performed as per PV3929-2008 and PV 3930-2008:
PV3929 test irradiance 0.6W/m 2 The black standard temperature is 90 ℃, the humidity is 20+/-10 percent, the illumination time is 1500 hours, and the sample is required to be irradiated and not allowed to change relative to the sample before irradiation, such as: color change, chalking and/or cracking phenomena. The required gray level is more than or equal to 4.
PV3930 test irradiance 0.5W/m 2 The black standard temperature is 65 ℃, the humidity is 70%, water spray is 18min, water spray is not carried out for 102min, continuous circulation illumination is carried out for 1600h, and the sample is required to be inadmissible to change after illumination relative to the sample before illumination, such as: color change, chalking and/or cracking phenomena. The required gray level is more than or equal to 4.
4. Solvent resistance test:
the FAM A solvent comprises the following main components in percentage by volume: 50% toluene, 30% isooctane (2, 4-trimethylpentane), 15% diisobutyronitrile, 5% ethanol; the test method is that the solvent is dripped on the sample plate, the diameter is about 10mm, the glass dish is covered, and after ten minutes, the surface state of the sample plate is observed. Rating at 0-5, preferably 0, no change in surface, worst at 5, obvious discoloration and swelling defects on surface.
The results of the performance test are shown in Table 4.
TABLE 4 Performance test results
From the data in table 3, it can be seen that the PMMA alloy material prepared in the embodiment of the present invention has high gloss, weather resistance, and impact strength, wherein the gloss of 20 ° before friction can be maintained between 70.1 and 77.8, the gloss of 20 ° after friction can be maintained between 21.2 and 36.1, the linear abrasion-resistant gloss retention can be realized in the range of 29 to 46%, the notched impact strength can be maintained between 4.1 and 8.5MPa, the unnotched impact strength can be maintained between 39.8 and 57.5MPa, and good solvent resistance can also be realized, and the level of 2 to 3 can be maintained.
From the experimental results of examples and comparative examples 1 to 3, it is known that when one or both of graphene oxide and siloxane are absent in the PMMA alloy material, the glossiness, abrasion resistance, weather resistance and chemical solvent resistance are poor; in comparative example 4, silicon carbide is selected to replace siloxane, and the prepared alloy material has obviously deteriorated glossiness after friction, linear abrasion-resistant glossiness retention, weather resistance and solvent resistance; in comparative example 5, the ABS toughening agent is selected to replace the ASA toughening agent, and the prepared material has obviously deteriorated 20 DEG glossiness before friction, 20 DEG glossiness after friction, ageing property, linear abrasion-resistant glossiness retention rate, solvent resistance and the like, so that the enhanced glossiness, abrasion resistance and chemical reagent resistance of graphene oxide and siloxane in the invention can be realized only in an alloy system formed by PMMA resin and the ASA toughening agent.
From the experimental results, the invention can effectively enhance the glossiness, the friction resistance, the ageing resistance and the solvent resistance of the PMMA alloy material through the interaction among the PMMA resin, the ASA toughening agent, the graphene oxide and the siloxane component, further widens the application range of the prepared material and prolongs the service life of the product.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The PMMA alloy material is characterized by comprising the following components in parts by weight:
60-78 parts of PMMA resin;
20-35 parts of ASA toughening agent;
0.5-3 parts of graphene oxide;
0.5-3 parts of siloxane;
1.5-9 parts of auxiliary agent;
the graphene oxide contains an epoxy group;
the siloxane is polyester modified silicone master batch, and the melting point is 50-60 ℃.
2. The PMMA alloy of claim 1 comprising the following components in parts by weight:
63-72 parts of PMMA resin;
25-30 parts of ASA toughening agent;
1-2 parts of graphene oxide;
1.5-2 parts of siloxane;
3-6 parts of auxiliary agent.
3. PMMA alloy material of claim 1, wherein the PMMA resin has a melt index of 8 to 12g/10min at 220 ℃ under 10kg test conditions in accordance with GB/T3682-2018 standard.
4. The PMMA alloy of claim 1, wherein the ASA toughening agent is a core-shell structured silicone/acrylic copolymer toughening agent, wherein the core layer is a silicon-containing acrylic resin and the shell layer is one or both of an epoxy modified methyl methacrylate copolymer or an acrylonitrile-styrene copolymer.
5. The PMMA alloy material according to claim 1 or 2, further comprising 0.5 to 3 parts of a high gloss black powder component.
6. PMMA alloy of claim 1 comprising at least one of the following (1) - (2):
(1) The sheet diameter of the graphene oxide is 0.5-5 mu m, and the single-layer thickness is 0.8-1.2nm;
(2) The auxiliary agent comprises at least one of an antioxidant, a lubricant and a light stabilizer.
7. The PMMA alloy material according to claim 6, wherein at least one of the following (1) to (3) is contained:
(1) The antioxidant is a mixture of phosphite antioxidants and hindered phenol antioxidants;
(2) The lubricant is an ester lubricant;
(3) The light stabilizer is at least one of benzotriazole light stabilizer, triazine light stabilizer and hindered amine light stabilizer.
8. A method for preparing a PMMA alloy material according to any one of claims 1 to 7, comprising the steps of:
uniformly mixing 1/2 of the total weight of PMMA resin and other all components to obtain a premix, adding the premix into a double screw extruder, mixing with the rest of PMMA resin to obtain a mixture, and finally melting, plasticizing, extruding, drawing, cooling and granulating to obtain the PMMA alloy material.
9. The preparation method according to claim 8, comprising at least one of the following (1) - (2):
(1) The length-diameter ratio of the double-screw extruder is 40:1, a step of;
(2) The process conditions of the double-screw extruder are as follows: the temperature of the first area is 120-140 ℃, the temperature of the second area is 140-180 ℃, the temperature of the third area is 200-230 ℃, the temperature of the fourth area is 240-250 ℃, the temperature of the fifth area is 240-250 ℃, the temperature of the sixth area is 240-250 ℃, the temperature of the seventh area is 240-250 ℃, the temperature of the eighth area is 240-250 ℃, the temperature of the ninth area is 240-250 ℃, the temperature of the machine head is 240-250 ℃, the rotating speed of a host machine is 450 revolutions per minute, the current of the host machine is 60-70%, the vacuum negative pressure is-0.075 to-0.08 MPa, and the melt pressure is 8-10MPa.
10. Use of a PMMA alloy material according to any one of claims 1 to 7 for the production of plastic articles for automotive exterior trim.
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