CN116041882A - Polymethyl methacrylate alloy and preparation method and application thereof - Google Patents
Polymethyl methacrylate alloy and preparation method and application thereof Download PDFInfo
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- CN116041882A CN116041882A CN202211703826.5A CN202211703826A CN116041882A CN 116041882 A CN116041882 A CN 116041882A CN 202211703826 A CN202211703826 A CN 202211703826A CN 116041882 A CN116041882 A CN 116041882A
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- polymethyl methacrylate
- asa
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- methacrylate alloy
- light absorber
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 35
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 35
- 239000000956 alloy Substances 0.000 title claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title description 9
- 239000006096 absorbing agent Substances 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 4
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 15
- 239000000975 dye Substances 0.000 claims description 7
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000003698 laser cutting Methods 0.000 claims description 3
- 238000010147 laser engraving Methods 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 238000005303 weighing Methods 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229960000956 coumarin Drugs 0.000 claims description 2
- 235000001671 coumarin Nutrition 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 claims description 2
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- 230000031700 light absorption Effects 0.000 abstract description 11
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- QMRNDFMLWNAFQR-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid;styrene Chemical compound C=CC#N.OC(=O)C=C.C=CC1=CC=CC=C1 QMRNDFMLWNAFQR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Images
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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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)
Abstract
The invention discloses a polymethyl methacrylate alloy, which comprises the following components in parts by weight: 50-85 parts of polymethyl methacrylate; 15-40 parts of acrylonitrile-acrylic ester-styrene copolymer; 0.5-4 parts of light absorber; 0.1-2 parts of antioxidant; 0.1-2 parts of weather-proof agent; 0.1-2 parts of toner. The polymethyl methacrylate alloy provided by the invention has the characteristics of good appearance, uniform light absorption and good toughness, and can be used for preparing a Gao Guanghei spray-free decorative part absorbing light with a specific wavelength.
Description
Technical Field
The invention belongs to the technical field of modified high polymer materials, and particularly relates to a polymethyl methacrylate alloy and a preparation method and application thereof.
Background
Polymethyl methacrylate (PMMA) is a high-molecular material with high transparency, high hardness and excellent weather resistance, and is commonly used for preparing decorative parts with high gloss and high vividness. However, the alloy has the defect of poor toughness, and the problem of fracture easily occurs when parts with fastening structures are prepared. Therefore, acrylonitrile-acrylate-styrene (ASA) is often blended with PMMA to prepare an alloy, which compensates for the lack of toughness of PMMA. However, since the refractive index of ASA and that of PMMA are different, the blend obtained by the method has a difference in appearance.
Generally, the better the light transmission of a PMMA/ASA blend system, the better the colorability of the system, and the easier the appearance to be high gloss and vivid in color. At present, high-gloss black spray-free materials representing technological sense are commonly used in the industries of automobiles, low-speed lines, household appliances and the like, and a large part of the high-gloss black spray-free materials are prepared from PMMA alloy materials. Consumers often seek high black and shiny effects, which require that the material system be made as light transmissive as possible. However, some application scenarios require that the high light black material absorbs light of a specific wavelength to meet the design, production, preparation, or use requirements, such as laser engraving, laser cutting, infrared detection, and the like.
Therefore, how to solve the contradiction between the colorability and the light absorptivity of the material, and to realize the optimal balance between the colorability and the light absorptivity of the material, and to give consideration to other properties of the material at the same time, is a problem to be solved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a polymethyl methacrylate alloy and a preparation method and application thereof. The specific technical scheme is as follows:
the polymethyl methacrylate alloy comprises the following components in parts by weight:
the weight ratio of the light absorber to D, ASA, the weight ratio E of the ASA and the rubber particle size F in ASA satisfy the following rules:
L∈(0.2，2.67)∩A∈(0.16，1.6)∩C∈(1，32)；
wherein, "weight ratio of light absorber" refers to the percentage of parts of light absorber to total parts, and "weight ratio of ASA" refers to the ratio of parts of ASA to total parts;
L＝(DF)/E×10 3 ；
A＝(DE)/F×10 4 ；
C＝(EF)/D×10 -3 ；
f is in nm and L is in nm -1 A is in nm -1 The unit of C is nm.
The weight ratio D of the light absorber increases over a range, which is advantageous for improving the absorption of visible light by the blend, and for making the blend appear darker, and likewise for the blend to absorb laser light. However, when the blend absorbs light to saturation, increasing the weight ratio of the absorber does not make the blend appear darker, but rather results in a dramatic decrease in the toughness of the blend. ASA acts to toughen the blend, increasing the weight ratio E is beneficial to improving the toughness of the blend, but because of the difference in refractive index between ASA and PMMA, it is detrimental to the coloring of the blend by the toner, and excessively increasing the weight ratio of ASA can degrade the blackness of the blend. The larger the particle size of the ASA rubber, the more advantageous it is to improve the toughness of the blend, but the larger particle size rubber is detrimental to the coloration of the toner and also weakens the blackness of the blend. In addition, the rubber dispersion density of the large-particle-diameter rubber is low, which is unfavorable for the laser absorption capability of the blend, so that the larger the rubber particle diameter is, the worse the light absorption uniformity of the blend is. In summary, the three factors of the light absorber content, ASA content and ASA rubber particle size affect each other, and affect the appearance, toughness and light absorption of the blend in a mutually restricted manner. The invention discloses a method for balancing the mutual influence of the three components, so that the PMMA/ASA blend has good appearance, uniform light absorption and good toughness.
Further, the rubber particle size F in ASA ranges from 100 to 300nm.
Preferably, the weight ratio D, ASA of the light absorber, E, and the rubber particle size F in ASA satisfy the following rules:
L∈(0.2，0.89)∩A∈(0.2，0.6)∩C∈(1，5)。
further, the light absorber is at least one of carbon black or carbon nanotubes.
Further, the antioxidant is one or more of tri (nonylphenyl) phosphite, tri (2, 4-di-tert-butylphenyl) phosphite, tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane or distearyl thiopropionate.
Further, the weather-proof agent is benzotriazole light stabilizer and/or triazine ultraviolet light absorber.
Further, the toner is an organic dye.
Further, the organic dye is at least one of coumarin dye, polycyclic aromatic hydrocarbon or noble metal complex and other dyes.
The invention also provides a preparation method of the polymethyl methacrylate alloy, which comprises the following steps:
s1: weighing the components according to the proportion, premixing, putting into an extruder, carrying out melt blending, extruding and granulating to obtain the polymethyl methacrylate alloy.
The invention also provides application of the polymethyl methacrylate alloy in laser engraving or laser cutting, such as production of grids, decorative strips and the like of automobiles.
Compared with the prior art, the invention has the following advantages:
the weight ratio of the light absorber to D, ASA in the formula and the rubber particle size F in ASA are enabled to meet L epsilon (0.2,2.67) U A epsilon (0.16,1.6) U C epsilon (1, 32), so that contradictory relations among blackness, light absorption and impact strength of the polymethyl methacrylate alloy material are balanced, and the polymethyl methacrylate alloy with uniform light absorption and good toughness is successfully prepared, a new material scheme is provided for manufacturing plastic parts, and flexibility in design parts is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing evaluation criteria for light absorption uniformity.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. 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.
< preparation of examples and comparative examples >
The raw materials used in the examples and comparative examples of the present invention are all commercially available, but are not limited to these materials:
PMMA: manufacturer Qimei, brand CM-205;
ASA: particle size 100nm, manufacturer jin lake petrochemical, XC510A; particle size 200nm, manufacturer jin lake petrochemical, XC520; particle size 300nm, manufacturer jin lake petrochemical, XC500A; particle size 600nm, manufacturer east China sea, Q350.
The light absorber is carbon black, and the manufacturer cabot and brand number M717;
an antioxidant: tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane, commercially available, the same commercially available product was used in parallel experiments;
weather-resistant agent: benzotriazole light stabilizer, commercially available, and the same commercially available product was used in parallel experiments;
toner: azo 1:2 chromium complexes are commercially available, and the same commercially available product is used in parallel experiments.
The preparation methods of the examples and comparative examples of the present invention are as follows:
s1: weighing the components according to the proportion, and premixing to obtain a premix;
s2: and (3) putting the premix in the step (S1) into a double-screw extruder, mixing, extruding and granulating at 260 ℃ and 500 r/min to obtain the polymethyl methacrylate alloy.
< test Standard >
The performance test criteria for each of the examples and comparative examples of the present invention are as follows:
(1) Blackness: instrument xrite, 64-bit integrating sphere mode;
(2) Light absorption uniformity: the mixture was prepared into a flat plate by injection molding. The apparatus DPF-M20 was used, the output power was 20W, the sweep frequency was 1000HZ, and the light intensity was 60%, and the sweep was performed on the above-mentioned preparation plate. The scanning part is observed by using an optical microscope DVM6-A, and the evaluation and judgment of the light absorption uniformity are carried out according to the attached figure 1:
(3) Notched impact strength: the test was carried out according to standard I SO 180-2019 at a temperature of 23℃in kJ/m 2 。
When the blackness is less than or equal to 26, the light absorption uniformity is excellent, the notch impact strength is more than or equal to 5, and the performance requirements of good appearance, uniform light absorption and good toughness can be met.
TABLE 1 formulations of examples 1-5 and test results
TABLE 2 formulations of comparative examples 1-5 and test results
The weight ratio of each component of comparative examples 1 and 2 was not within the range of the present invention, and the performance could not be satisfied.
The weight of each component in comparative examples 3, 4 and 5 was within the range of the present invention, but the blending of each component did not satisfy the rule of characteristic coefficients, and therefore the performance was poor.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The polymethyl methacrylate alloy is characterized by comprising the following components in parts by weight:
the weight ratio of the light absorber to D, ASA, the weight ratio E of the ASA and the rubber particle size F in ASA satisfy the following rules:
L∈(0.2，2.67)∩A∈(0.16，1.6)∩C∈(1，32)；
wherein,,
L＝(DF)/E×10 3 ；
A＝(DE)/F×10 4 ；
C＝(EF)/D×10 -3 ；
"weight ratio of light absorber" refers to the percentage of parts of light absorber to total parts, and "weight ratio of ASA" refers to the ratio of parts of ASA to total parts;
wherein F is in nm and L is in nm -1 A is in nm -1 The unit of C is nm.
2. Polymethyl methacrylate alloy according to claim 1, characterized in that the rubber particle size F in ASA ranges from 100 to 300nm.
3. Polymethyl methacrylate alloy according to claim 1, characterized in that the weight ratio of light absorber D, ASA E and the rubber particle size F in ASA satisfy the following rules:
L∈(0.2，0.89)∩A∈(0.2，0.6)∩C∈(1，5)。
4. the polymethyl methacrylate alloy of claim 1 wherein the light absorber is at least one of carbon black or carbon nanotubes.
5. The polymethyl methacrylate alloy of claim 1 wherein the antioxidant is one or more of tris (nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tetrakis [ methylene (3, 5-di-t-butyl-4-hydroxyhydrocinnamate) ] methane, or distearylthiopropionate.
6. The polymethyl methacrylate alloy of claim 1 wherein the weathering agent is a benzotriazole-based light stabilizer and/or a triazine-based ultraviolet light absorber.
7. The polymethyl methacrylate alloy of claim 1 wherein the toner is an organic dye.
8. The polymethyl methacrylate alloy of claim 7 wherein the organic dye is at least one of coumarin dyes, polycyclic aromatic hydrocarbons, or noble metal complexes.
9. A method for producing a polymethyl methacrylate alloy according to any one of claims 1 to 8, comprising the steps of:
weighing the components according to the proportion, premixing, putting into an extruder, carrying out melt blending, extruding and granulating to obtain the polymethyl methacrylate alloy.
10. Use of the polymethyl methacrylate alloy according to any one of claims 1-8 in laser engraving or laser cutting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211703826.5A CN116041882A (en) | 2022-12-29 | 2022-12-29 | Polymethyl methacrylate alloy and preparation method and application thereof |
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| CN202211703826.5A CN116041882A (en) | 2022-12-29 | 2022-12-29 | Polymethyl methacrylate alloy and preparation method and application thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690222A (en) * | 2020-07-09 | 2020-09-22 | 东莞市奥能工程塑料有限公司 | PMMA/ASA alloy material with high heat resistance and high blackness and brightness, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690222A (en) * | 2020-07-09 | 2020-09-22 | 东莞市奥能工程塑料有限公司 | PMMA/ASA alloy material with high heat resistance and high blackness and brightness, preparation method and application thereof |
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