CN116589813A - PMMA alloy material and preparation method thereof - Google Patents
PMMA alloy material and preparation method thereof Download PDFInfo
- Publication number
- CN116589813A CN116589813A CN202310310995.0A CN202310310995A CN116589813A CN 116589813 A CN116589813 A CN 116589813A CN 202310310995 A CN202310310995 A CN 202310310995A CN 116589813 A CN116589813 A CN 116589813A
- Authority
- CN
- China
- Prior art keywords
- parts
- alloy material
- pmma
- maleic anhydride
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 63
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 63
- 239000000956 alloy Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical group O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims abstract description 23
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- 239000004595 color masterbatch Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- MEPDWZCRGIWINX-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enenitrile;styrene Chemical compound C=CC#N.CC(=C)C(O)=O.C=CC1=CC=CC=C1 MEPDWZCRGIWINX-UHFFFAOYSA-N 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- 210000003195 fascia Anatomy 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- 238000000465 moulding Methods 0.000 abstract description 18
- 239000000047 product Substances 0.000 description 67
- 230000000052 comparative effect Effects 0.000 description 35
- 238000001746 injection moulding Methods 0.000 description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 239000002041 carbon nanotube Substances 0.000 description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- -1 amino carbon nano tube Chemical compound 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a PMMA alloy material and a preparation method thereof, and belongs to the technical field of high polymer alloy materials. The product provided by the invention comprises the following components in parts by weight: 45-60 parts of PMMA resin, 20-35 parts of toughening agent, 15-25 parts of heat resistant agent, 0.5-2 parts of aminated carbon nano tube, 1-3 parts of color master batch and 0.5-2 parts of processing aid; the heat-resistant agent is a styrene-maleic anhydride copolymer; the N element content of the aminated carbon nano tube is 0.3-1 wt%. The product has ideal highlight black effect and enough impact resistance, and meanwhile, the product components can realize excellent heat resistance and short molding cycle by matching a specific heat-resistant agent with a specific aminated carbon nanotube.
Description
Technical Field
The invention relates to the technical field of high polymer alloy materials, in particular to a PMMA alloy material and a preparation method thereof.
Background
In the appearance of automobiles, the effect of highlighting black tends to give a high-grade feel to the product, and this appearance effect can be achieved mainly by paint spraying, in-mold transfer printing or injection molding of a highlight black material (highlight mold). Compared with the spraying and in-mold transfer printing processes, the injection molding process directly adopting the material with high brightness and black texture is more environment-friendly, convenient and low in cost.
In the injection molding material, the conditions required to achieve the effect of highlighting black texture are that the scattering phenomenon of light inside the substrate is low, so that transparent substrates with low scattering, such as PMMA (polymethyl methacrylate), PC (polycarbonate), SAN (acrylonitrile copolymer), PS (polystyrene), etc., are often used. In the prior art, more than two kinds of the materials are adopted to realize the compatibility of molecular level, thereby preparing the composite alloy material with high bright black effect. For example, CN110256798A, CN106046643A and the like adopt PMMA and ASA to prepare PMMA alloy materials with both appearance effect and excellent mechanical property.
However, the heat resistance and the processing performance of the alloy material are not explored in the prior art, and in the actual production and application process, the material is often required to be stored at high temperature, processed for the second time or used after being prepared into the automobile part, and if the heat resistance is poor, the problem of deformation of the part during high-temperature storage is likely to occur; if the molding period of the parts is too long in the process of processing and injection molding, the productivity is reduced, and the risks of appearance problems such as silver wires, material flowers and the like of the parts caused by material degradation are increased. Therefore, the development of PMMA alloy material with high heat resistance and short molding cycle has important significance.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide a PMMA alloy material, which has ideal highlight black effect and enough impact resistance, and simultaneously, the product components can realize excellent heat resistance and short molding cycle by matching a specific heat-resistant agent with a specific aminated carbon nano tube.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the PMMA alloy material comprises the following components in parts by weight:
45-60 parts of PMMA resin, 20-35 parts of toughening agent, 15-25 parts of heat resistant agent, 0.5-2 parts of aminated carbon nano tube, 1-3 parts of color master batch and 0.5-2 parts of processing aid;
the heat-resistant agent is a styrene-maleic anhydride copolymer; the N element content of the aminated carbon nano tube is 0.3-1 wt%.
In the components of the PMMA alloy material, the styrene-maleic anhydride copolymer with high compatibility contains the maleic anhydride group in the molecular chain, so that the styrene-maleic anhydride copolymer and the methyl methacrylate group in the PMMA resin can be attracted mutually and realize fusion, the transparent characteristic of the PMMA resin is not influenced, and the glass transition temperature of an integral product can be effectively improved by introducing the maleic anhydride group. On the other hand, the amino carbon nano tube has pi-pi interaction with benzene ring in the styrene-maleic anhydride copolymer, and the amino contained in the amino carbon nano tube can react with maleic anhydride group of the styrene-maleic anhydride copolymer, so that the inorganic filler can be uniformly dispersed and effectively entangled with molecular chains in an alloy resin matrix, and the nano filler can not influence the highlight-black characteristic of PMMA resin, and can also improve the heat resistance of the alloy material. Meanwhile, the uniformly distributed aminated carbon nanotubes can quickly absorb heat and conduct the heat to the outside in the process of heating, melting and injection molding of the PMMA alloy material, so that the temperature difference between the inside and the outside of the product after injection molding is quickly eliminated, the forming period is shortened, and meanwhile, the heat-resistant stability and the high-temperature stability of the product are improved (the heat-resistant stability of the PMMA alloy material generally refers to the performance of the product in the high-temperature injection molding process, if the heat-resistant stability of the product is poor, serious silver silk phenomenon can appear in the product in the injection molding process, and the high-temperature stability refers to the stability of the product after injection molding at high temperature or during use, if the high-temperature stability of the product is poor, serious deformation can appear in the product, and although the two properties are related, the influence trends are different).
In addition, the inventor also noted that the aminated carbon nanotube has a specific stacked structure compared with other heat conductive fillers, so the heat dissipation effect is better, but if the content of the amino group is too small, the good dispersion in the PMMA resin matrix cannot be realized, and the heat dissipation effect cannot be fully exerted; if the amino group content is too high, the basic structure of the carbon nanotube is seriously damaged, which may impair its own characteristics. Through researches, the N element content (namely the amino content) of the aminated carbon nano tube needs to be maintained in the range of 0.3-1 wt%.
Preferably, the preparation method of the aminated carbon nanotube comprises the following steps:
uniformly mixing carboxylated carbon nanotubes, ethylenediamine and dicyclohexylcarbodiimide, preserving heat for 24-36 hours at 120-140 ℃, washing the obtained solid with alcohol, sieving, and drying to obtain the aminated carbon nanotubes.
The amination carbon nanotube can be aminated by adopting the carboxylated carbon nanotube which is sold in the market or self-made (the carboxylation technology of carbon materials is well-done and conventional), and the corresponding molar weight of ethylenediamine and dicyclohexylcarbodiimide.
The content of N element in the aminated carbon nanotube can be confirmed and verified by adopting an element analysis method, and meanwhile, a person skilled in the art can also adopt other feasible methods for confirmation and verification according to actual conditions.
Preferably, the PMMA resin has a melt flow rate of less than or equal to 10g/10min at 230 ℃ under a load of 3.8kg according to ISO 1133-2012;
more preferably, the PMMA resin has a melt flow rate of 8g/10min or less at 230 ℃ under a load of 3.8kg according to ISO 1133-2012;
more preferably, the PMMA resin has a melt flow rate of 3 to 6g/10min at 230℃under a load of 3.8 kg.
The fluidity of the PMMA resin as a matrix resin of the product determines the processing difficulty of the product, but in contrast, if the melt flow rate is higher, the thermal stability, particularly the high temperature resistance of the prepared product is reduced, and the heat resistance of the prepared product of the PMMA resin maintained in the range is better.
Preferably, the toughening agent is a silicon-containing acrylate toughening agent.
More preferably, the silicon-containing acrylic acid ester toughening agent is a core-shell structure polymer taking organic silicon/acrylic acid ester copolymer as a core and acrylonitrile-styrene-methyl acrylic acid ester as a shell.
Preferably, the particle size of the toughening agent is 85-300 nm.
More preferably, the particle size of the toughening agent is 90 to 120nm.
In order to ensure the shock resistance of the product, the toughening property is indispensable, and when PMMA resin and styrene-maleic anhydride copolymer are compounded, the particle size of the introduced silicon-containing acrylic toughening agent becomes larger, so that the molding cycle and the high blackness and brightness effect of the product are influenced.
Preferably, the mass fraction of the maleic anhydride groups in the styrene-maleic anhydride copolymer is 10-28%.
More preferably, the mass fraction of maleic anhydride groups in the styrene-maleic anhydride copolymer is 15 to 25%.
As described above, the maleic anhydride group contained in the styrene-maleic anhydride copolymer helps to raise the glass transition temperature of the product and further raise the heat resistance, so that if the content thereof is too small, the degree of improvement of the high temperature stability is not high, but the maleic anhydride group is respectively crosslinked and fused with PMMA resin and aminated carbon nanotubes, so that the maleic anhydride group is relatively active, and if the content thereof is too large, the maleic anhydride group is easily oxidized in a high temperature processing environment, and further the heat resistance stability in the processing process of the product is reduced to some extent. The styrene-maleic anhydride copolymer with the content of the maleic anhydride groups has the best use effect through screening.
Preferably, the color master batch is a SAN resin master batch loaded with carbon black, and the loading amount of the carbon black is 30-40 wt%.
Preferably, the processing aid is at least one of an antioxidant and a weather-proof agent.
More preferably, the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants; the weather-proof agent is benzotriazole ultraviolet absorber;
more preferably, the antioxidant is a mixture of hindered phenol antioxidants and phosphite antioxidants according to a mass ratio of 1:2.
The invention further aims at providing a preparation method of the PMMA alloy material, which comprises the following steps of:
and mixing the components, and then placing the mixture into a double-screw extruder for melt extrusion and granulation to obtain the PMMA alloy material.
The preparation method of the PMMA alloy material has simple operation steps and can realize industrialized mass production.
Preferably, the double-screw extruder is used for melt extrusion granulation, wherein the temperature of a feeding section is 180-210 ℃, the temperature of a plasticizing section is 200-230 ℃, the temperature of a homogenizing section is 210-240 ℃, and the rotating speed of a screw is 300-500 rpm.
It is still another object of the present invention to provide an application of the PMMA alloy material in preparing automobile decoration parts.
Preferably, the automobile decorative parts comprise a grille, a B/C outer column, a triangle and a bumper lower guard plate.
The PMMA alloy material has the high blackness and brightness appearance effect and the impact resistance effect similar to those of the existing similar products in the market, and most importantly, the PMMA alloy material has good heat resistance and a shorter molding cycle, so that the PMMA alloy material is very suitable for preparing some automobile decorative parts, after injection molding, the product can realize long-acting high-temperature stability performance (keeping 240 hours at 90 ℃ without deformation) without spraying protective paint on the appearance, and has higher production value and use value.
The PMMA alloy material has the advantages that the PMMA alloy material provided by the invention has ideal highlight black effect and enough shock resistance, and meanwhile, the product components can realize excellent heat resistance (including heat resistance stability and high temperature stability) and short molding cycle by matching a specific heat-resistant agent with a specific aminated carbon nanotube.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present invention, and the object of the present invention is to be understood in detail, not to limit the present invention. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments involved in the practice of the present invention are common reagents and instruments unless otherwise specified.
Examples 1 to 11
In the embodiment of the PMMA alloy material and the preparation method thereof, the component compositions of the PMMA alloy material are shown in the table 1.
The preparation method of the PMMA alloy material comprises the following steps:
mixing the components, and then placing the mixture into a double-screw extruder for melt extrusion and granulation to obtain the PMMA alloy material;
in the melt extrusion granulation of the double-screw extruder, the temperature of a feeding section is 200 ℃, the temperature of a plasticizing section is 220 ℃, the temperature of a homogenizing section is 240 ℃, and the rotating speed of a screw is 400rpm.
Comparative examples 1 to 9
The comparative examples differ from the examples only in the kinds and proportions of the components, as shown in Table 2.
Among the components described in each example and comparative example,
PMMA resin 1 is a VH001 product produced by Mitsubishi chemical production, and the melt flow rate under the load of 3.8kg at 230 ℃ is 3g/10min;
PMMA resin 2 is a VH5001 product produced by Mitsubishi chemistry, and has a melt flow rate of 6g/10min under a load of 3.8kg at 230 ℃;
PMMA resin 3 is CM207 produced by Taiwan Qimei, and the melt flow rate under the load of 3.8kg at 230 ℃ is 10g/10min;
the toughening agent 1 is a core-shell structure polymer which is produced by the eastern sea plastic industry Co., ltd in Anchu and takes organosilicon/acrylic ester copolymer as a core and acrylonitrile-styrene-methyl acrylic ester as a shell, and the grain diameter is 90-120 nm;
the toughening agent 2 is a core-shell structure polymer which is produced by the eastern sea plastic industry Co., ltd. In Anchu, takes organosilicon/acrylic ester copolymer as a core and acrylonitrile-styrene-methyl acrylic ester as a shell, and has the particle size of 200-300 nm;
the heat resistant agent 1 is SMA-700 produced by Jiaxing Hua, and the mass fraction of maleic anhydride groups is 18% of a styrene-maleic anhydride copolymer;
the heat resistant agent 2 is SMA-725 produced by Jiaxing Hua, and the mass fraction of maleic anhydride groups is 25% of a styrene-maleic anhydride copolymer;
the heat resistant agent 3 is SZ28110 produced by PLOYSCOPE company of Netherlands, and the mass fraction of the maleic anhydride group is 28% of the styrene-maleic anhydride copolymer;
the heat resistant agent 4 is SMA-800 produced by Jiaxing Hua, and the mass fraction of maleic anhydride groups is 10% of that of a styrene-maleic anhydride copolymer;
the heat resistant agent 5 is HW-320, styrene-maleic anhydride-N phenyl maleimide copolymer produced by Jiaxing Hua;
aminated carbon nanotube 1: self-made, wherein the content of N element is 0.8wt%;
aminated carbon nanotubes 2: self-made, wherein the content of N element is 0.3wt%;
aminated carbon nanotubes 3: self-made, wherein the content of N element is 1wt%;
aminated carbon nanotubes 4: self-made, wherein the content of N element is 0.1wt%;
aminated carbon nanotubes 5: self-made, wherein the content of N element is 1.3wt%;
hydroxylated carbon nanotubes: the hydroxyl group content was 1.85wt%, brand TNGMH2, purchased from Chengdu organic chemistry Co., ltd. Of the national academy of sciences;
amino carbon black: self-made, wherein the content of N element is 0.8wt%;
color master batch: 6399D is produced by Shanghai Kaposite chemical industry Co., ltd, and is loaded with SAN resin master batch of carbon black, wherein the loading amount of the carbon black is 30-40 wt%;
an antioxidant: a mixture of commercially available hindered phenol antioxidants and phosphite antioxidants according to a mass ratio of 1:2;
weather-resistant agent: benzotriazole ultraviolet absorbers are commercially available.
The raw materials of the antioxidant and the weather-resistant agent used in each example and comparative example of the present invention are all commercially available raw materials unless otherwise specified, and the raw materials of the components used in each parallel experiment are all the same.
The preparation method of the self-made aminated carbon nano tube and the aminated carbon black comprises the following steps:
mixing the commercial carboxylated carbon nano tube (carbon black) with different carboxylation contents, the ethylenediamine with corresponding contents and dicyclohexylcarbodiimide uniformly, preserving the temperature at 120-140 ℃ for 24-36 hours, washing off excessive reactants and reaction byproducts from the obtained solid by using ethanol, carrying out suction filtration by using a polyvinylidene fluoride micro-filtration membrane with the pore diameter of 0.2 mu m, and finally drying at 80 ℃ for 24 hours to obtain the aminated carbon nano tube (carbon black).
TABLE 1
TABLE 2
| The weight portions of the components | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 |
| PMMA resin 1 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 65 |
| Toughening agent 1 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 35 |
| Heat resistant agent 1 | 20 | 20 | 20 | 20 | 20 | 20 | 35 | ||
| Heat resistant agent 5 | 20 | ||||||||
| Aminated carbon nanotube 1 | 5 | 1.5 | 1.5 | ||||||
| Aminated carbon nanotubes 4 | 1.5 | ||||||||
| Aminated carbon nanotubes 5 | 1.5 | ||||||||
| Hydroxylated carbon nanotubes | 1.5 | ||||||||
| Aminated carbon black | 1.5 | ||||||||
| Color master batch | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Antioxidant | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Weather-proof agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
In order to verify the performance of the PMMA alloy material, the products prepared in each example and comparative example are subjected to the following performance tests, and the specific steps are as follows:
(1) And (3) testing impact strength of the simply supported beam: the products obtained in each example and comparative example were injection molded into notched impact bars according to the ISO 179-2010 standard, and tested at 80X 10X 4mm, with an impact energy of 4J at a temperature of 23 ℃;
(2) And (3) molding cycle test: the products obtained in each example and comparative example are subjected to injection molding for 3 times in parallel by adopting an injection molding machine at 250 ℃ to form a test flat plate with the size of 356 multiplied by 100 multiplied by 3mm, and the average value of the parallel injection molding time of each product is counted to be used as the molding period of the product;
(3) Heat stability test: observing the surface of the molded flat plate prepared by injection molding in the step (2), and observing the severity of silver wires; quantitatively grading the percentage of the silver wire area of the flat plate to the total area of the flat plate, wherein the percentage of the silver wire area is less than or equal to 3%, and considering that no silver wire exists in the flat plate; the percentage is more than 3% and less than or equal to 10%, the flat plate is considered to have slight silver wires; a percentage greater than 10% is considered to be a severe silver streak on the plate.
(4) High temperature stability test: placing the molded flat plate prepared by injection molding in the step (2) in a baking oven at 90 ℃ for 240 hours, and observing whether deformation occurs to the flat plate before and after the flat plate is placed; the deformation grade adopts a fixed flat plate corner, and the height of the other end of the diagonal out of the plane is measured for quantification, wherein the height is smaller than or equal to 0.5mm, and the flat plate is considered to be free from deformation; the flat plate is considered to be slightly deformed when the height is more than 0.5mm and less than or equal to 1.5 mm; a height greater than 1.5mm would be considered a severe deformation of the plate.
(5) Blackness test: the L values of the products were tested with a high light plate using Airy 700A for each example and comparative example, wherein the lower the L value, the better the highlight black effect of the product.
The test results are shown in tables 3 and 4.
TABLE 3 Table 3
TABLE 4 Table 4
| Test item | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 |
| Notched impact Strength (KJ/m) 2 ) | 10.5 | 6.5 | 8.2 | 7.9 | 7.4 | 7.6 | 7.3 | 6.8 | 12.1 |
| Period of formation(s) | 52 | 49 | 48 | 47 | 48 | 45 | 49 | 40 | 55 |
| Whether or not silver silk is present | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Slight | Whether or not | Severe severity of | Slight |
| Whether or not to deform | Slight | Whether or not | Slight | Whether or not | Slight | Slight | Whether or not | Whether or not | Severe severity of |
| Blackness L value | 24.35 | 24.75 | 24.62 | 24.48 | 24.43 | 24.36 | 27.68 | 25.14 | 24.37 |
As can be seen from tables 3 and 4, the products of each example exhibited a high overall performance, wherein the products maintained 8KJ/m 2 The notch impact strength is less than or equal to 45s, the serious silver wire and deformation phenomenon do not occur in injection molding and heat treatment, meanwhile, the product can keep a high black and bright appearance, and the blackness L value is lower than 24.5. As can be seen from comparison of the products of examples 1, 4 and 5, the melt mass flow rate of PMMA resin in the product has an effect on the notched impact strength, molding cycle and appearance performance of the product, wherein the product prepared by selecting PMMA resin with the melt mass flow rate of 3-6 g/10min can achieve better notched impact strength and appearance effect, and the molding cycle can be maintained within 40 s. In contrast, according to the comparison between example 1 and example 6, when the particle size of the toughening agent used is large, the notched impact strength of the product is improved to some extent, but the molding cycle of the product is relatively long, and the effect of high blackness and brightness is low. As is clear from comparison of the products of examples 1 and examples 7 to 9, when the maleic anhydride groups of the styrene-maleic anhydride copolymer in the product are small, the degree of improvement of the heat resistance of the product is weak, and the molding cycle of the product is long, but if the group content is too large, the product may have a low heat stability and a low appearance effect due to its high reactivity, so that the product performance is optimal when the mass fraction of the maleic anhydride groups in the styrene-maleic anhydride copolymer is 15 to 25%. In contrast, the comparative example 9 product of the conventional PMMA alloy material-like product, although slightly compared to the notched impact strength of the PMMA alloy material product of the present inventionThe product has high blackness and brightness effects, but the heat resistance of the product is not ideal, serious deformation occurs at high temperature, and the molding period is longer; in the product of the present invention, however, the styrene-maleic anhydride copolymer as a key component is indispensable, otherwise, as shown in the product of comparative example 1, although the heat resistance is improved as compared with the product of comparative example 9, a shorter molding cycle is still not achieved. The heat-resistant agent and the aminated carbon nanotubes were both present in the product of comparative example 2, but the aminated carbon nanotubes were too much, and the notched impact strength of the product was drastically reduced, and the molding cycle was also prolonged, as compared with the product of example 1. As is clear from the comparison of example 1, examples 10 to 11 and comparative examples 3 to 4, the amino group content of the aminated carbon nanotubes cannot be too much or too little, otherwise the molding cycle of the product is affected to lengthen. From the properties of the products of comparative examples 5 and 6, it is known that the aminated carbon nanotube cannot be replaced at will either by its own main body or by the group contained therein, and if the carbon nanotube has no amino group on its surface, the reaction crosslinking with the heat-resistant agent becomes low; the stacking structure of the carbon nano tubes is not adopted, so that the heat resistance stability and the high temperature stability of the product are also affected, and the equivalent performance of the product of the embodiment is difficult to achieve. The product of comparative example 7 does not use a styrene-maleic anhydride copolymer as a heat-resistant agent, but uses a common styrene-maleic anhydride-N-phenyl maleimide copolymer as a heat-resistant agent, and the heat resistance of the product is good, but the molding cycle of the product is not improved, and most importantly, the high blackish and shiny appearance effect of the product is destroyed. While according to the performance of the product of comparative example 8, too much styrene-maleic anhydride copolymer can not be added as a heat-resistant agent, otherwise the heat-resistant stability of the product is significantly impaired.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The PMMA alloy material is characterized by comprising the following components in parts by weight:
45-60 parts of PMMA resin, 20-35 parts of toughening agent, 15-25 parts of heat resistant agent, 0.5-2 parts of aminated carbon nano tube, 1-3 parts of color master batch and 0.5-2 parts of processing aid;
the heat-resistant agent is a styrene-maleic anhydride copolymer; the N element content of the aminated carbon nano tube is 0.3-1 wt%.
2. The PMMA alloy material according to claim 1, wherein the PMMA resin has a melt flow rate of 10g/10min or less under a load of 3.8kg at 230 ℃.
3. The PMMA alloy material according to claim 2, wherein the PMMA resin has a melt flow rate of less than or equal to 8g/10min at 230 ℃ under a load of 3.8 kg; preferably, the PMMA resin has a melt flow rate of 3-6 g/10min at 230 ℃ under a load of 3.8 kg.
4. The PMMA alloy material according to claim 1, wherein the toughening agent is silicon-containing acrylic toughening agent with the particle size of 85-300 nm; preferably, the silicon-containing acrylic acid ester toughening agent is a core-shell structure polymer with an organosilicon/acrylic acid ester copolymer as a core and acrylonitrile-styrene-methyl acrylic acid ester as a shell, and the particle size is 90-120 nm.
5. The PMMA alloy material according to claim 1, wherein the mass fraction of maleic anhydride groups in the styrene-maleic anhydride copolymer is 10-28%; preferably, the mass fraction of the maleic anhydride groups in the styrene-maleic anhydride copolymer is 15-25%.
6. The PMMA alloy of claim 1, comprising at least one of the following (a) - (b):
(a) The color master batch is a SAN resin master batch loaded with carbon black, and the loading amount of the carbon black is 30-40 wt%;
(b) The processing aid is at least one of an antioxidant and a weather-proof agent; the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants; the weather-proof agent is benzotriazole ultraviolet absorber.
7. The method for producing a PMMA alloy material according to any one of claims 1 to 6, comprising the steps of:
and mixing the components, and then placing the mixture into a double-screw extruder for melt extrusion and granulation to obtain the PMMA alloy material.
8. The method for preparing PMMA alloy material according to claim 7, wherein the twin-screw extruder is used for melt extrusion granulation, the temperature of the feeding section is 180-210 ℃, the temperature of the plasticizing section is 200-230 ℃, the temperature of the homogenizing section is 210-240 ℃, and the screw rotation speed is 300-500 rpm.
9. Use of a PMMA alloy material according to any one of claims 1 to 6 for the production of automotive trim parts.
10. The use of claim 9, wherein the automotive trim component comprises a grille, a B/C outer post, a triangle, and a bumper fascia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310310995.0A CN116589813B (en) | 2023-03-28 | 2023-03-28 | PMMA alloy material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310310995.0A CN116589813B (en) | 2023-03-28 | 2023-03-28 | PMMA alloy material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116589813A true CN116589813A (en) | 2023-08-15 |
| CN116589813B CN116589813B (en) | 2024-08-06 |
Family
ID=87605085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310310995.0A Active CN116589813B (en) | 2023-03-28 | 2023-03-28 | PMMA alloy material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116589813B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759945A (en) * | 2008-12-26 | 2010-06-30 | 金发科技股份有限公司 | Thermoplastic composition, and preparation method and application thereof |
| CN104497461A (en) * | 2014-12-15 | 2015-04-08 | 上海锦湖日丽塑料有限公司 | Heat-resistant scratch-resistant high-transmittance PMMA alloy resin composition and preparation method thereof |
| CN105733026A (en) * | 2016-05-12 | 2016-07-06 | 鲁东大学 | Preparation method of functionalized carbon nanotube material |
| CN109810439A (en) * | 2017-11-22 | 2019-05-28 | 万华化学集团股份有限公司 | Plexiglass composition and its preparation method and application with aesthetic look and improvement heat resistance |
| KR102402965B1 (en) * | 2021-11-10 | 2022-05-31 | 대진첨단소재 주식회사 | Method for manufacturing modified carbonnano materials and conductive structure |
-
2023
- 2023-03-28 CN CN202310310995.0A patent/CN116589813B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759945A (en) * | 2008-12-26 | 2010-06-30 | 金发科技股份有限公司 | Thermoplastic composition, and preparation method and application thereof |
| CN104497461A (en) * | 2014-12-15 | 2015-04-08 | 上海锦湖日丽塑料有限公司 | Heat-resistant scratch-resistant high-transmittance PMMA alloy resin composition and preparation method thereof |
| CN105733026A (en) * | 2016-05-12 | 2016-07-06 | 鲁东大学 | Preparation method of functionalized carbon nanotube material |
| CN109810439A (en) * | 2017-11-22 | 2019-05-28 | 万华化学集团股份有限公司 | Plexiglass composition and its preparation method and application with aesthetic look and improvement heat resistance |
| KR102402965B1 (en) * | 2021-11-10 | 2022-05-31 | 대진첨단소재 주식회사 | Method for manufacturing modified carbonnano materials and conductive structure |
Non-Patent Citations (4)
| Title |
|---|
| CHOPRA, D 等: "Effect of maleic anhydride content on the rheology and phase behavior of poly(styrene-co-maleic anhydride)/poly(methyl methacrylate) blends", RHEOLOGICA ACTA, vol. 41, no. 1, 31 January 2002 (2002-01-31), pages 10 - 24 * |
| ZHANG, K 等: "Amino functionalization and characteristics of multi-walled carbon nanotube/poly(methyl methacrylate) nanocomposite", 2ND INTERNATIONAL CONFERENCE ON NEW DIAMOND AND NANO CARBONS, vol. 18, no. 2, 31 March 2009 (2009-03-31), pages 316 - 318 * |
| 王亮 等: "透明PMMA/SMA合金制备及其性能研究", 塑料工业, vol. 47, no. 04, 31 December 2019 (2019-12-31), pages 43 - 46 * |
| 王楠 等: "PMMA/SMA共混体系流变行为与温度依赖性的研究", 中国塑料, vol. 26, no. 5, 31 May 2012 (2012-05-31), pages 69 - 73 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116589813B (en) | 2024-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111592730A (en) | High-gloss heat-resistant scratch-resistant weather-resistant PMMA/ASA alloy resin material and preparation method thereof | |
| CN109836786A (en) | A kind of PC/ASA/PBT alloy material and preparation method thereof for 3D printing | |
| CN111087748B (en) | Antistatic ABS resin composition with improved chemical resistance and preparation method thereof | |
| CN113603994B (en) | High-thermal-oxidative-stability high-heat-resistance spraying-free PMMA/ASA alloy resin composition and preparation method thereof | |
| CN112457645A (en) | Polycarbonate alloy composition and preparation method and application thereof | |
| CN112480660A (en) | High-strength high-weather-resistance good-appearance PA6 composition and preparation method thereof | |
| CN116589813B (en) | PMMA alloy material and preparation method thereof | |
| CN108285609B (en) | High melt strength styrene resin composition and preparation method thereof | |
| CN115926415B (en) | PC/PMMA/ASA ternary alloy material and preparation method and application thereof | |
| CN102108176B (en) | ABS material with low gloss, high shock resistance, and high fluidity | |
| CN106893250B (en) | A kind of ABS resin composition being blow molded with high fondant-strength, good appearance | |
| CN114213792B (en) | PMMA alloy material with high scratch resistance and preparation method thereof | |
| CN114605741A (en) | Polypropylene composite material and preparation method and application thereof | |
| CN111647259A (en) | Biodegradable composite cable and preparation method thereof | |
| CN109320839B (en) | Photodiffusion polypropylene composite material for LED | |
| CN115537006A (en) | Preparation method and application of high-impact low-linear-expansion-coefficient PC/ABS alloy material | |
| CN112480615A (en) | Carbon fiber/PET composite material and preparation method and application thereof | |
| CN106905650B (en) | High impact polymethyl methacrylate alloy resin composition and preparation method thereof | |
| CN110903567A (en) | Modified ASA material for vehicles and preparation method thereof | |
| CN115490978B (en) | Impact-resistant transparent PMMA material and preparation method thereof | |
| KR20010062986A (en) | Thermoplastic resin composition with good heat resistance | |
| CN114276612B (en) | Transparent polypropylene composition for food packaging and preparation method thereof | |
| CN112266563B (en) | Polyamide-polymethyl methacrylate alloy material and preparation method thereof | |
| CN112812431B (en) | High-performance low-shrinkage polypropylene and preparation method thereof | |
| CN112480634B (en) | Polycarbonate alloy composite material with adjustable surface hardness and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |