CN114196151B - Polyacrylate resin composition and preparation method and application thereof - Google Patents
Polyacrylate resin composition and preparation method and application thereof Download PDFInfo
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- CN114196151B CN114196151B CN202111448466.4A CN202111448466A CN114196151B CN 114196151 B CN114196151 B CN 114196151B CN 202111448466 A CN202111448466 A CN 202111448466A CN 114196151 B CN114196151 B CN 114196151B
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- 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
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Abstract
The invention relates to the technical field of high polymer materials, and particularly discloses a polyacrylate resin composition, a preparation method and application thereof. The polyacrylate resin composition comprises the following components in parts by weight: 39-98 parts of polyacrylate resin, 1-20 parts of lamellar matting agent and 0.5-54 parts of processing aid, wherein the refractive index of the lamellar matting agent is 1.53-1.63. According to the invention, the layered matting agent with special properties and specific refractive indexes is mixed with the polyacrylate resin, so that the semitransparent performance and the frosting performance of the polyacrylate resin composition are obviously improved. The polyacrylate resin composition with semitransparent frosting effect can be obtained by using the high-light mold without adopting a dermatoglyph mold, so that the cost and complicated processing process of mold design are greatly saved, and the high-efficiency application of the polyacrylate resin composition in household appliances, automobile panels, windows, stationery or toys can be realized.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyacrylate resin composition and a preparation method and application thereof.
Background
The polyacrylate resin has the advantages of high transparency, high surface hardness, easy molding and the like, and is widely applied to windows and panels in the fields of household appliances, automobiles and the like. At present, in addition to molding directly using a resin with high transparency, many applications often require the addition of a modifier so that the prepared material forms a translucent effect. In the prior art, two methods are generally used for achieving the semitransparent effect of the material, the first method is to add organosilicon microspheres to be compounded with PC resin or ABS resin, so that the material forms a milky and vaporific semitransparent effect after light is scattered, and the prepared composite material is generally used for LED lamp covers and the like. The second is to design fine dermatoglyph on the surface of the mould by means of the manufacturing method of frosted glass (sand blasting or chemical corrosion to form a surface concave-convex structure), thereby helping the material to realize the frosting effect, which is a clear but hazy effect.
However, there are some drawbacks to using both of the above methods: the material obtained by the first method only achieves some translucency effect, it does not have a frosting effect; the second method material can obtain the frosting effect only by means of the leather grain grinding tool, so that the cost and the complicated processing process of the grinding tool design are greatly increased, and the transparency of the material is not high.
Therefore, there is a need for a polyacrylate resin composition which does not require a leather-grain grinding tool, has low processing cost, and has excellent translucency and sanding properties, and a preparation method thereof.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polyacrylate resin composition with excellent semitransparent and frosting properties, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a polyacrylate resin composition comprises the following components in parts by weight:
39-98 parts of polyacrylate resin, 1-20 parts of lamellar matting agent and 0.5-54 parts of processing aid, wherein the refractive index of the lamellar matting agent is 1.53-1.63, and the lamellar matting agent is lamellar silicate;
the layered silicate is KAl 2 (AlSi 3 O 10 )(OH) 2 And/or KMg 3 (AlSi 3 O 10 )F 2 。
The invention utilizes the lamellar structure in the lamellar matting agent and the difference between the refractive index of the lamellar structure and the refractive index of the polyacrylate resin to uniformly disperse the lamellar structure in the polyacrylate resin, and light rays are subjected to double refraction of the lamellar structure in the lamellar matting agent and the polyacrylate resin, so that the semitransparent frosting effect of the composition is realized.
The lamellar matting agent is lamellar silicate, and the lamellar structure is uniformly dispersed in the polyacrylate resin, so that the composition can achieve semitransparent frosting effect.
With the layered silicate having the above composition, the polishing smoothness and light transmittance of the polyacrylate resin composition (wherein the light transmittance is measured according to the ASTM D1003 method) can be improved. The applicant of the invention has proved through experiments that the natural layered silicate is Mg 3 [Si 4 O 10 ](OH) 2 When the composition prepared by the method has no frosting effect, the transmittance of the composition is less than 10 percent, the composition becomes opaque in solid color, and not all layered silicate can realize the technical effect.
More preferably, the layered matting agent has a aspect ratio greater than 80. The adoption of the layered silicate with a large enough diameter-thickness ratio shows that the crystal sheet layer is peeled off to be thin enough, and the light transmission effect can be better realized.
As a preferred embodiment of the polyacrylate resin composition of the present invention, the polyacrylate resin composition comprises the following components in parts by weight:
39-89 parts of polyacrylic resin and 10-20 parts of lamellar matting agent, wherein the refractive index of the lamellar matting agent is 1.55-1.61.
The ratio of the polyacrylate resin to the lamellar matting agent and the refractive index of the lamellar matting agent have a great influence on the performance of the polyacrylate resin composition, and when the ratio of the polyacrylate resin to the lamellar matting agent and the refractive index of the lamellar matting agent meet the above limits, the prepared polyacrylate resin composition has a better semitransparent frosting effect.
As a preferred embodiment of the polyacrylate resin composition of the present invention, the polyacrylate resin has a refractive index of 1.49 to 1.51.
The invention utilizes the difference between the refractive indexes of the polyacrylate resin (1.49-1.51) and the layered silicate (1.53-1.63), and after the two are blended, the light rays pass through the lamellar structure in the layered matting agent and the double refraction of the polyacrylate resin, so that the frosting effect of the polyacrylate resin composition can be realized. When the refractive index of the polyacrylate resin is out of the range of the present invention, it is mixed with the layered silicate, and the sanding effect of the present invention is not achieved.
As a preferred embodiment of the polyacrylate resin composition of the present invention, the number of the lamellar matting agent is 10 to 500 mesh, more preferably 40 to 100 mesh.
The invention adopts the layered matting agents with different mesh numbers to ensure that the composition has glass frosting effects with different fineness, and when the mesh number of the layered matting agent is 40-100 meshes, the frosting fineness of the composition is higher.
As a preferred embodiment of the polyacrylate resin composition, the processing aid comprises 0-50 parts of toughening agent, 0.3-2 parts of dispersing agent and 0.2-2 parts of auxiliary agent, wherein the toughening agent is a core-shell type toughening agent; the dispersant is at least one of amide type lubricant, stearic acid and stearate type lubricant, ester type lubricant, silicone type lubricant, polyethylene wax and modified polyethylene wax; the auxiliary agent comprises an antioxidant and/or a weather-proof agent.
More preferably, the dispersant is zinc stearate.
More preferably, the shell layer of the core-shell toughening agent is polymethyl methacrylate, the core layer is cross-linked polybutyl acrylate, for example, the core-shell toughening agent is M-210, etc.
More preferably, the antioxidant is at least one of hindered phenol antioxidants, phosphite antioxidants and thioether antioxidants.
More preferably, the weathering agent is at least one of a benzophenone-based ultraviolet light absorber, a benzotriazole-based ultraviolet light absorber, and a hindered amine.
The composition of the invention is also added with a toughening agent, so that the impact resistance of the polyacrylate resin composition can be improved, and the comprehensive performance of the composition is improved.
The antioxidant and the weather-resistant agent are added, so that the oxidation resistance and the stability of the polyacrylate resin composition can be improved, wherein the antioxidant is optimally compounded of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and phenyl tri (2, 4-di-tert-butyl) phosphite, and the weather-resistant agent is optimally 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.
As a preferred embodiment of the polyacrylate resin composition, the polyacrylate resin is at least one of polymethyl acrylate polymer, polyethyl acrylate polymer, polypropylene acrylate polymer, polybutyl acrylate polymer and polymethyl acrylate polymer; more preferably, the polyacrylate resin is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and an acrylic ester compound, and the acrylic ester compound is at least one of methyl acrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, and 2-ethylhexyl methacrylate. Most preferably, the polyacrylate resin is polymethyl methacrylate (PMMA).
When the polyacrylate resin of the type is selected to be mixed with the lamellar matting agent, the prepared polyacrylate resin composition has better frosting effect, proper light transmittance, haze and stronger notch impact strength, and has strong comprehensive performance.
Meanwhile, the invention also discloses a preparation method of the polyacrylate resin composition, which comprises the following steps:
(1) Adding the components into a high-speed mixer according to the proportion and uniformly mixing;
(2) Feeding the mixed materials into a double-screw extruder from a main feeding port, and extruding and granulating to obtain the polyacrylate resin composition.
In addition, the invention also discloses application of the polyacrylate resin composition in household appliances, automobile panels, windows, stationery or toys.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the layered matting agent with special properties and specific refractive indexes is mixed with the polyacrylate resin, so that the semitransparent performance and the frosting performance of the polyacrylate resin composition are obviously improved. The invention further optimizes the composition of the polyacrylate resin composition and improves the comprehensive performance of the polyacrylate resin composition by selecting the weight ratio of the lamellar matting agent to the polyacrylate resin. In addition, the polyacrylate resin composition with semitransparent frosting effect can be obtained by using the high-light mold without adopting a dermatoglyph mold, so that the cost and the complicated processing process of mold design are greatly saved, and the high-efficiency application of the polyacrylate resin composition in household appliances, automobiles or electronic and electric appliances can be realized.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
In the following examples and comparative examples, the experimental methods used were conventional methods unless otherwise specified, and the materials, reagents and the like used, unless otherwise specified, were all commercially available.
The materials selected in the examples and comparative examples of the present invention are as follows:
polymethyl methacrylate 1: PMMA1, brand 7N, desoxase, 7.2g/10min (230 ℃,3.8 kg) of melt flow rate and 1.49 of refractive index;
polymethyl methacrylate 2: PMMA2, trade name FT15, desoxace of manufacturer, melt flow rate of 5.4g/10min (230 ℃,3.8 kg), refractive index of 1.50;
polymethyl methacrylate 3: PMMA3, brand HW55, desoxase, melt flow rate of 1.5g/10min (230 ℃,3.8 kg) and refractive index of 1.51;
methyl methacrylate-methyl acrylate copolymer: the trade name is IR H50, the manufacturer is Mitsubishi chemical, the melt flow rate is 1.0g/10min (230 ℃,3.8 kg), and the refractive index is 1.49;
lamellar matting agent 1: synthetic layered silicate of composition KMg 3 (AlSi 3 O 10 )F 2 The manufacturer is Chuzhou Gray mining, 10 meshes, and the refractive index is 1.58;
lamellar matting agent 2: synthetic layered silicate of composition KMg 3 (AlSi 3 O 10 )F 2 The manufacturer is Chuzhou Gray mining, 40 meshes, and the refractive index is 1.58;
lamellar matting agent 3: synthetic layered silicate of composition KMg 3 (AlSi 3 O 10 )F 2 The manufacturer is Chuzhou Gray mining, 60 meshes, and the refractive index is 1.58;
lamellar matting agent 4: synthetic layered silicate of composition KMg 3 (AlSi 3 O 10 )F 2 The manufacturer is Chuzhou Gray mining, 100 meshes, and the refractive index is 1.58;
lamellar matting agent 5: synthetic layered silicate of composition KMg 3 (AlSi 3 O 10 )F 2 The manufacturer is Chuzhou Gray mining, 500 meshes, and the refractive index is 1.58;
lamellar matting agent 6: natural layered silicate of KAl composition 2 (AlSi 3 O 10 )(OH) 2 The manufacturer is Chuzhou Gray mining, 100 meshes, and the refractive index is 1.58;
lamellar matting agent 7: synthetic layered silicate of composition KMg 3 (AlSi 3 O 10 )F 2 Production plantThe family is Chuzhou Gray mining, 100 meshes, and the refractive index is 1.53;
lamellar matting agent 8: synthetic layered silicate of composition KMg 3 (AlSi 3 O 10 )F 2 The manufacturer is Chuzhou Gray mining, 100 meshes, and the refractive index is 1.55;
lamellar matting agent 9: synthetic layered silicate of composition KMg 3 (AlSi 3 O 10 )F 2 The manufacturer is Chuzhou Gray mining, 100 meshes, and the refractive index is 1.61;
lamellar matting agent 10: synthetic layered silicate of composition KMg 3 (AlSi 3 O 10 )F 2 The manufacturer is Chuzhou Gray mining, 100 meshes, and the refractive index is 1.63;
lamellar matting agent 11: natural layered silicate with 77-5 weight, and its composition is Mg 3 [Si 4 O 10 ](OH) 2 The manufacturer is new brocade material with 500 meshes and refractive index of 1.58;
lamellar matting agent 12: synthetic layered silicate of composition KMg 3 (AlSi 3 O 10 )F 2 The manufacturer is Chuzhou Gray mining, 100 meshes, and the refractive index is 1.50;
lamellar matting agent 13: synthetic layered silicate of composition KMg 3 (AlSi 3 O 10 )F 2 The manufacturer is Chuzhou Gray mining, 100 meshes, and the refractive index is 1.67;
spherical matting agent: the average grain diameter of the organosilicon microsphere is 2 microns, the manufacturer is Korean Sanxingxing, and the trademark is SL-200M;
toughening agent: the core-shell type toughening agent is produced by the manufacturer of Brillouin in Japan and has the brand number of M-210;
dispersing agent: zinc stearate;
an antioxidant: compounding pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and phenyl tri (2, 4-di-tert-butyl) phosphite (mass ratio of 1:2);
weather-resistant agent: 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole. The same commercially available raw materials were used for the toughening agent, the dispersing agent, the antioxidant and the weathering agent in the examples and comparative examples.
Examples 1 to 17
In the examples of the polyacrylate resin composition of the present invention, the formulations of examples 1 to 17 are shown in Table 1, and the preparation method is as follows: the components are added into a high-speed mixer according to the proportion, are mixed uniformly, are fed into a double-screw extruder from a main feeding port, and are subjected to melt extrusion and granulation to obtain the polyacrylate resin composition. Wherein, the temperature settings of each heating area from the feeding port to the die head are respectively: 160 ℃ in the first region, 190 ℃ in the second region, 210 ℃ in the third region to the fifth region, 200 ℃ in the sixth region to the eighth region, 210 ℃ in the ninth region and 220 ℃ in the tenth region.
Comparative examples 1 to 4
Comparative examples 1 to 4 were polyacrylate resin compositions, the formulations of which are shown in Table 1, and the preparation methods were the same as in examples 1 to 17.
TABLE 1
The properties of the polyacrylate resin compositions prepared in examples 1 to 17 and comparative examples 1 to 4 were tested, and the respective properties were tested as follows:
(1) The polishing effect is molded into a 2.0mm template for visual comparison, the polishing fineness is expressed by (+) and the more the (+), the finer the polishing fineness is, and (X) the solid or milky non-polishing effect is expressed;
(2) Light transmittance and haze were tested according to ASTM D1003-2013;
(3) The notched impact strength of the cantilever beam is tested according to the standard ISO 180-2019 method, the size of the sample is 80mm multiplied by 10mm multiplied by 4mm, and the sample is a type A notch;
when the product isThe light transmittance is more than or equal to 75 percent, the haze is 20 to 70 percent, the semitransparent frosting effect with different haziness degrees can be realized, and the impact strength is more than 2kJ/m 2 Can meet the use requirements of a panel, a window and the like.
The test results are shown in Table 2.
TABLE 2
| Group of | Frosting effect | Transmittance% | Haze% | Notched impact strength kJ/m 2 |
| Example 1 | + | 89 | 24 | 2.7 |
| Example 2 | + | 82 | 41 | 2.4 |
| Example 3 | + | 75 | 58 | 2.1 |
| Example 4 | ++ | 83 | 61 | 2.5 |
| Example 5 | ++ | 83 | 63 | 2.6 |
| Example 6 | +++ | 86 | 66 | 2.6 |
| Example 7 | +++ | 87 | 66 | 2.1 |
| Example 8 | +++ | 80 | 65 | 2.4 |
| Example 9 | +++ | 86 | 60 | 2.5 |
| Example 10 | +++ | 86 | 62 | 2.8 |
| Example 11 | +++ | 84 | 66 | 2.9 |
| Example 12 | +++ | 83 | 69 | 2.6 |
| Example 13 | +++ | 86 | 65 | 3.0 |
| Example 14 | +++ | 86 | 64 | 2.3 |
| Example 15 | +++ | 83 | 67 | 4.7 |
| Example 16 | +++ | 81 | 68 | 5.6 |
| Example 17 | +++ | 86 | 65 | 2.9 |
| Comparative example 1 | × | ＜10 | ＞100 | 1.9 |
| Comparative example 2 | × | 51 | 98 | 2.3 |
| Comparative example 3 | × | 90 | 8 | 2.6 |
| Comparative example 4 | × | 70 | 88 | 2.5 |
As can be seen from the test results in Table 2, the polyacrylate resin compositions prepared in examples 1 to 3 can achieve a translucent frosting effect, and the notched impact strength also meets the product use requirements.
The polyacrylate resin compositions prepared in examples 2 and 4-7 adopt 10-500 mesh synthetic lamellar matting agents, so that glass frosting effects with different fineness are realized, the polyacrylate resin compositions prepared in examples 4-6 (mesh number is 40-100 mesh) have better frosting fineness, and the light transmittance, the haze and the impact strength are all higher than those of example 2 (10 mesh lamellar matting agents), and the impact strength is reduced in example 7 (500 mesh lamellar matting agents) although the light transmittance is higher than that of example 6.
In comparison with example 6 (use of a synthetic lamellar matting agent), example 8 uses a natural lamellar matting agent KAl 2 (AlSi 3 O 10 )(OH) 2 The prepared polyacrylate resin composition realizes similar semitransparent frosting effect.
The refractive index of the layered matting agent in examples 9 to 12 was changed, and the prepared composition was excellent in semitransparent frosting effect and notched impact strength, and when the refractive index of the layered matting agent was 1.53 to 1.63, the transmittance of the composition was 83% to 86%, the haze was 60 to 69%, the semitransparent frosting effect was excellent, and the notched impact strength of the composition was also high. When the refractive index of the lamellar matting agent is 1.55-1.61, the transmittance of the composition is 84-86%, the haze is 62-66%, the lamellar matting agent is relatively balanced, the semitransparent frosting effect is better, and the impact performance is better.
Examples 13 to 14 and 17 used PMMA2 or PMMA3 or methyl methacrylate-methyl acrylate copolymer with refractive index of 1.49-1.51, and the difference between the refractive index of the polyacrylate resin and the lamellar matting agent was reduced, so that the semitransparent frosting effect of the composition was good.
In examples 15-16, a toughening agent in a certain weight part is added, the notch impact strength of the prepared polyacrylate resin composition is obviously improved, the frosting effect is maintained, the light transmittance is slightly reduced, and the semitransparent frosting effect can be realized.
Comparative examples 1 to 4 all have no frosting effect, and comparative example 1 uses natural layered silicate as Mg 3 [Si 4 O 10 ](OH) 2 When it is used, the prepared composition has no frosting effect and is combinedThe transmittance of the material is less than 10%, the composition becomes opaque in solid color, and it is found that not all the layered silicate can achieve the above technical effects.
Comparative example 2 uses a spherical matting agent, and a composition obtained by mixing the spherical matting agent with a polyacrylate resin is milky semitransparent, a frosting effect cannot be obtained, the composition has poor light transmittance, high haze and poor notched impact strength, and is substantially different from the composition of the present invention; comparative example 3 used a layered matting agent 12 (refractive index 1.5) whose composition had too high transmittance and low haze, and comparative example 4 used a layered matting agent 13 (refractive index 1.67) whose composition had lower transmittance and higher haze, and the translucent matte effect of the present invention could not be comprehensively achieved.
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 (8)
1. The polyacrylate resin composition is characterized by comprising the following components in parts by weight:
39-98 parts of polyacrylate resin, 1-20 parts of lamellar matting agent and 0.5-54 parts of processing aid, wherein the refractive index of the lamellar matting agent is 1.53-1.63; the lamellar matting agent is lamellar silicate;
the layered silicate is KAl 2 (AlSi 3 O 10 )(OH) 2 And/or KMg 3 (AlSi 3 O 10 )F 2 ；
The refractive index of the polyacrylate resin is 1.49-1.51;
the mesh number of the layered matting agent is 10-500 meshes;
the light transmittance of the polyacrylate resin composition is more than or equal to 75%, the haze is 20-70%, and the impact strength is more than 2kJ/m 2 。
2. The polyacrylate resin composition according to claim 1, which comprises the following components in parts by weight:
39-89 parts of polyacrylic resin and 10-20 parts of lamellar matting agent, wherein the refractive index of the lamellar matting agent is 1.55-1.61.
3. The polyacrylate resin composition according to claim 1, wherein the number of the lamellar matting agent is 40 to 100 mesh.
4. The polyacrylate resin composition according to claim 1 or 2, wherein the processing aid is 0 to 50 parts of a toughening agent, 0.3 to 2 parts of a dispersing agent and 0.2 to 2 parts of an auxiliary agent, and the toughening agent is a core-shell type toughening agent; the dispersant is at least one of amide type lubricant, stearic acid and stearate type lubricant, ester type lubricant, silicone type lubricant, polyethylene wax and modified polyethylene wax; the auxiliary agent comprises an antioxidant and/or a weather-proof agent.
5. The polyacrylate resin composition according to claim 1 or 2, wherein the polyacrylate resin is at least one of a polymethyl acrylate polymer, a polyethyl acrylate polymer, a polypropylene propyl acrylate polymer, a polybutyl acrylate polymer, and a polyhydroxypentyl acrylate polymer.
6. The polyacrylate resin composition according to claim 5, wherein the polyacrylate resin is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and an acrylic acid ester compound, and the acrylic acid ester compound is at least one of methyl acrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, and 2-ethylhexyl methacrylate.
7. A method for producing the polyacrylate resin composition according to any one of claims 1 to 6, comprising the steps of:
(1) Adding the components into a high-speed mixer according to the proportion and uniformly mixing;
(2) Feeding the mixed materials into a double-screw extruder from a main feeding port, and extruding and granulating to obtain the polyacrylate resin composition.
8. Use of the polyacrylate resin composition according to any one of claims 1 to 6 in household appliances, automobile panels, windows, stationery or toys.
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