CN114196151A - 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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- CN114196151A CN114196151A CN202111448466.4A CN202111448466A CN114196151A CN 114196151 A CN114196151 A CN 114196151A CN 202111448466 A CN202111448466 A CN 202111448466A CN 114196151 A CN114196151 A CN 114196151A
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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
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
Abstract
The invention relates to the technical field of high polymer materials, and particularly discloses a polyacrylate resin composition and 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 layered matting agent and 0.5-54 parts of processing aid, wherein the refractive index of the layered matting agent is 1.53-1.63. According to the invention, the lamellar flatting agent with special properties and specific refractive index is selected and mixed with the polyacrylate resin, so that the translucency and the frosting performance of the polyacrylate resin composition are obviously improved. According to the invention, the polyacrylate resin composition with the semitransparent frosted effect can be obtained by using the highlight die without adopting a dermatoglyph die, so that the cost and the complicated processing process of die 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
Polyacrylate resins have many advantages such as high transparency, high surface hardness, and easy molding, and are widely used in windows and panels in the fields of home appliances, automobiles, and the like. At present, besides directly using resin with high transparency for molding, a modifier is often required to be added for many applications, so that the prepared material has a semitransparent effect. In the prior art, two methods are available for achieving a semitransparent effect of a material, the first method is to compound the material with PC resin or ABS resin by adding organic silicon microspheres, so that the material forms a milky-white vaporous semitransparent effect after light is scattered, and the prepared composite material is generally used for LED lamp shades and the like. The second method is to design fine dermatoglyph on the surface of a mould by using a manufacturing method of ground glass (sand blasting or chemical corrosion to form a surface concave-convex structure), so as to help the material to realize a grinding effect, wherein the grinding effect is a clear but hazy effect.
However, both of the above methods have some disadvantages: the material obtained by the first method can only obtain some translucent effect, and does not have a frosted effect; the second method material can obtain the sanding effect only by means of a dermatoglyph grinding tool, greatly increases the design cost of the grinding tool and the complicated processing process, and has low material transparency.
Therefore, a polyacrylate resin composition which does not need a dermatoglyph grinding tool, has low processing cost and better translucency and frosting performance and a preparation method thereof are needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polyacrylate resin composition with excellent translucency and frosting performance, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the polyacrylate resin composition comprises the following components in parts by weight:
39-98 parts of polyacrylate resin, 1-20 parts of a layered matting agent and 0.5-54 parts of a processing aid, wherein the refractive index of the layered matting agent is 1.53-1.63, and the layered matting agent is layered silicate;
the phyllosilicate is KAl2(AlSi3O10)(OH)2And/or KMg3(AlSi3O10)F2。
According to the invention, the lamellar structure in the lamellar matting agent and the difference between the refractive index of the lamellar matting agent and the refractive index of the polyacrylate resin are utilized to uniformly disperse the lamellar structure in the polyacrylate resin, and light rays are refracted by the lamellar structure in the lamellar matting agent and the polyacrylate resin, so that the semitransparent frosted effect of the composition is realized.
The lamellar matting agent is phyllosilicate, and the lamellar structure of the lamellar matting agent is uniformly dispersed in polyacrylate resin, so that the composition can achieve a semitransparent frosted effect.
By using the layered silicate having the above composition, the frosting fineness and the light transmittance (wherein the light transmittance is measured according to the ASTM D1003 method) of the polyacrylate resin composition can be improved. The applicant of the present invention has proved through experiments that the natural phyllosilicate is Mg3[Si4O10](OH)2When they are preparedThe compound has no frosting effect, the light transmittance of the composition is less than 10 percent, the composition becomes solid opaque, and thus, the technical effect can be realized by not all the phyllosilicates.
More preferably, the diameter to thickness ratio of the layered matting agent is greater than 80. The adoption of the phyllosilicate with a large enough diameter-thickness ratio shows that the crystal lamella is stripped to be thin enough, so that 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 layered matting agent, wherein the refractive index of the layered matting agent is 1.55-1.61.
The proportion of the polyacrylate resin and the layered matting agent and the refractive index of the layered matting agent have great influence on the performance of the polyacrylate resin composition, and when the proportion of the polyacrylate resin and the layered matting agent and the refractive index of the layered matting agent meet the above limits, the prepared polyacrylate resin composition has better translucent frosting effect.
In a preferred embodiment of the polyacrylate resin composition of the present invention, the refractive index of the polyacrylate resin is 1.49 to 1.51.
According to the invention, by utilizing the difference between the refractive indexes of the polyacrylate resin (1.49-1.51) and the layered silicate (1.53-1.63), after the polyacrylate resin and the layered silicate are blended, light passes through a lamellar structure in the layered matting agent and double refraction of the polyacrylate resin, and 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, the matting effect of the present invention is not obtained by mixing it with the layered silicate.
In a preferred embodiment of the polyacrylate resin composition of the present invention, the mesh number of the layered matting agent is 10 to 500 mesh, and more preferably, the mesh number of the layered matting agent is 40 to 100 mesh.
According to the invention, the layered matting agents with different meshes are adopted, so 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 higher the fineness of frosting of the composition is.
As a preferred embodiment of the polyacrylate resin composition, the processing aid is 0-50 parts of a toughening agent, 0.3-2 parts of a dispersing agent and 0.2-2 parts of an auxiliary agent, and the toughening agent is a core-shell type toughening agent; the dispersant is at least one of amide lubricant, stearic acid and stearate lubricant, ester lubricant, silicone lubricant, polyethylene wax and modified polyethylene wax; the auxiliary agent comprises an antioxidant and/or a weather resisting agent.
More preferably, the dispersant is zinc stearate.
More preferably, the shell layer of the core-shell type toughening agent is polymethyl methacrylate, and the core layer is crosslinked polybutyl acrylate, for example, the core-shell type toughening agent is M-210.
More preferably, the antioxidant is at least one of hindered phenol type antioxidants, phosphite type antioxidants, and thioether type antioxidants.
More preferably, the weather resistant agent is at least one of a benzophenone-based ultraviolet light absorber, a benzotriazole-based ultraviolet light absorber, and a hindered amine.
The toughening agent is added into the composition, so that the impact resistance of the polyacrylate resin composition can be improved, and the comprehensive performance of the composition is improved.
According to the invention, the antioxidant and the weather resisting agent are added, so that the oxidation resistance and the stability of the polyacrylate resin composition can be improved, wherein the antioxidant is optimally a compound of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris (2, 4-di-tert-butyl) phenyl phosphite, and the weather resisting agent is optimally 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.
In a preferred embodiment of the polyacrylate resin composition of the present invention, the polyacrylate resin is at least one of a polymethyl acrylate polymer, a polyethyl acrylate polymer, a polypropyl acrylate polymer, a polybutyl acrylate polymer, and a polypentyl acrylate polymer; more preferably, the polyacrylate resin is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and an acrylate compound, and the acrylate compound is at least one of methyl acrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, amyl methacrylate and 2-ethylhexyl methacrylate. Most preferably, the polyacrylate resin is polymethyl methacrylate (PMMA).
When the polyacrylate resin of the types is selected and mixed with the layered matting agent, the prepared polyacrylate resin composition has good frosting effect, proper light transmittance, haze and strong 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) and feeding the mixed material 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 lamellar flatting agent with special properties and specific refractive index is selected and mixed with the polyacrylate resin, so that the translucency and the frosting performance of the polyacrylate resin composition are obviously improved. According to the invention, the weight ratio of the layered matting agent to the polyacrylate resin is selected, so that the composition of the polyacrylate resin composition is further optimized, and the comprehensive performance of the polyacrylate resin composition is improved. In addition, the polyacrylate resin composition with the semitransparent frosted effect can be obtained by using a highlight die without adopting a dermatoglyph die, so that the cost and the complicated processing process of die 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
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
In the following examples and comparative examples, the experimental methods used were conventional ones unless otherwise specified, and the materials, reagents and the like used were commercially available ones unless otherwise specified.
The materials selected in the examples and comparative examples of the present invention are as follows:
polymethyl methacrylate 1: PMMA1, 7N, Degussa, melt flow rate of 7.2g/10min (230 ℃, 3.8kg), refractive index of 1.49;
polymethyl methacrylate 2: PMMA2, trademark FT15, manufactured by Degussa, melt flow rate of 5.4g/10min (230 ℃, 3.8kg), refractive index of 1.50;
polymethyl methacrylate 3: PMMA3, brand HW55, manufactured by Degussa, melt flow rate of 1.5g/10min (230 ℃, 3.8kg), refractive index of 1.51;
methyl methacrylate-methyl acrylate copolymer: the product is IR H50, the manufacturer is Mitsubishi chemical, the melt flow rate is 1.0g/10min (230 ℃, 3.8kg), and the refractive index is 1.49;
layered matting agent 1: synthetic phyllosilicate with a composition of KMg3(AlSi3O10)F2The manufacturer is Chuzhou gurui mining, 10 meshes, and the refractive index is 1.58;
layered matting agent 2: synthetic phyllosilicate with a composition of KMg3(AlSi3O10)F2The manufacturer is Chuzhou gurui mining, 40 meshes, and the refractive index is 1.58;
layered matting agent 3: synthetic phyllosilicate with a composition of KMg3(AlSi3O10)F2The manufacturer is Chuzhou gurui mining, 60 meshes, and the refractive index is 1.58;
layered matting agent 4: a synthetic layered silicate consisting ofKMg3(AlSi3O10)F2The manufacturer is Chuzhou keen mining, 100 meshes, and the refractive index is 1.58;
layered matting agent 5: synthetic phyllosilicate with a composition of KMg3(AlSi3O10)F2The manufacturer is Chuzhou gurui mining, 500 meshes, and the refractive index is 1.58;
layered matting agent 6: natural layered silicate having the composition KAl2(AlSi3O10)(OH)2The manufacturer is Chuzhou keen mining, 100 meshes, and the refractive index is 1.58;
layered matting agent 7: synthetic phyllosilicate with a composition of KMg3(AlSi3O10)F2The manufacturer is Chuzhou keen mining, 100 meshes, and the refractive index is 1.53;
layered matting agent 8: synthetic phyllosilicate with a composition of KMg3(AlSi3O10)F2The manufacturer is Chuzhou gurui mining, 100 meshes, and the refractive index is 1.55;
layered matting agent 9: synthetic phyllosilicate with a composition of KMg3(AlSi3O10)F2The manufacturer is Chuzhou keen mining, 100 meshes, and the refractive index is 1.61;
layered matting agent 10: synthetic phyllosilicate with a composition of KMg3(AlSi3O10)F2The manufacturer is Chuzhou keen mining, 100 meshes, and the refractive index is 1.63;
layered matting agent 11: natural layered silicate with a brand number of 77-5 and Mg as the component3[Si4O10](OH)2The manufacturer is a new material of Jintong, 500 meshes and the refractive index is 1.58;
layered matting agent 12: synthetic phyllosilicate with a composition of KMg3(AlSi3O10)F2The manufacturer is Chuzhou keen mining, 100 meshes, and the refractive index is 1.50;
layered matting agent 13: synthetic phyllosilicate with a composition of KMg3(AlSi3O10)F2The manufacturer is Chuzhou gelie ore100 mesh, refractive index 1.67;
spherical matting agent: the organic silicon microspheres have the average particle size of 2 microns, are manufactured by Korea Samsung and have the brand number of SL-200M;
a toughening agent: the core-shell type toughening agent is produced by Japanese Brillouin with the brand number of M-210;
dispersing agent: zinc stearate;
antioxidant: compounding pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butyl) phenyl phosphite (the mass ratio is 1: 2);
weather resisting agent: 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole. The same commercial raw materials were used for the toughening agent, the dispersing agent, the antioxidant and the weather resistant 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 comprises: adding the components into a high-speed mixer according to a certain proportion, uniformly mixing, feeding into a double-screw extruder from a main feeding port, performing melt extrusion, and granulating to obtain the polyacrylate resin composition. Wherein the temperature of each heating area from the feeding port to the die head is respectively set as follows: 160 ℃ in the first zone, 190 ℃ in the second zone, 210 ℃ in the third to fifth zones, 200 ℃ in the sixth to eighth zones, 210 ℃ in the ninth zone and 220 ℃ in the tenth zone.
Comparative examples 1 to 4
Comparative examples 1 to 4 are polyacrylate resin compositions, the formulation of which is shown in Table 1, and the preparation method is the same as in examples 1 to 17.
TABLE 1
The polyacrylate resin compositions prepared in examples 1 to 17 and comparative examples 1 to 4 were tested for their properties by the following methods:
(1) the frosted effect is injection-molded by a 2.0mm sample plate for visual comparison, the frosted fineness is represented by (+) and more (+) represents more fineness, and (X) represents a real color or milky white non-frosted effect;
(2) the light transmittance and haze were measured according to ASTM D1003-2013;
(3) the cantilever beam notch impact strength is tested according to a method of ISO 180-;
when the light transmittance of the product is more than or equal to 75 percent and the haze is 20 to 70 percent, the semitransparent frosted effect with different haze degrees can be realized, and the impact strength is more than 2kJ/m2Can meet the use requirements of panels, windows and the like.
The test results are shown in table 2.
TABLE 2
| Group of | Frosting effect | Light transmittance% | Haze%) | Notched impact strength kJ/m2 |
| 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 use requirements of the product.
The polyacrylate resin compositions prepared in examples 2 and 4-7 adopt the synthetic layered matting agent with 10-500 meshes, so that glass frosting effects with different fineness degrees are realized, the polyacrylate resin compositions (with 40-100 meshes) prepared in examples 4-6 have better frosting fineness degree, and the light transmittance, the haze and the impact strength are higher than those of the polyacrylate resin composition (with 10 meshes) prepared in example 2, and the polyacrylate resin composition (with 500 meshes) prepared in example 7 has higher light transmittance but lower impact strength than that of the polyacrylate resin composition prepared in example 6.
Example 8 uses the natural layered matting agent KAl in comparison to example 6 (using the synthetic layered matting agent)2(AlSi3O10)(OH)2The prepared polyacrylate resin composition realizes a similar translucent frosting effect.
In examples 9 to 12, the refractive index of the layered matting agent was changed, and the prepared composition had a good translucent matte effect and a good notched impact strength, and when the refractive index of the layered matting agent was 1.53 to 1.63, the light transmittance of the composition was 83% to 86%, the haze was 60 to 69%, the translucent matte effect was good, and the notched impact strength of the composition was also high. When the refractive index of the layered matting agent is 1.55 to 1.61, the light transmittance of the composition is 84 to 86%, the haze is 62 to 66%, the relative balance is achieved, the translucent frosting effect is better, and the impact performance is better.
In examples 13 to 14 and 17, the refractive index of the polyacrylate resin is reduced from that of the layered matting agent by adopting PMMA2 or PMMA3 or methyl methacrylate-methyl acrylate copolymer with the refractive index of 1.49 to 1.51, so that the translucent frosting effect of the composition is good.
In examples 15 to 16, a certain amount of the toughening agent was added, and the obtained polyacrylate resin composition had significantly improved notched impact strength, retained matte effect, and slightly reduced light transmittance, but still achieved translucent matte effect.
None of comparative examples 1-4 had a frosting effect, and comparative example 1 used a natural layered silicate as Mg3[Si4O10](OH)2Meanwhile, the prepared composition has no frosting effect, the light transmittance of the composition is less than 10%, the composition becomes solid and opaque, and thus, the technical effect can not be realized by all the phyllosilicates.
Comparative example 2 adopts a spherical matting agent, and the composition obtained by mixing the spherical matting agent with polyacrylate resin is milky and translucent, so that a frosted effect cannot be obtained, the composition has poor light transmittance and high haze, the notch impact strength is lower than that of example 6, and the composition is substantially different from the composition of the invention; comparative example 3, in which the layered matting agent 12 (refractive index of 1.5) was used, had too high a light transmittance and very low haze, and comparative example 4, in which the layered matting agent 13 (refractive index of 1.67) was used, had a low light transmittance and a high haze, and the translucent frosting effect of the present invention could not be achieved in combination.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
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 layered matting agent and 0.5-54 parts of processing aid, wherein the refractive index of the layered matting agent is 1.53-1.63; the layered matting agent is layered silicate;
the phyllosilicate is KAl2(AlSi3O10)(OH)2And/or KMg3(AlSi3O10)F2。
2. The polyacrylate resin composition according to claim 1, comprising the following components in parts by weight:
39-89 parts of polyacrylic resin and 10-20 parts of layered matting agent, wherein the refractive index of the layered matting agent is 1.55-1.61.
3. The polyacrylate resin composition according to claim 1, wherein the refractive index of the polyacrylate resin is 1.49 to 1.51.
4. The polyacrylate resin composition according to claim 1, wherein the layered matting agent has a mesh size of 10 to 500 mesh.
5. The polyacrylate resin composition according to claim 4, wherein the layered matting agent has a mesh size of 40 to 100 mesh.
6. 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 dispersant 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 lubricant, stearic acid and stearate lubricant, ester lubricant, silicone lubricant, polyethylene wax and modified polyethylene wax; the auxiliary agent comprises an antioxidant and/or a weather resisting agent.
7. 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 propyl acrylate polymer, a butyl acrylate polymer, and a pentyl acrylate polymer.
8. The polyacrylate resin composition according to claim 7, wherein the polyacrylate resin is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and an acrylate compound, and the acrylate 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.
9. The method for preparing the polyacrylate resin composition according to any one of claims 1 to 8, comprising the steps of:
(1) adding the components into a high-speed mixer according to the proportion and uniformly mixing;
(2) and feeding the mixed material into a double-screw extruder from a main feeding port, and extruding and granulating to obtain the polyacrylate resin composition.
10. Use of the polyacrylate resin composition according to any one of claims 1 to 8 in home appliances, automobile panels, windows, stationery or toys.
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