CN109161151B - Transparent ABS (acrylonitrile-butadiene-styrene) frosted resin and preparation method thereof - Google Patents
Transparent ABS (acrylonitrile-butadiene-styrene) frosted resin and preparation method thereof Download PDFInfo
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- CN109161151B CN109161151B CN201810655908.4A CN201810655908A CN109161151B CN 109161151 B CN109161151 B CN 109161151B CN 201810655908 A CN201810655908 A CN 201810655908A CN 109161151 B CN109161151 B CN 109161151B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
Abstract
The invention relates to frosted resin, in particular to transparent ABS frosted resin and a preparation method thereof. Aims to solve the problems that the ground glass is heavier than ground resin and is easy to break. The key points of the technical scheme are as follows: comprises the following components in percentage by weight: 80-97% of ABS resin and 3-20% of organic silicon microspheres. By adopting the proportion, the refractive index of the ABS resin is improved to 1.6-1.7, the light transmittance is reduced by 5-15%, so that the light emitted by the LED lamp is softer, the intensity is high, the toughness is good, the formula is simple, the preparation is easy, the cost is low, and the requirements of consumers are met.
Description
Technical Field
The invention relates to frosted resin, in particular to transparent ABS frosted resin and a preparation method thereof.
Background
In general, sanding is a process of making an originally smooth surface uneven and irradiating light to form a diffuse reflection on the surface, and the resulting product becomes a sanded product.
Ground glass or resin is usually selected for the lamp to achieve the effect of soft light, but the ground glass or resin is produced by a machining method, such as a sand blasting process, so that the labor intensity is high, and the effect is not ideal enough.
In order to solve the problems, at present, chinese patent with publication number CN103342952A discloses a polyurethane resin frosted paint and a preparation method thereof, and the key points of the technical scheme are as follows: firstly, producing a multi-component polyurethane frosted coating, then spraying the polyurethane frosted coating on cleaned glass, and baking to obtain the sand-imitating effect.
Although the proposal improves the frosting effect of the glass, the frosted glass prepared by the invention is heavier than frosted resin and is easy to break.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the transparent ABS frosted resin, the resin has a frosted effect, the weight is light, the toughness is good, and the light of the prepared LED lamp is softer.
The technical purpose of the invention is realized by the following technical scheme: the transparent ABS frosted resin comprises the following components in percentage by weight:
80 to 97 percent of ABS resin
3-20% of organic silicon microspheres.
By adopting the technical scheme, the ABS resin is fully called acrylonitrile-butadiene-styrene copolymer, and is a thermoplastic high polymer material structure which has high strength and good toughness and is easy to machine and mold. The ABS resin is a terpolymer of acrylonitrile, 1, 3-butadiene and styrene, can normally perform in an environment of-25-60 ℃, has good formability, can be processed into a product with a smooth surface, is easy to dye and electroplate, and can be mixed with various resins to form a blend.
By adding the regular organic silicon microspheres with higher surface gloss, the whole ABS resin has a frosted effect after being extruded, has a better light ray blocking effect, reduces the vertical reflection and reflectivity of surface light rays, and better reduces the light loss, and when the ABS resin is used as a lampshade, the frosted effect does not need to be manufactured on the surface of the lampshade through reprocessing;
the organic silicon microsphere is a multifunctional special organic silicon resin microsphere, is snowy white regular free-flowing spherical fine powder, has a three-dimensional cross-linked reticular molecular structure, presents excellent heat resistance and dispersion performance, is uniformly dispersed in a matrix by a fine transparent glass sphere when entering ABS resin, and is refracted in a light source penetrating mode through the difference of refractive indexes in the ABS to change the advancing route of light, so that the frosted effect is achieved.
By adopting the proportion, the refractive index of the ABS resin is increased by 1.6-1.7, the light transmittance is reduced by 5-15%, so that the light emitted by the prepared LED lamp is softer, the intensity is high, the toughness is good, the formula is simple, the cost is low, and the requirements of consumers are met.
The invention is further configured to: the transparent ABS frosted resin also comprises a coupling agent.
By adopting the technical scheme, the coupling agent is used as a surface modifier, the viscosity of the synthetic resin melt can be reduced in the plastic processing process, the dispersity of the filler is improved to improve the processing performance, and the product can obtain good surface quality and mechanical, thermal and electrical properties by applying the coupling agent to the plastic processing process, so that the prepared ABS resin has good sanding effect and good mechanical strength, thermal stability and electrical resistance.
The invention is further configured to: the coupling agent comprises one or the combination of more than two of zirconium coupling agent, titanate coupling agent and silane coupling agent.
By adopting the technical scheme, the zirconium coupling agent is a low-molecular-weight inorganic polymer containing zirconium aluminate. The adhesive can promote the adhesion between ABS resin and organic silicon microspheres, and can improve the performance, especially the rheological property, of a composite material system;
the titanate coupling agent can promote better adhesion between the ABS resin and the organic silicon microspheres and has good coupling effect;
the general formula of the silane coupling agent is RSiX3In the formula, R represents amino, sulfydryl, vinyl, epoxy, cyano, methacryloxy and other groups, and the groups have stronger reaction capability with different matrix resins and can promote the adhesion between the ABS resin and the organic silicon microspheres.
The invention is further configured to: the transparent ABS frosted resin also comprises a lubricant.
By adopting the technical scheme, the lubricant has good compatibility with the ABS resin and the organic silicon microspheres, and plays a role in reducing the cohesion between the molecules of the ABS resin and the organic silicon microspheres, thereby improving the internal friction heat generation of the plastic melting material and the fluidity of the melting material. The combination of the internal lubricant with the ABS resin and the organic silicon microsphere molecules is not strong, and the effect similar to that of a rolling bearing can be generated, so that the internal lubricant can be arranged in the melt flow direction to slide with each other, the internal friction is reduced, and the time and the energy required by the ABS resin and the organic silicon microsphere to finish the mixing process can be effectively reduced.
The invention is further configured to: the lubricant is one or the combination of more than two of polyethylene lubricant, polytetrafluoroethylene lubricant and polypropylene lubricant.
By adopting the technical scheme, the polyethylene lubricant, the polytetrafluoroethylene lubricant and the polypropylene lubricant have good compatibility with the ABS resin and the organic silicon microspheres, so that the ABS resin and the organic silicon microspheres are uniformly mixed more simply and conveniently.
The invention is further configured to: the transparent ABS frosted resin also comprises an antioxidant.
By adopting the technical scheme, the antioxidant can prevent the adverse effect of oxygen, prevent or delay the oxidation of the ABS resin and the organic silicon microspheres, improve the stability of the ABS resin and the organic silicon microspheres and prolong the service life.
The invention is further configured to: the antioxidant is one or the combination of more than two of tetra [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tri [2, 4-di-tert-butylphenyl ] phosphite and dilauryl thiodipropionate.
By adopting the technical scheme, the tetra [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester is white crystalline powder and has stable chemical properties; the volatility is small, the extraction resistance is good, the thermal stability is high, the persistent effect is long, and the paint is not colored, polluted and nontoxic; is a hindered phenol antioxidant with high molecular weight, has very low volatility, is not easy to migrate and is extraction-resistant; the ABS resin can be effectively prevented from thermal oxidation degradation in the long-term aging process, is also an efficient processing stabilizer, and can improve the color change resistance of a polymer material under a high-temperature processing condition;
the tris [2, 4-di-tert-butylphenyl ] phosphite ester has good compatibility with ABS resin, relieves thermal oxidative degradation of the ABS resin in a long-term aging process, and has excellent performances of high efficiency, no discoloration, no pollution, no odor and the like;
dilauryl thiodipropionate, DLTP for short, relieves thermal oxidation degradation of ABS resin in a long-term aging process, and is non-toxic, green and environment-friendly;
the tetra [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, DLTP and tri [2, 4-di-tert-butylphenyl ] phosphite have a good synergistic effect, and the thermal stability of the ABS resin in the thermal processing process can be improved.
The invention also aims to provide a preparation method of the transparent ABS frosted resin, which has the advantages of simple formula, simple preparation operation and low cost.
The second technical purpose of the invention is realized by the following technical scheme: the preparation method of the transparent ABS frosted resin comprises the following steps:
s1: weighing the corresponding components according to the proportion;
s2: pouring the materials into a high-speed stirrer to be stirred for 10-20 minutes;
s3: and (3) putting the mixed materials into a screw extruder for extrusion molding.
Through adopting above-mentioned technical scheme, mix each component batching to make whole more even, put into screw extruder again and extrude, help the formation of ABS resin dull polish effect, make the comparatively even dull polish effect of overall distribution in extrusion process simultaneously.
The invention is further configured to: in the extrusion molding process of the screw extruder, the screw temperature is 190-240 ℃.
Through adopting above-mentioned technical scheme, because the screw rod drives advancing of material, in order to make the material melt and take place the reaction, need the suitable temperature of screw rod control, thereby reduce the condition that the high temperature appears carbonization, blackening, and the temperature is crossed low and is made the material not get into the molten state, thereby makes the condition of extruding failure appear.
The invention is further configured to: the screw extruder comprises a feeding zone, a melting zone, a mixing zone, a die head zone and a die head outlet, wherein the temperature of the feeding zone is 185-minus 193 ℃, the temperature of the melting zone is 195-minus 205 ℃, the temperature of the mixing zone is 215-minus 222 ℃, the temperature of the die head zone is 228-minus 235 ℃, and the temperature of the die head outlet is 205-minus 215 ℃.
Through adopting above-mentioned technical scheme, the temperature control of each section is all inequality, the temperature that is close to the feeding district is lower relative the rest, prevent that pan feeding mouth material from melting and leading to blockking up, also can not hang down, if the feeding temperature is crossed lowly, make the extension of solid conveying district, the length in plastify district and fuse-element conveying district has been reduced, can arouse that the plastify is bad, influence product quality, and to melting district and mixing district, the vacuum degree that controls this section through the control temperature is an important technological index, if the vacuum degree is lower, can influence the exhaust effect, lead to having the bubble in the tubular product, the mechanical properties of tubular product has seriously been reduced. In order to make the gas in the material easily escape, the plasticizing degree of the material in the section should be controlled not to be too high, and the exhaust pipeline should be frequently cleaned to avoid blocking the material barrel, the rotation speed of the screw rod in the die head area should be increased, the resistance of the machine head should be reduced, and the pressure of the thermometer in the plasticizing area should be increased to facilitate the increase of the conveying speed, and the outlet of the die head is an important part for forming the extruded product, and the function of the outlet of the die head is to generate higher melt pressure and form the melt into the required shape, and the shape is formed by proper temperature reduction and is no longer in a molten state.
In conclusion, the invention has the following beneficial effects:
1. by the formula and the preparation method, the prepared ABS resin has a good frosting effect, is wholly dispersed, has a good manufacturing effect, has good shading performance and good light reflectivity, is softer in light of a lampshade of an LED lamp, is low in cost, and meets the requirements of consumers.
2. The prepared finished product has high strength, good toughness and long service life.
3. The preparation method is simple, and the prepared finished product has high quality and is easy to popularize.
Detailed Description
The present invention is described in detail below with reference to tables and examples.
The lubricant has no special class requirement, and can be selected from one of polyethylene lubricant, polytetrafluoroethylene lubricant and polypropylene lubricant or the combination of more than two of polyethylene lubricant, polytetrafluoroethylene lubricant and polypropylene lubricant.
The coupling agent has no special class requirement, and can be one of zirconium coupling agent, titanate coupling agent and silane coupling agent or the combination of more than two of zirconium coupling agent, titanate coupling agent and silane coupling agent.
The antioxidant is not particularly limited, and may be selected from pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite and dilauryl thiodipropionate (DLTP for short), or a combination of two or more thereof.
The organic silicon microspheres are purchased from Shenzhen treasure plastic materials Limited, and other raw materials are purchased from the market.
ABS resins, all known as acrylonitrile-butadiene-styrene copolymers.
Example one
The transparent ABS frosted resin comprises the following components in percentage by weight:
80 parts of ABS resin
20 parts of organic silicon microspheres
0.002 part of polyethylene lubricant
0.002 part of zirconium coupling agent
0.001 part of tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester
0.001 part of tris [2, 4-di-tert-butylphenyl ] phosphite
Wherein the particle size of the organic silicon microsphere is 30 microns.
Example two
The difference between the second embodiment and the first embodiment is that the weight of ABS resin and the weight of organosilicon microsphere are respectively adjusted to 85 parts and 15 parts.
EXAMPLE III
The third embodiment is different from the first embodiment in that the weights of the ABS resin and the silicone microspheres are respectively adjusted to 90 parts and 10 parts.
Example four
The fourth example is different from the first example in that the weight of the ABS resin and the weight of the organic silicon microspheres are respectively adjusted to 95 parts and 5 parts.
EXAMPLE five
The fifth embodiment is different from the first embodiment in that the weights of the ABS resin and the silicone microspheres are adjusted to 97 parts and 3 parts, respectively.
EXAMPLE six
A transparent ABS frosted resin, example six is different from example five in that polyethylene lubricant, zirconium coupling agent, tetra [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite are not added.
EXAMPLE seven
The seventh embodiment is different from the first embodiment in that the particle size of the silicone microspheres is 40 microns.
Example eight
The difference between the eighth embodiment and the first embodiment is that the particle size of the organic silicon microspheres is 60 microns.
Example nine
The ninth embodiment is different from the first embodiment in that the particle size of the silicone microspheres is 80 microns.
Comparative example 1
The ABS resin is prepared by adding 100 parts of ABS resin.
TABLE 1 summary of the components and proportions of the examples and comparative examples data
Table 2 summary of examples containing silicone microspheres of different particle sizes
TABLE 3 analysis of the Properties of the examples and comparative examples
Table 1 is a summary of the components and the proportions of the data of the above examples and comparative examples, and Table 2 is a summary of the examples containing the organosilicon microspheres with different particle sizes, so that the differences of the added components and the proportions of the examples and comparative examples and the differences of the particle sizes of the organosilicon microspheres are more visually shown.
The performance analysis of each example in table 1 and table 2 is performed to obtain table 3, and the analysis of each item of data in table 3 can find that, under the condition that other conditions are not changed, the refractive index of the ABS resin gradually increases and the light transmittance gradually decreases with the increase of the specific gravity of the silicone microspheres; the haze gradually increases and the surface roughness also gradually increases. In addition, experiments show that the concave-convex density of the surface of the obtained ABS resin is increased along with the increase of the specific gravity of the organic silicon microspheres; the larger the particle size of the organic silicon microspheres is, the larger the surface concave-convex degree of the obtained ABS resin is. It is obvious from the experimental results that due to the addition of the organic silicon microspheres, the frosting effect of the ABS resin surface is well improved, and the light scattering plate or the light scattering film as an LED can make the light softer.
Although the influence of the addition of the polyethylene lubricant, the zirconium-based coupling agent, the pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and the tris [2, 4-di-tert-butylphenyl ] phosphite on the transparent ABS sanding resin cannot be directly reflected from the data in table 3, the four compounds affect the time of the preparation process and the quality of the prepared transparent ABS sanding resin, and play very important roles.
Example 10
The preparation method of the transparent ABS frosted resin comprises the following steps of:
s1, weighing the corresponding components according to the proportion;
s2, pouring the materials into a high-speed stirrer to be stirred for 10-20 minutes;
s3, putting the mixed materials into a screw extruder for extrusion molding;
the screw extruder comprises a feeding zone, a melting zone, a mixing zone, a die head zone and a die head outlet, wherein the temperature of the feeding zone is 190 ℃, the temperature of the melting zone is 200 ℃, the temperature of the mixing zone is 220 ℃, the temperature of the die head zone is 230 ℃, and the temperature of the die head outlet is 210 ℃.
In order to control the quality of the finished product, the temperature of each zone of the screw extruder is well controlled, wherein the temperature of the feeding zone is 185-193 ℃, the temperature of the melting zone is 195-205 ℃, the temperature of the mixing zone is 215-222 ℃, the temperature of the die head zone is 228-235 ℃, the temperature of the outlet of the die head is 205-215 ℃, and the quality of the finished product prepared in the above range is good.
Examples 11 to 19
The preparation methods of the transparent ABS frosted resin, examples 11 to 19 are the preparation steps of the preparation examples 2 to 9 and the comparative example 1, and the differences from the example 10 are only the differences of the weighed components or the weight.
In addition, the invention also makes a routine performance test on the finished products prepared in the examples 1 and 7, and the following table specifically shows:
the heat resistance in the examples was determined using the Vicat softening temperature standard of German Industrial Standard DIN 53460, specifically the temperature at which a certain indenter penetrates the sample vertically to a depth of 1mm under the action of a certain force; according to the test principle, the higher the vicat temperature, the better the heat resistance of the material, and conversely, the worse the heat resistance. The aging resistance is measured by adopting a national standard GB-T16422 xenon lamp accelerated aging experiment, specifically, a mechanical property test sample strip is subjected to the xenon lamp accelerated aging experiment according to the standard of GB29344, the color change degrees before xenon lamp aging and after 1000h are respectively tested by a color tester, and a color difference value delta E is obtained; according to the testing principle, the larger the Delta E value is, the poorer the aging resistance of the material is, and otherwise, the better the aging resistance is.
As can be seen from the above table, the tensile strength, notch impact strength and bending strength of the finished products prepared in examples 1 and 7 are improved to a certain extent, and the mechanical strength is good; the Vicat temperature is obviously improved, so the heat resistance is better; the ageing resistance is also obviously improved.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (8)
1. Transparent ABS dull polish resin, its characterized in that: comprises the following components in percentage by weight:
80 to 97 percent of ABS resin
3-20% of organic silicon microspheres;
the particle size of the organic silicon microsphere is 30, 40, 60 or 80 microns
The transparent ABS frosted resin also comprises a lubricant; the lubricant is one or the combination of more than two of polyethylene lubricant, polytetrafluoroethylene lubricant and polypropylene lubricant;
compared with ABS resin, the prepared ABS ground resin has the advantages that the refractive index is improved to 1.6-1.7 or 1.74, and the light transmittance is reduced by 5-15%.
2. The transparent ABS frosted resin according to claim 1, wherein: the transparent ABS frosted resin also comprises a coupling agent.
3. The transparent ABS scrub resin according to claim 2, wherein: the coupling agent comprises one or the combination of more than two of zirconium coupling agent, titanate coupling agent and silane coupling agent.
4. The transparent ABS frosted resin according to claim 1, wherein: the transparent ABS frosted resin also comprises an antioxidant.
5. The transparent ABS frosted resin according to claim 4, wherein: the antioxidant is one or the combination of more than two of tetra [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tri [2, 4-di-tert-butylphenyl ] phosphite and dilauryl thiodipropionate.
6. The preparation method of the transparent ABS frosted resin is characterized by comprising the following steps: the method comprises the following steps:
s1: weighing the components according to the proportion of the ABS frosted resin of any one of claims 1 to 5;
s2: pouring the materials into a high-speed stirrer to be stirred for 10-20 minutes;
s3: and (3) putting the mixed materials into a screw extruder for extrusion molding.
7. The method for preparing the transparent ABS frosted resin according to claim 6, wherein: in the extrusion molding process of the screw extruder, the screw temperature is 190-240 ℃.
8. The method for preparing the transparent ABS frosted resin according to claim 6, wherein: the screw extruder comprises a feeding zone, a melting zone, a mixing zone, a die head zone and a die head outlet, wherein the temperature of the feeding zone is 185-minus 193 ℃, the temperature of the melting zone is 195-minus 205 ℃, the temperature of the mixing zone is 215-minus 222 ℃, the temperature of the die head zone is 228-minus 235 ℃, and the temperature of the die head outlet is 205-minus 215 ℃.
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| CN102807723A (en) * | 2011-05-31 | 2012-12-05 | 合肥杰事杰新材料股份有限公司 | ABS resin and preparation method thereof |
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