CN111690216A - High-temperature-resistant light diffusion PVC material and preparation method thereof - Google Patents
High-temperature-resistant light diffusion PVC material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-temperature-resistant photodiffusion PVC material and a preparation method thereof, wherein the PVC material is prepared from the following raw materials in parts by weight: 100 parts of PVC resin, 105 parts of methyl vinyl silicone rubber, 5-20 parts of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 0.1-0.4 part of methyl hydrogen-containing silicone oil, 0.1-0.4 part of polyethylene wax, 2-5 parts of epoxidized soybean oil, 4-8 parts of calcium-zinc stabilizer, 1-2 parts of calcium stearate, 2-3 parts of anti-aging agent, 5-40 parts of dioctyl phthalate, 5-40 parts of tris (2-ethylhexyl) trimellitate, 0.4-0.8 part of organic silicon microspheres, OB: 0.03-0.05 part, wherein the preparation method comprises the steps of preparing a first mixture, a second mixture and a third mixture respectively, then mixing the three mixtures to prepare the mixture, and finally preparing the PVC material.
Description
Technical Field
The invention relates to a PVC material, in particular to a high-temperature-resistant light diffusion PVC material and a preparation method thereof.
Background
The PVC material is one of five general-purpose plastics, has excellent comprehensive performance after modification, has the total yield second to that of polyethylene, and is widely applied to various fields of industry, agriculture, buildings, electronics and electrics, transportation, electric power, telecommunication, packaging and the like.
The PVC material is a polymer material which is widely applied in the fields of communication, electronics and lamp decoration at present, has chemical corrosion resistance, strong resistance to oxidant, reducing agent and strong acid, is easy to produce and low in cost, and is widely applied to products such as LED lamp belts, lampshade lamp panels and the like. However, PVC materials have poor stability under the action of light and heat, and can be decomposed and discolored under the action of high temperature or after long-time sunlight solarization, and the physical and mechanical properties are rapidly reduced.
Among the prior art, PVC materials generally have some drawbacks, such as: the defects of high-temperature oil yielding, aging and stickiness, brittleness, poor signal transmission attenuation and the like are overcome, and therefore the self-developed high-temperature-resistant light diffusion PVC material is urgently needed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a high-temperature-resistant light diffusion PVC material and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a high-temperature-resistant light diffusion PVC material is prepared from the following raw materials in parts by weight: 100 portions of PVC resin, 105 portions of methyl vinyl silicone rubber, 5-20 portions of 1, 3-divinyl-1, 1,3, 3-tetramethyl disiloxane platinum, 0.1-0.4 portion of methyl hydrogen-containing silicone oil, 0.1-0.4 portion of polyethylene wax, 2-5 portions of epoxy soybean oil, 4-8 portions of calcium-zinc stabilizer, 1-2 portions of calcium stearate, 2-3 portions of anti-aging agent, 5-40 portions of dioctyl phthalate, 5-40 portions of tris (2-ethylhexyl) trimellitate, 0.4-0.8 portion of organic silicon microsphere and OB: 0.03-0.05 part.
Preferably, 103 parts of PVC resin 101-vinyl silicone rubber, 8-15 parts of methyl vinyl silicone rubber, 0.2-0.3 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 8-15 parts of methyl hydrogen silicone oil, 0.1-0.3 part of polyethylene wax, 2-3 parts of epoxidized soybean oil, 4-6 parts of calcium zinc stabilizer, 1-2 parts of calcium stearate, 2-3 parts of anti-aging agent, 15-35 parts of dioctyl phthalate, 15-35 parts of tris (2-ethylhexyl) trimellitate, 0.5-0.7 part of organic silicon microspheres and OB: 0.04-0.05 part.
Preferably, 101 parts of PVC resin, 8 parts of methyl vinyl silicone rubber, 0.2 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 8 parts of methyl hydrogen-containing silicone oil, 0.1 part of polyethylene wax, 2 parts of epoxidized soybean oil, 4 parts of calcium-zinc stabilizer, 1 part of calcium stearate, 2 parts of anti-aging agent, 15 parts of dioctyl phthalate, 15 parts of tri (2-ethylhexyl) trimellitate, 0.5 part of organic silicon microsphere and 0.04 part of OB.
Preferably, the PVC resin comprises 103 parts of PVC resin, 15 parts of methyl vinyl silicone rubber, 0.3 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 15 parts of methyl hydrogen-containing silicone oil, 0.3 part of polyethylene wax, 3 parts of epoxidized soybean oil, 6 parts of calcium-zinc stabilizer, 2 parts of calcium stearate, 3 parts of anti-aging agent, 35 parts of dioctyl phthalate, 35 parts of tris (2-ethylhexyl) trimellitate, 0.7 part of organic silicon microspheres and 0.05 part of OB.
Preferably, 100 parts of PVC resin, 5 parts of methyl vinyl silicone rubber, 0.1 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 5 parts of methyl hydrogen-containing silicone oil, 0.1 part of polyethylene wax, 2 parts of epoxidized soybean oil, 4 parts of calcium-zinc stabilizer, 1 part of calcium stearate, 2 parts of anti-aging agent, 5 parts of dioctyl phthalate, 5 parts of tris (2-ethylhexyl) trimellitate, 0.4 part of organic silicon microsphere, OB: 0.03 part.
Preferably, 102 parts of PVC resin, 12 parts of methyl vinyl silicone rubber, 0.25 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 12 parts of methyl hydrogen-containing silicone oil, 0.25 part of polyethylene wax, 0.25 part of epoxidized soybean oil, 6 parts of calcium zinc stabilizer, 1.5 parts of calcium stearate, 2.5 parts of anti-aging agent, 22.5 parts of dioctyl phthalate, 22.5 parts of tri (2-ethylhexyl) trimellitate, 0.6 part of silicone microspheres, OB: 0.04 part.
Preferably, 105 parts of PVC resin, 20 parts of methyl vinyl silicone rubber, 0.4 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 20 parts of methyl hydrogen silicone oil, 0.4 part of polyethylene wax, 5 parts of epoxidized soybean oil, 8 parts of calcium-zinc stabilizer, 2 parts of calcium stearate, 3 parts of anti-aging agent, 40 parts of dioctyl phthalate, 40 parts of tri (2-ethylhexyl) trimellitate, 0.8 part of organic silicon microsphere, OB: 0.05 part.
The anti-aging agent is composed of 2,2 '-thiobis (4-methyl-6-tert-butylphenol) and tris (2, 4-di-tert-butyl) phenyl phosphite, wherein the weight part ratio of the 2,2' -thiobis (4-methyl-6-tert-butylphenol) to the tris (2, 4-di-tert-butyl) phenyl phosphite is 2: 1.
A method for preparing the high-temperature-resistant light diffusion PVC material comprises the following steps:
(1) preparing a first mixture: mixing the methyl vinyl silicone rubber, 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, methyl hydrogen-containing silicone oil, epoxidized soybean oil and polyethylene wax in a weight portion of 0.05-0.2 in a mixer with the rotation speed of 20-150rpm for 15-30min, then adding 1-2 weight portions of anti-aging agent, and continuously mixing for 5-10min to prepare the first mixture.
(2) Preparing a second mixture: and mixing the calcium zinc stabilizer, the calcium stearate, the OB, the dioctyl phthalate in 10-20 parts by weight, the tris (2-ethylhexyl) trimellitate in 10-20 parts by weight, the organic silicon microspheres and the anti-aging agent in the rest parts by weight in a mixer with the rotating speed of 20-150rpm for 15-30min to prepare the second mixture.
(3) Preparing a third mixture: and (3) mixing the PVC resin with the rest parts by weight of dioctyl phthalate, tri (2-ethylhexyl) trimellitate, the organic silicon microspheres and the polyethylene wax in a high-speed mixer at the rotating speed of 20-150rpm for 8-10min to obtain a third mixture.
(4) Preparing a mixture: and sequentially adding the first mixture, the second mixture and the third mixture into a mixer with the rotation speed of 30-150rpm, mixing for 25-30min, putting into a cooling mixer with the temperature of 0-65 ℃ and the rotation speed of 50-150rpm, performing cold stirring for 10-30min, and discharging to obtain the mixture.
(5) Preparing a PVC material: and extruding and granulating the mixture in a double-screw extrusion granulator with the rotating speed of 30-150rpm to obtain the PVC material.
The invention has the beneficial effects that: the PVC material prepared by the invention has excellent toughness and high temperature resistance, and in addition, the obtained material is non-toxic, transparent, pollution-free, light in weight, wear-resistant, free of oil generation and low in dielectric loss, and the use requirements of electronic signal transmission, LED lamp belt sizing materials and lampshade materials are met.
Detailed Description
In the present example, the temperature and pressure are not particularly emphasized, and both are normal temperature and normal pressure.
Example 1:
a high-temperature-resistant light diffusion PVC material is prepared from the following raw materials in parts by weight: 100 portions of PVC resin, 105 portions of methyl vinyl silicone rubber, 5-20 portions of 1, 3-divinyl-1, 1,3, 3-tetramethyl disiloxane platinum, 0.1-0.4 portion of methyl hydrogen-containing silicone oil, 0.1-0.4 portion of polyethylene wax, 2-5 portions of epoxy soybean oil, 4-8 portions of calcium-zinc stabilizer, 1-2 portions of calcium stearate, 2-3 portions of anti-aging agent, 5-40 portions of dioctyl phthalate, 5-40 portions of tri (2-ethylhexyl) trimellitate, 0.4-0.8 portion of organic silicon microsphere and 0.03-0.05 portion of OB.
Preferably, 103 parts of PVC resin 101-103, 8-15 parts of methyl vinyl silicone rubber, 0.2-0.3 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 8-15 parts of methyl hydrogen silicone oil, 0.1-0.3 part of polyethylene wax, 2-3 parts of epoxidized soybean oil, 4-6 parts of calcium zinc stabilizer, 1-2 parts of calcium stearate, 2-3 parts of anti-aging agent, 15-35 parts of dioctyl phthalate, 15-35 parts of tris (2-ethylhexyl) trimellitate, 0.5-0.7 part of organosilicon microspheres and 0.04-0.05 part of OB.
Preferably, 101 parts of PVC resin, 8 parts of methyl vinyl silicone rubber, 0.2 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 8 parts of methyl hydrogen-containing silicone oil, 0.1 part of polyethylene wax, 2 parts of epoxidized soybean oil, 4 parts of calcium-zinc stabilizer, 1 part of calcium stearate, 2 parts of anti-aging agent, 15 parts of dioctyl phthalate, 15 parts of tri (2-ethylhexyl) trimellitate, 0.5 part of organic silicon microsphere and 0.04 part of OB.
The PVC resin adopts general PVC resin, the average polymerization degree range is 700-1700, the low polymerization degree PVC resin is 400-600, and the high polymerization degree PVC resin is 1800-8000. In this example, the polymerization degree of the PVC resin was 1900.
The calcium zinc stabilizer is a heat stabilizer, the heat stabilizer can also be an alkaline earth metal chloride, a hydrotalcite base, an epoxy base, an organic phosphite base, a diketone base or a tin laurate base and the like, and in the plasticizing process, as the electronegativity is large, a polar group of the heat stabilizer has certain affinity with a polar node of PVC resin to form a combination with strong bond energy, the attraction of ionic bonds of all layers of PVC is weakened or eliminated, the mutually wound chain segments of PVC are easy to diffuse, the boundary between molecular groups is easy to be small, and the plasticization of the PVC resin is promoted.
The antioxidant comprises 1.67 parts by weight of 2,2' -thiobis (4-methyl-6-tert-butylphenol) and 0.83 part by weight of tris (2, 4-di-tert-butyl) phenyl phosphite, and the antioxidant can also be one or more of a phenol antioxidant, a phosphorus antioxidant and a sulfur antioxidant.
Due to the stability of the benzene ring conjugated large pi bond structure of the dioctyl phthalate, the plasticizer has better durability, the important product index of the trimellitate plasticizer is the volume resistance coefficient, the electric insulation performance of the PVC product can be effectively improved, the PVC product exceeds the international UL90 ℃ and 105 ℃ cable material standard, the rework rate is reduced in the processing process of the product, and the wire drawing forming is convenient. The trimellitic acid tri (2-ethylhexyl) has the advantages of large molecular weight, three benzene rings on the molecule, monomer plasticizer and polymeric plasticizer, less migration, extraction resistance and high heat resistance, and the weight loss is only below 0.15% after heating for 3 hours at 125 ℃. The high temperature resistance, the water resistance, the soap water resistance and the paint property of the trimellitic acid tris (2-ethylhexyl) are superior to those of phthalate plasticizers, the volume resistivity of a PVC product is usually 2-3 times that of the phthalate plasticizer, and the trimellitic acid triester plasticizer can endow the PVC resin with better plasticity and processability no matter the trimellitic acid triester plasticizer is used alone or is used together with other plasticizers, so that the prepared PVC material has the processability such as heat resistance, durability and the like in the embodiment.
The preparation method comprises the following steps:
(1) preparing a first mixture: mixing the methyl vinyl silicone rubber, 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, methyl hydrogen-containing silicone oil, epoxidized soybean oil and 0.05 part by weight of polyethylene wax in a mixer with the rotation speed of 45rpm for 20min, then adding 1 part by weight of anti-aging agent, and continuously mixing for 7min to obtain the first mixture.
(2) Preparing a second mixture: and mixing the calcium zinc stabilizer, the calcium stearate, the OB, the dioctyl phthalate in 12 parts by weight, the tri (2-ethylhexyl) trimellitate in 12 parts by weight and the anti-aging agent in 1 part by weight in a mixer with the rotation speed of 45rpm for 20min to prepare the second mixture.
(3) Preparing a third mixture: and (3) mixing the PVC resin with the mass fraction, the residual parts by weight of dioctyl phthalate and tri (2-ethylhexyl) trimellitate, 0.6 part by weight of organic silicon microspheres and 0.25 part by weight of polyethylene wax in a high-speed mixer with the rotating speed of 45rpm at a high speed for 9min to obtain a third mixture.
(4) Preparing a mixture: and sequentially adding the first mixture, the second mixture and the third mixture into a mixer with the rotating speed of 65rpm, mixing for 28min, putting into a cooling mixer with the temperature of 20 ℃ and the rotating speed of 70rpm, performing cold stirring for 20min, and discharging to obtain the mixture.
(5) Preparing a PVC material: and extruding and granulating the mixture in a double-screw extrusion granulator with the rotating speed of 65rpm to obtain the PVC material.
In the embodiment, an in-situ method for crosslinking silicone rubber is adopted to toughen PVC, and the elastomer obtained by heating reaction of methyl vinyl silicone rubber and methyl hydrogen-containing silicone oil under the action of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (platinum catalyst) is dispersed in PVC to toughen the PVC, improve the heat resistance and avoid precipitation. The in-situ polymerized silicone rubber generates synergistic effect on PVC and other assistants, so that the PVC and other assistants are not easy to separate out.
In the embodiment, the organic silicon microspheres are added as a light diffusing agent in PVC, and the organic silicon microspheres are added into the PVC to obtain excellent light diffusing performance, and simultaneously keep the balance of impact toughness, haze and light transmittance. Compared with other inorganic microsphere particles, the inorganic microsphere particles have the advantages of small relative density, large specific surface area, good lubricating property and good light transmittance. Compared with other organic microsphere particles, the silicon photodiffusion agent has higher efficiency, higher heat resistance, more stable color and luster and no yellowing or black spot phenomenon. Meanwhile, the method has more precise and fine particle micro-form control and narrower particle size distribution. The light diffusion agent can be selected from phenyl-containing high-refractive-index organic silicon microspheres, methyl-containing low-refractive-index organic silicon microspheres or phenyl-containing methyl-containing organic silicon microspheres.
The synthesis steps of the organic silicon microspheres in the embodiment are as follows:
(1) adding 400g of phenyltrimethoxysilane (or methyltrimethoxysilane), 400g of diphenyldimethoxysilane (or dimethyldimethoxysilane) and 200g of dimethyldiethoxysilane into a 5L three-necked bottle, adding toluene, ethanol and water, stirring uniformly, raising the temperature to 80 ℃, then dripping hydrochloric acid (dripping off after about 30 minutes), reacting for 6 hours, washing the reactant with water to be neutral, putting the reactant into an oven for drying, and controlling the conditions of temperature, reaction time and the like to obtain the organosilicon microspheres with the diameter of 1-5 um.
The PVC material prepared by the embodiment has excellent toughness and high temperature resistance, and in addition, the obtained material is non-toxic, pollution-free, light in weight, wear-resistant and free of oil, and the use requirements of LED light diffusion sizing materials and panel lampshade materials are met.
Example 2:
a high-temperature-resistant light diffusion PVC material is prepared from the following raw materials in parts by weight: 103 parts of PVC resin, 15 parts of methyl vinyl silicone rubber, 0.3 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 15 parts of methyl hydrogen-containing silicone oil, 0.3 part of polyethylene wax, 3 parts of epoxidized soybean oil, 6 parts of calcium-zinc stabilizer, 2 parts of calcium stearate, 3 parts of anti-aging agent, 35 parts of dioctyl phthalate, 35 parts of tris (2-ethylhexyl) trimellitate, 0.7 part of organic silicon microsphere and 0.05 part of OB.
The anti-aging agent consists of 1.34 parts by weight of 2,2' -thiobis (4-methyl-6-tert-butylphenol) and 0.67 part by weight of tris (2, 4-di-tert-butyl) phenyl phosphite and 1.34 parts by weight of tris (2, 4-di-tert-butyl) phenyl phosphite.
The preparation method comprises the following steps:
(1) preparing a first mixture: mixing the methyl vinyl silicone rubber, 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, methyl hydrogen-containing silicone oil, epoxidized soybean oil and 0.05 part by weight of polyethylene wax in a mixer with the rotation speed of 20rpm for 30min, then adding 1 part by weight of anti-aging agent, and continuing to mix for 10min to prepare the first mixture.
(2) Preparing a second mixture: mixing the calcium zinc stabilizer, the calcium stearate, the OB, the dioctyl phthalate with the weight parts, the tris (2-ethylhexyl) trimellitate with the weight parts, the trimellitic acid with the weight parts, and the anti-aging agent with the weight parts in a mixer with the rotation speed of 20rpm for 30min to prepare the second mixture.
(3) Preparing a third mixture: and (3) mixing the PVC resin with the mass fraction, the residual parts by weight of dioctyl phthalate, tri (2-ethylhexyl) trimellitate, 0.8 part by weight of organic silicon microspheres and 0.05 part by weight of polyethylene wax in a high-speed mixer with the rotating speed of 20rpm at a high speed for 10min to obtain a third mixture.
(4) Preparing a mixture: and sequentially adding the first mixture, the second mixture and the third mixture into a mixer with the rotation speed of 30rpm, mixing for 30min, putting into a cooling mixer with the temperature of 0 ℃ and the rotation speed of 50rpm, performing cold stirring for 30min, and discharging to obtain the mixture.
(5) Preparing a PVC material: and extruding and granulating the mixture in a double-screw extrusion granulator with the rotating speed of 30rpm to obtain the PVC material.
Example 3:
a high-temperature-resistant light diffusion PVC material is prepared from the following raw materials in parts by weight: 100 parts of PVC resin, 5 parts of methyl vinyl silicone rubber, 0.1 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 5 parts of methyl hydrogen-containing silicone oil, 0.1 part of polyethylene wax, 2 parts of epoxidized soybean oil, 4 parts of calcium-zinc stabilizer, 1 part of calcium stearate, 2 parts of anti-aging agent, 5 parts of dioctyl phthalate, 5 parts of tri (2-ethylhexyl) trimellitate, 0.4 part of organic silicon microsphere and OB: 0.03 part of the antioxidant consists of 1.67 parts by weight of 2,2 '-thiobis (4-methyl-6-tert-butylphenol) and 0.83 part by weight of tris (2, 4-di-tert-butyl) phenyl phosphite, wherein the 2,2' -thiobis (4-methyl-6-tert-butylphenol) is used as a main component.
The preparation method comprises the following steps:
(1) preparing a first mixture: mixing the methyl vinyl silicone rubber, 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, methyl hydrogen-containing silicone oil, epoxidized soybean oil and 0.15 part by weight of polyethylene wax in a mixer with the rotation speed of 85rpm for 22min, then adding 1.5 parts by weight of anti-aging agent, and continuing to mix for 8min to obtain the first mixture.
(2) Preparing a second mixture: mixing the calcium zinc stabilizer, the calcium stearate, the OB, the dioctyl phthalate in 15 parts by weight, the tris (2-ethylhexyl) trimellitate in 15 parts by weight, the organic silicon microspheres in 0.2 part by weight and the anti-aging agent in 1 part by weight in a mixer with the rotation speed of 85rpm for 22min to prepare the second mixture.
(3) Preparing a third mixture: and (3) mixing the PVC resin with the mass fraction, the residual parts by weight of dioctyl phthalate and tri (2-ethylhexyl) trimellitate, 0.4 part by weight of organic silicon microspheres and 0.1 part by weight of polyethylene wax in a high-speed mixer with the rotating speed of 85rpm at a high speed for 9min to prepare the third mixture.
(4) Preparing a mixture: and sequentially adding the first mixture, the second mixture and the third mixture into a mixer with the rotation speed of 90rpm, mixing for 27min, putting into a cooling mixer with the temperature of 32 ℃ and the rotation speed of 100rpm, performing cold stirring for 20min, and discharging to obtain the mixture.
(5) Preparing a PVC material: and extruding and granulating the mixture in a twin-screw extrusion granulator with the rotating speed of 85rpm to obtain the PVC material.
Example 4:
a high-temperature-resistant light diffusion PVC material is prepared from the following raw materials in parts by weight: 102 parts of PVC resin, 12 parts of methyl vinyl silicone rubber, 0.25 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 12 parts of methyl hydrogen-containing silicone oil, 0.25 part of polyethylene wax, 0.25 part of epoxidized soybean oil, 6 parts of calcium-zinc stabilizer, 1.5 parts of calcium stearate, 2.5 parts of anti-aging agent, 22.5 parts of dioctyl phthalate, 22.5 parts of tri (2-ethylhexyl) trimellitate, 0.6 part of organic silicon microsphere and OB: 0.04 part.
The anti-aging agent is composed of 2,2 '-thiobis (4-methyl-6-tert-butylphenol) and tris (2, 4-di-tert-butyl) phenyl phosphite, wherein the weight part of the 2,2' -thiobis (4-methyl-6-tert-butylphenol) is 2 parts, and the weight part of the tris (2, 4-di-tert-butyl) phenyl phosphite is 1 part.
The preparation method comprises the following steps:
(1) preparing a first mixture: mixing the methyl vinyl silicone rubber, 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, methyl hydrogen-containing silicone oil, epoxidized soybean oil and 0.2 part by weight of polyethylene wax in a mixer with the rotation speed of 150rpm for 15min, then adding 2 parts by weight of anti-aging agent, and continuing to mix for 5min to prepare the first mixture.
(2) Preparing a second mixture: mixing the calcium zinc stabilizer, the calcium stearate, the OB, the dioctyl phthalate in 12 parts by weight, the tris (2-ethylhexyl) trimellitate in 15 parts by weight, the organic silicon microspheres in 0.4 part by weight and the anti-aging agent in 1 part by weight in a mixer with the rotation speed of 150rpm for 15min to prepare the second mixture.
(3) Preparing a third mixture: and (3) mixing the PVC resin with the mass fraction, the residual parts by weight of dioctyl phthalate and tri (2-ethylhexyl) trimellitate, 0.3 part by weight of organic silicon microspheres and 0.2 part by weight of polyethylene wax in a high-speed mixer with the rotating speed of 150rpm at a high speed for 8min to obtain a third mixture.
(4) Preparing a mixture: and sequentially adding the first mixture, the second mixture and the third mixture into a mixer with the rotation speed of 150rpm, mixing for 25min, putting into a cooling mixer with the temperature of 65 ℃ and the rotation speed of 150rpm, performing cold stirring for 10min, and discharging to obtain the mixture.
(5) Preparing a PVC material: and extruding and granulating the mixture in a double-screw extrusion granulator with the rotating speed of 150rpm to obtain the PVC material.
Example 5:
a high-temperature-resistant light diffusion PVC material is prepared from the following raw materials in parts by weight: 105 parts of PVC resin, 20 parts of methyl vinyl silicone rubber, 0.4 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 20 parts of methyl hydrogen-containing silicone oil, 0.4 part of polyethylene wax, 5 parts of epoxidized soybean oil, 8 parts of calcium-zinc stabilizer, 2 parts of calcium stearate, 3 parts of anti-aging agent, 40 parts of dioctyl phthalate, 40 parts of tri (2-ethylhexyl) trimellitate, 0.8 part of organic silicon microsphere and OB: 0.05 part.
The anti-aging agent is composed of 2,2 '-thiobis (4-methyl-6-tert-butylphenol) and tris (2, 4-di-tert-butyl) phenyl phosphite, wherein the weight part of the 2,2' -thiobis (4-methyl-6-tert-butylphenol) is 2 parts, and the weight part of the tris (2, 4-di-tert-butyl) phenyl phosphite is 1 part.
The preparation method comprises the following steps:
(1) preparing a first mixture: mixing the methyl vinyl silicone rubber, 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, methyl hydrogen-containing silicone oil, epoxidized soybean oil and 0.1 part by weight of polyethylene wax in a mixer with the rotation speed of 80rpm for 20min, then adding 2 parts by weight of anti-aging agent, and continuously mixing for 6min to obtain the first mixture.
(2) Preparing a second mixture: mixing the calcium zinc stabilizer, the calcium stearate, the OB, the dioctyl phthalate with 8 parts by weight, the tris (2-ethylhexyl) trimellitate with 12 parts by weight, the organic silicon microspheres with 0.4 part by weight and the anti-aging agent with 1 part by weight in a mixer with the rotating speed of 80rpm for 20min to prepare the second mixture.
(3) Preparing a third mixture: and (3) mixing the PVC resin with the mass fraction, the residual parts by weight of dioctyl phthalate and tri (2-ethylhexyl) trimellitate, 0.2 part by weight of organic silicon microspheres and 0.1 part by weight of polyethylene wax in a high-speed mixer with the rotating speed of 80rpm at a high speed for 9min to obtain a third mixture.
(4) Preparing a mixture: and sequentially adding the first mixture, the second mixture and the third mixture into a mixer with the rotation speed of 80rpm, mixing for 28min, putting into a cooling mixer with the temperature of 45 ℃ and the rotation speed of 80rpm, performing cold stirring for 15min, and discharging to obtain the mixture.
(5) Preparing a PVC material: and extruding and granulating the mixture in a double-screw extrusion granulator with the rotating speed of 80rpm to obtain the PVC material.
In addition, three comparative examples were set to perform the performance tests on the PVC material obtained therefrom and the PVC materials obtained in examples 1-2, and the test results are shown in table 1.
Comparative example 1: compared with the embodiment 2, the organic silicon microspheres are not contained, and the rest is the same as the embodiment 2.
Comparative example 2: the composition was the same as in example 3 except that the methyl vinyl silicone rubber, 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, and methyl hydrogen silicone oil were not contained in the composition in example 3.
Comparative example 3: compared with the example 4, the organic silicon microspheres, the methyl vinyl silicone rubber, the 1, 3-divinyl-1, 1,3, 3-tetramethyl disiloxane platinum and the methyl hydrogen-containing silicone oil are not contained, and the rest is the same as the example 4.
TABLE 1 Performance test Table
It can be seen from the above results that the mechanical properties of the high-temperature-resistant light diffusion PVC material prepared by the embodiment can meet the market demand, and has excellent anti-aging performance, and the aged PVC material can still maintain high tensile strength, so that the high-temperature-resistant light diffusion PVC material can provide good protection for the LED lamp strip, ensures the service life of the lamp strip, and has a wide market prospect.
The above embodiments do not limit the scope of the present invention, and those skilled in the art can make equivalent modifications and variations without departing from the overall concept of the present invention.
Claims (9)
1. A high-temperature-resistant light diffusion PVC material is characterized by being prepared from the following raw materials in parts by weight: 100 portions of PVC resin, 105 portions of methyl vinyl silicone rubber, 5-20 portions of 1, 3-divinyl-1, 1,3, 3-tetramethyl disiloxane platinum, 0.1-0.4 portion of methyl hydrogen-containing silicone oil, 0.1-0.4 portion of polyethylene wax, 2-5 portions of epoxy soybean oil, 4-8 portions of calcium-zinc stabilizer, 1-2 portions of calcium stearate, 2-3 portions of anti-aging agent, 5-40 portions of dioctyl phthalate, 5-40 portions of tris (2-ethylhexyl) trimellitate, 0.4-0.8 portion of organic silicon microsphere and OB: 0.03-0.05 part.
2. The high-temperature-resistant light-diffusing PVC material according to claim 1, characterized in that it is made from the following raw materials in parts by weight: 103 parts of PVC resin 101-containing material, 8-15 parts of methyl vinyl silicone rubber, 0.2-0.3 part of 1, 3-divinyl-1, 1,3, 3-tetramethyl disiloxane platinum, 8-15 parts of methyl hydrogen-containing silicone oil, 0.1-0.3 part of polyethylene wax, 2-3 parts of epoxy soybean oil, 4-6 parts of calcium-zinc stabilizer, 1-2 parts of calcium stearate, 2-3 parts of anti-aging agent, 15-35 parts of dioctyl phthalate, 15-35 parts of tri (2-ethylhexyl) trimellitate, 0.5-0.7 part of organic silicon microspheres and 0.04-0.05 part of OB.
3. The high-temperature-resistant light-diffusing PVC material according to claim 2, characterized in that it is made from the following raw materials in parts by weight: 101 parts of PVC resin, 8 parts of methyl vinyl silicone rubber, 0.2 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 8 parts of methyl hydrogen-containing silicone oil, 0.1 part of polyethylene wax, 2 parts of epoxidized soybean oil, 4 parts of calcium-zinc stabilizer, 1 part of calcium stearate, 2 parts of anti-aging agent, 15 parts of dioctyl phthalate, 15 parts of tri (2-ethylhexyl) trimellitate, 0.5 part of organic silicon microsphere and 0.04 part of OB.
4. The high-temperature-resistant light-diffusing PVC material according to claim 2, characterized in that it is made from the following raw materials in parts by weight: 103 parts of PVC resin, 15 parts of methyl vinyl silicone rubber, 0.3 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 15 parts of methyl hydrogen-containing silicone oil, 0.3 part of polyethylene wax, 3 parts of epoxidized soybean oil, 6 parts of calcium-zinc stabilizer, 2 parts of calcium stearate, 3 parts of anti-aging agent, 35 parts of dioctyl phthalate, 35 parts of tris (2-ethylhexyl) trimellitate, 0.7 part of organic silicon microsphere and 0.05 part of OB.
5. The high-temperature-resistant light-diffusing PVC material according to claim 1, characterized in that it is made from the following raw materials in parts by weight: 100 parts of PVC resin, 5 parts of methyl vinyl silicone rubber, 0.1 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 5 parts of methyl hydrogen-containing silicone oil, 0.1 part of polyethylene wax, 2 parts of epoxidized soybean oil, 4 parts of calcium-zinc stabilizer, 1 part of calcium stearate, 2 parts of anti-aging agent, 5 parts of dioctyl phthalate, 5 parts of tri (2-ethylhexyl) trimellitate, 0.4 part of organic silicon microsphere and OB: 0.03 part.
6. The high-temperature-resistant light-diffusing PVC material according to claim 1, characterized in that it is made from the following raw materials in parts by weight: 102 parts of PVC resin, 12 parts of methyl vinyl silicone rubber, 0.25 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 12 parts of methyl hydrogen-containing silicone oil, 0.25 part of polyethylene wax, 0.25 part of epoxidized soybean oil, 6 parts of calcium-zinc stabilizer, 1.5 parts of calcium stearate, 2.5 parts of anti-aging agent, 22.5 parts of dioctyl phthalate, 22.5 parts of tri (2-ethylhexyl) trimellitate, 0.6 part of organic silicon microsphere and OB: 0.04 part.
7. The high-temperature-resistant light-diffusing PVC material according to claim 1, characterized in that it is made from the following raw materials in parts by weight: 105 parts of PVC resin, 20 parts of methyl vinyl silicone rubber, 0.4 part of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, 20 parts of methyl hydrogen-containing silicone oil, 0.4 part of polyethylene wax, 5 parts of epoxidized soybean oil, 8 parts of calcium-zinc stabilizer, 2 parts of calcium stearate, 3 parts of anti-aging agent, 40 parts of dioctyl phthalate, 40 parts of tri (2-ethylhexyl) trimellitate, 0.8 part of organic silicon microsphere and OB: 0.05 part.
8. The high-temperature-resistant photodiffusion PVC material according to any one of claims 1 to 7, characterized in that the anti-aging agent is composed of 2,2 '-thiobis (4-methyl-6-tert-butylphenol) and tris (2, 4-di-tert-butyl) phenyl phosphite, and the weight part ratio of the 2,2' -thiobis (4-methyl-6-tert-butylphenol) to the tris (2, 4-di-tert-butyl) phenyl phosphite is 2: 1.
9. A process for the preparation of the high temperature resistant photodiffusion PVC material of claim 8, characterized by the following steps:
(1) preparing a first mixture: mixing the methyl vinyl silicone rubber, 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum, methyl hydrogen-containing silicone oil, epoxidized soybean oil and polyethylene wax in a weight part of 0.05-0.2 in a mixer with the rotation speed of 20-150rpm for 15-30min, then adding 1-2 weight parts of anti-aging agent, and continuously mixing for 5-10min to prepare a first mixture;
(2) preparing a second mixture: mixing the calcium zinc stabilizer, the calcium stearate, the OB, the dioctyl phthalate in 10-20 parts by weight, the tri (2-ethylhexyl) trimellitate in 10-20 parts by weight and the anti-aging agent in the rest parts by weight in a mixer with the rotation speed of 20-150rpm for 15-30min to prepare a second mixture;
(3) preparing a third mixture: mixing the PVC resin with the mass fraction, the dioctyl phthalate, the tri (2-ethylhexyl) trimellitate and the polyethylene wax in a high-speed mixer at the rotating speed of 20-150rpm for 8-10min to prepare a third mixture;
(4) preparing a mixture: sequentially adding the first mixture, the second mixture and the third mixture into a mixer with the rotation speed of 30-150rpm, mixing for 25-30min, then placing into a cooling mixer with the temperature of 0-65 ℃ and the rotation speed of 50-150rpm, carrying out cold stirring for 10-30min, discharging, and obtaining the mixture;
(5) preparing a PVC material: and extruding and granulating the mixture in a double-screw extrusion granulator with the rotating speed of 30-150rpm to obtain the PVC material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112406132A (en) * | 2020-10-19 | 2021-02-26 | 广西北海跃达玻璃钢制品有限公司 | Flame-retardant glass fiber reinforced plastic pipe and production process thereof |
| CN115109366A (en) * | 2022-08-01 | 2022-09-27 | 电子科技大学中山学院 | Conductive polyvinyl alcohol modified composition and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496858A (en) * | 2016-11-04 | 2017-03-15 | 江门市中联塑化科技有限公司 | A kind of soft colored PVC composition of smooth diffused and its application |
| CN106893225A (en) * | 2015-12-17 | 2017-06-27 | 宁波荣辉纳米技术有限公司 | A kind of color lamp lampshade and preparation method thereof |
| CN107698893A (en) * | 2017-10-24 | 2018-02-16 | 惠州市元塑高分子材料有限公司 | A kind of high grade of transparency high glaze PVC material |
-
2020
- 2020-06-30 CN CN202010614598.9A patent/CN111690216B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893225A (en) * | 2015-12-17 | 2017-06-27 | 宁波荣辉纳米技术有限公司 | A kind of color lamp lampshade and preparation method thereof |
| CN106496858A (en) * | 2016-11-04 | 2017-03-15 | 江门市中联塑化科技有限公司 | A kind of soft colored PVC composition of smooth diffused and its application |
| CN107698893A (en) * | 2017-10-24 | 2018-02-16 | 惠州市元塑高分子材料有限公司 | A kind of high grade of transparency high glaze PVC material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112406132A (en) * | 2020-10-19 | 2021-02-26 | 广西北海跃达玻璃钢制品有限公司 | Flame-retardant glass fiber reinforced plastic pipe and production process thereof |
| CN115109366A (en) * | 2022-08-01 | 2022-09-27 | 电子科技大学中山学院 | Conductive polyvinyl alcohol modified composition and preparation method thereof |
| CN115109366B (en) * | 2022-08-01 | 2023-07-21 | 电子科技大学中山学院 | Conductive polyvinyl alcohol modified composition and preparation method thereof |
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