Heat-resistant, easy-to-process and high-transparency PVC / MS alloy material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of PVC alloy materials, and provides a heat-resistant, easy-to-process and high-transparency PVC / MS alloy material as well as a preparation method and application thereof. The alloy material comprises PVC resin, MS resin, a heat stabilizer, a lubricant, a flexibilizer, an antioxidant and an anti-yellowing agent, the MS resin is dried and then smashed, the PVC resin and the stabilizer are stirred and mixed at a low speed and heated, the lubricant, the antioxidant and the anti-yellowing agent are added, stirred and mixed at a low speed and heated, then the flexibilizer and the smashed MS resin are added, stirred and mixed at a high speed and heated, and the alloy material is obtained. And finally, transferring the mixed material into a low-speed mixer, cooling, feeding the obtained dry mixture into a granulating device, and granulating to obtain the PVC / MS alloy material. According to the PVC / MS alloy material, the MS resin, the yellowing eliminating agent and the lubricant are blended, the light transmittance can reach 90.5%, the addition of the MS resin plays a very good plasticizing effect and a very good heat-resistant effect, the Vicat softening point temperature of PVC can be increased, the PVC / MS alloy material can have better temperature resistance, and the use occasion of the material can be expanded.

Description

Technical Field

[0001] The invention belongs to the technical field of PVC alloy materials, and in particular relates to a heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and a preparation method thereof. Background Art

[0002] PVC resin (polyvinyl chloride) is the world's third largest synthetic polymer plastic. PVC plastic has the advantages of high strength, good weather resistance, corrosion resistance, flame retardancy, geometric stability, and adjustable hardness and softness. It is widely used in pipes and fittings, wires and cables, building profiles, medical equipment, floor coverings, films, furniture and home decoration, toys and other fields. However, the poor processing performance and low heat resistance of PVC have seriously affected the production and further application of PVC products. The transparency of PVC is better than that of polyethylene and polypropylene, but worse than that of polystyrene.

[0003] MS resin is a copolymer of methyl methacrylate and styrene. It not only has the good processing fluidity, thermal stability and low hygroscopicity of polystyrene, but also has the weather resistance, excellent optical properties and high transparency of methyl methacrylate. Its refractive index is 1.56 and its transmittance can reach 91%, which is close to PMMA.

[0004] The current PVC transparent materials are all PVC transparent granules obtained by using PVC as the main resin and adding additives for blending and modification. However, the weather resistance, heat resistance and transparency of existing PVC transparent materials cannot meet market demand. A large number of additives have poor compatibility with PVC, which seriously affects the transparency. Patent 202111371516.3 discloses a weather-resistant and antistatic transparent PVC / PMMA alloy material and a preparation method thereof. The PVC / PMMA alloy material described in the patent includes the following raw materials by mass: 100 parts of PVC resin, 5-20 parts of PMMA resin, 1-3 parts of heat stabilizer, 5-10 parts of impact modifier, 10-20 parts of antistatic agent, 0.5-1.5 parts of weathering agent and 0.01-0.02 parts of yellowing agent. The PVC / PMMA alloy in the patent is prepared by extrusion granulation, achieving excellent effects such as high light transmittance, good weather resistance and antistatic. However, PVC / PMMA alloys are generally used in transparent films and packaging materials, and the requirements for physical properties such as impact strength and tensile strength of the finished product are not high. At the same time, the high price of PMMA also hinders its application in highly transparent products.

[0005] For home appliance housings, transparent plates and other uses, plasticizers are generally required to meet the mechanical properties of the material. Plasticizers easily migrate to the surface of the product, and the addition of plasticizers reduces the application temperature range and transparency of PVC transparent materials, greatly limiting the application areas of PVC transparent materials.

[0006] Therefore, it is necessary to research new transparent materials, on the basis of achieving the transparency of PVC / PMMA material parameters, solve the defects caused by the addition of plasticizers, improve the heat resistance and plasticization basis of transparent materials, and thus reduce the cost of transparent materials. Summary of the invention

[0007] The invention provides a heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and a preparation method thereof. The PVC / MS alloy prepared by the method has good processing performance, heat resistance and transparency, and has good glossiness.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions: A heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and a preparation method thereof, characterized in that the components thereof include, by weight: 100 parts of PVC resin, 5-20 parts of MS resin, 1-3 parts of heat stabilizer, 0.4-1.6 parts of lubricant, 5-15 parts of toughening agent, 0.01-0.5 parts of antioxidant, and 0.01-0.015 parts of anti-yellowing agent; the average polymerization degree of the PVC resin is 650-845, the MS resin is an MS resin with a melt flow index of more than 20g / 10min, and the melt flow index of the MS resin is 20-35g / 10min when tested under the conditions of 220°C and 10kg; The preparation method of the PVC / MS alloy material comprises the following steps: Step 1: Dry the MS resin for 2-3 hours at a temperature of 60-80°C; Step 2: Crush the dried MS resin to a size of 200 meshes. The crushed MS resin can be better blended with PVC. Step 3: Use a stirring kettle to stir and mix the PVC resin and stabilizer at a low speed in the stirring kettle, and at the same time heat the materials to 60°C, then add lubricant, antioxidant, and anti-yellowing agent in proportion, continue to mix at a low speed and heat to 80°C, then add toughening agent and crushed MS resin, mix at a high speed and heat to 105-120°C, finally, transfer the mixed material to a low-speed mixer, cool it to 35-45°C, and obtain a dry blend; Step 4: sending the dry blended material into a granulation device for granulation to obtain the PVC / MS alloy material.

[0009] The granulation process in the fourth step is: first feed the dry mixed material into a conical twin-screw extruder for extrusion granulation, the feeding speed of the twin-screw extruder is 5-7rpm, the main engine speed is 12-16rpm, and the processing temperature is 155-175°C; then cool it down by hot cutting and air cooling.

[0010] Furthermore, the heat stabilizer is one of methyl tin mercaptan and calcium zinc stabilizer, or a combination of the two.

[0011] Furthermore, the lubricant is a composite of one or more of stearic acid (Hst), ethylene bis stearamide (EBS), polyethylene wax (PE wax), oxidized polyethylene wax (OPE), etc.

[0012] Furthermore, the toughening agent is one or a combination of two of a terpolymer of methyl methacrylate-butadiene-styrene (MBS), chlorinated polyethylene (CPE), etc.

[0013] Furthermore, the antioxidant is one or a combination of two of 1010, 168, etc.

[0014] Furthermore, the anti-yellowing agent is one of ultramarine blue and triazine aminobenzene, or a combination of two of them.

[0015] The invention discloses an application of a heat-resistant, easy-to-process and highly transparent PVC / MS alloy material. The PVC / MS alloy material is applied to household appliance housings, transparent plates and blister packaging.

[0016] Compared with the PVC / PMMA products in the prior art, the advantages of the present invention are as follows: 1. The PVC / MS alloy material prepared by the present invention is blended with MS resin, anti-yellowing agent and lubricant, which has a good transparent effect, and the light transmittance can reach 90.5%, which is close to the light transmittance of MS resin; the addition of MS resin has a good plasticizing effect, which can advance the plasticizing time of PVC, facilitate processing, and solve the defects of migration and precipitation of other plasticizers; at the same time, the addition of MS resin has a good heat-resistant effect, which can improve the Vicat softening point temperature of PVC, can have good temperature resistance, and can expand the use occasions of the material.

[0017] 2. The PVC / MS alloy material prepared by the present invention can be used in the fields of home appliance housings, transparent plates, blister packaging, etc., and can replace the application of PMMA products; the preparation method of the PVC / MS alloy material is simple and easy to operate, and can be used in multiple fields of transparent products. DETAILED DESCRIPTION

[0018] The present invention will be further described in detail below with reference to the embodiments, which are only a part of the present invention, rather than all the embodiments.

[0019] Example 1 A heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and a preparation method thereof include the following steps: (1) Dry 5-20 parts of MS resin at 80°C for 2 hours and crush; (2) Add 100 parts of PVC resin and 2.5 parts of methyl tin mercaptan into a high-speed mixer, mix at a low speed and heat to 60°C; (3) Add 0.5 parts of Hst, 0.5 parts of EBS, 0.5 parts of antioxidant 1010, and 0.01 parts of ultramarine to (2), mix at low speed, and heat to 80°C; (4) Add 10 parts of MBS and 15 parts of MS resin to (3), mix at high speed and heat to 110°C, put it into a low-speed mixer, and cool it to 40°C to obtain a dry blend.

[0020] (5) The dry blend obtained in (4) is added into a twin-screw extruder at a feed speed of 7 rpm, a main engine speed of 16 rpm, a processing temperature of 155-175°C, and hot-cut air cooling to obtain a PVC / MS alloy material.

[0021] Example 2 A heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and a preparation method thereof include the following steps: (1) Dry 5-20 parts of MS resin at 80°C for 2 hours and crush; (2) Add 100 parts of PVC resin and 3 parts of calcium zinc stabilizer into a high-speed mixer, mix at a low speed and heat to 60°C; (3) Add 0.6 parts of Hst, 0.8 parts of PE wax, 0.4 parts of antioxidant 168, 0.01 parts of ultramarine blue, and 0.005 parts of triazine aminobenzene to (2), mix at low speed and raise the temperature to 80°C; (4) Add 12 parts of MBS and 20 parts of MS resin to (3), mix at high speed and heat to 120°C, put it into a low-speed mixer, and cool it to 45°C to obtain a dry blend.

[0022] (5) The dry blend obtained in (4) is added into a twin-screw extruder at a feed speed of 7 rpm, a main engine speed of 14 rpm, a processing temperature of 155-175°C, and hot-cut air cooling to obtain a PVC / MS alloy material.

[0023] Example 3 A heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and a preparation method thereof include the following steps: (1) Dry 5-20 parts of MS resin at 80°C for 2 hours and crush; (2) Add 100 parts of PVC resin and 2.3 parts of methyl tin mercaptan into a high-speed mixer, mix at a low speed and heat to 60°C; (3) Add 0.7 parts of EBS, 0.6 parts of PE wax, 0.3 parts of OPE, 0.01 parts of antioxidant 1010, and 0.01 parts of ultramarine to (2), mix at low speed and heat to 80°C; (4) Add 15 parts of CPE and 5 parts of MS resin to (3), mix at high speed and heat to 105°C, put it into a low-speed mixer, and cool it to 40°C to obtain a dry blend.

[0024] (5) The dry blend obtained in (4) is added into a twin-screw extruder at a feed speed of 5 rpm, a main engine speed of 15 rpm, a processing temperature of 155-175°C, and hot-cut air cooling to obtain a PVC / MS alloy material.

[0025] Example 4 A heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and a preparation method thereof include the following steps: (1) Dry 5-20 parts of MS resin at 80°C for 2 hours and crush; (2) Add 100 parts of PVC resin, 1 part of methyl tin mercaptan, and 1.5 parts of calcium zinc stabilizer into a high-speed mixer, mix at a low speed, and heat to 60°C; (3) Add 0.3 parts of Hst, 0.7 parts of PE wax, 0.09 parts of antioxidant 1010, 0.01 parts of ultramarine blue, and 0.002 parts of triazine aminobenzene to (2), mix at low speed and raise the temperature to 80°C; (4) Add 15 parts of MBS and 20 parts of MS resin to (3), mix at high speed and heat to 110°C, put it into a low-speed mixer, and cool it to 45°C to obtain a dry blend.

[0026] (5) The dry blend obtained in (4) is added into a twin-screw extruder at a feed speed of 7 rpm, a main engine speed of 16 rpm, a processing temperature of 155-175°C, and hot-cut air cooling to obtain a PVC / MS alloy material.

[0027] Comparative Example 1 Compared with Example 1, comparative example 1 is obtained, comprising the following steps: (1) Add 100 parts of PVC resin, 1 part of methyl tin mercaptan, and 1.5 parts of calcium zinc stabilizer into a high-speed mixer, mix at a low speed and heat to 60°C; (2) Add 0.3 parts of Hst, 0.7 parts of PE wax, 0.09 parts of antioxidant 1010, 0.01 parts of ultramarine blue, and 0.002 parts of triazine amino diphenylethylene to (1), mix at low speed and raise the temperature to 80°C; (3) Add 15 parts of MBS to (2), mix at high speed and heat to 110°C, place in a low-speed mixer, and cool to 45°C to obtain a dry mix.

[0028] (4) The dry blend obtained in (3) was added into a twin-screw extruder with a feed speed of 7 rpm, a main engine speed of 16 rpm, a processing temperature of 155-175°C, and hot air cooling to obtain Comparative Example 1.

[0029] Comparative Example 2 The MS resin in Example 2 was replaced with the same amount of conventional plasticizer tributyl citrate (TBC), and the plasticizing effect of the MS resin was compared to obtain Comparative Example 2; (1) Add 100 parts of PVC resin, 3 parts of calcium zinc stabilizer, and 20 parts of TBC into a high-speed mixer, mix at a low speed and heat to 60°C; (2) Add 0.6 parts of Hst, 0.8 parts of PE wax, 0.4 parts of antioxidant 168, 0.01 parts of ultramarine blue, and 0.005 parts of triazine aminobenzene to (1), mix at low speed and heat to 80°C; (3) Add 12 parts of MBS to (2), mix at high speed and heat to 120°C, put it into a low-speed mixer, and cool it to 45°C to obtain a dry mix.

[0030] (4) The dry blend obtained in (3) was added into a twin-screw extruder at a feed speed of 6 rpm, a main engine speed of 13 rpm, a processing temperature of 155-175°C, and hot-cut air cooling to obtain Comparative Example 2.

[0031] Comparative Example 3 The MS resin in Example 3 was replaced with the same amount of ACR (acrylic polymer) transparent modifier, and the transparent modification effect of the MS resin was compared; (1) Add 100 parts of PVC resin and 2.3 parts of methyl tin mercaptan into a high-speed mixer, mix at a low speed and heat to 60°C; (2) Add 0.7 parts of EBS, 0.6 parts of PE wax, 0.3 parts of OPE, 0.01 parts of antioxidant 1010, and 0.01 parts of ultramarine to (1), mix at low speed and heat to 80°C; (3) Add 15 parts of CPE and 5 parts of ACR resin to (2), mix at high speed and heat to 105°C, put it into a low-speed mixer, and cool it to 40°C to obtain a dry blend.

[0032] (4) The dry blend obtained in (3) was added into a twin-screw extruder with a feed speed of 5 rpm, a main engine speed of 15 rpm, a processing temperature of 155-175°C, and hot-cut air cooling to obtain Comparative Example 3.

[0033] Comparative Example 4 Compared with Example 4, comparative example 4 is obtained, comprising the following steps: (1) Add 100 parts of PVC resin, 1 part of methyl tin mercaptan, and 1.5 parts of calcium zinc stabilizer into a high-speed mixer, mix at a low speed and heat to 60°C; (2) Add 0.3 parts of Hst, 0.7 parts of PE wax, 0.09 parts of antioxidant 1010, 0.01 parts of ultramarine blue, and 0.002 parts of triazine amino diphenylethylene to (1), mix at low speed and raise the temperature to 80°C; (3) Add 15 parts of MBS and 20 parts of MS resin to (2), mix at high speed and heat to 110°C, put it into a low-speed mixer, and cool it to 45°C to obtain a dry blend.

[0034] (4) The dry blend obtained in (3) was added into a twin-screw extruder at a feed speed of 7 rpm, a main engine speed of 16 rpm, a processing temperature of 155-175°C, and hot-cut air cooling to obtain comparative material 4.

[0035] The pellets obtained in the above steps were tested for rheological properties of the pellets in the embodiment and the comparative example by a torque rheometer, and the test conditions were: The amount of material added was 65 g, the temperature was 175 ° C, and the rotation speed was 45 rpm; The pellets obtained in the above steps were used to prepare tensile, impact and Vicat softening point test specimens through a double-roll mill, a flat vulcanizer and a dumbbell sample making machine. The test results are shown in the following table:

[0036] Compared with the data of Example 1 and Comparative Example 1, from the perspective of balanced torque, the addition of MS resin reduces the balanced torque and shortens the plasticizing time, indicating that the styrene group of MS resin has a good external lubrication effect and improves the processing performance of the plastic. The addition of high proportions will not affect the lubrication system of the formula; from the perspective of Vicat softening point temperature, MS resin increases the Vicat softening point temperature of the formula system, indicating that the addition of MS resin plays the role of a heat-resistant additive.

[0037] Compared with the data of Example 2 and Comparative Example 2, from the perspective of plasticization time, MS resin has a good plasticizing effect on PVC and can replace conventional plasticizers; from the perspective of Vicat softening point temperature, MS resin has a good heat resistance effect under the effect of plasticization, and can be used as an improvement additive for maintaining the Vicat softening point temperature of soft products.

[0038] Comparing the data of Example 3 and Comparative Example 3, from the perspective of transmittance, the transparency modification effect of MS resin on PVC after addition is more obvious than that of conventional transparent modifier ACR (acrylic high molecular polymer), and the transmittance is close to that of MS resin, playing the role of transparent modifier.

[0039] Compared with the data of Example 4 and Comparative Example 4, from the perspective of tensile strength, the addition of MS resin has an effect of improving the tensile strength.

[0040] In summary, the addition of MS resin can plasticize PVC, make it easier to process, increase heat resistance and improve transparency.

[0041] The heat-resistant, easy-to-process, highly transparent PVC / MS alloy material prepared by the present invention has good properties, reduces the processing temperature, and the Vicat softening point temperature can reach 83.4°C, has good transparency, and the light transmittance can reach more than 90%. The present invention can be used in the fields of electronic instrument panels, transparent sheets, automobiles, home appliances, etc.

[0042] The above description is only for illustrating the relevant contents of the present invention, and is not all embodiments of the present invention. As long as it does not deviate from the principle of the present invention, any modification and improvement made shall be included in the protection scope of the present invention.

Claims

1. A heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and a preparation method thereof, characterized in that: The composition includes, by weight: 100 parts of PVC resin, 5-20 parts of MS resin, 1-3 parts of heat stabilizer, 0.4-1.6 parts of lubricant, 5-15 parts of toughening agent, 0.01-0.5 parts of antioxidant, 0.01-0.015 parts of anti-yellowing agent; the average polymerization degree of the PVC resin is 650-845, the MS resin is an MS resin with a melt flow index of more than 20g / 10min, and the melt flow index of the MS resin is 20-35g / 10min when tested under the conditions of 220°C and 10kg; The preparation method comprises the following steps: Step 1: Dry the MS resin for 2-3 hours at a temperature of 60-80°C; Step 2: crush the dried MS resin to a size of 200 meshes; Step 3: Stir and mix the PVC resin and stabilizer at a low speed and raise the temperature to 60°C, add the lubricant, antioxidant and anti-yellowing agent, stir and mix at a low speed and raise the temperature to 80°C, then add the toughening agent and the crushed MS resin, stir and mix at a high speed and raise the temperature to 105-120°C, finally, transfer the mixed materials to a low-speed mixer, cool to 35-45°C, and obtain a dry blend; Step 4: sending the dry blended material into a granulation device for granulation to obtain the PVC / MS alloy material.

2. A heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and a preparation method thereof according to claim 1, characterized in that: The granulation process in the fourth step is: the dry mixed material is fed into a conical twin-screw extruder for extrusion granulation, the feeding speed of the twin-screw extruder is 5-7rpm, the main engine speed is 12-16rpm, and the extrusion temperature is 155-175°C; and then the temperature is reduced by hot cutting and air cooling.

3. The heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and its preparation method according to claim 1, characterized in that: The heat stabilizer is one of methyl tin mercaptan and calcium zinc stabilizer or a combination of the two.

4. The heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and its preparation method according to claim 1, characterized in that: The lubricant is a composite of one or more of stearic acid (Hst), ethylene bis stearamide (EBS), polyethylene wax (PE wax), oxidized polyethylene wax (OPE), etc.

5. The heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and its preparation method according to claim 1, characterized in that: The toughening agent is one or a combination of two of a terpolymer of methyl methacrylate-butadiene-styrene (MBS), chlorinated polyethylene (CPE), etc.

6. The heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and its preparation method according to claim 1, characterized in that: The antioxidant is one or a combination of 1010, 168, etc.

7. The heat-resistant, easy-to-process, highly transparent PVC / MS alloy material and its preparation method according to claim 1, characterized in that: The anti-yellowing agent is one of ultramarine blue and triazine aminobenzene or a combination of the two.

8. The use of a heat-resistant, easy-to-process, highly transparent PVC / MS alloy material as claimed in claim 1, characterized in that: The PVC / MS alloy material is applied to household appliance housings, transparent plates and blister packaging.

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