A polyvinyl chloride alloy material, a preparation method and application thereof

Abstract

The present application relates to a kind of polyvinyl chloride alloy material and its preparation method and application, belong to polymer material technical field.The polyvinyl chloride alloy material provided by the present application, by weight fraction, includes the following components: polyvinyl chloride resin 59-81 parts, styrene-acrylonitrile-acrylic rubber terpolymer 18-42 parts, pure monomer resin 4-21 parts, inorganic rigid material 2-16 parts, stabilizer 0.5-5.5 parts and acrylic ester processing aid 1-5 parts.The present application introduces pure monomer resin and inorganic rigid material into PVC / ASA simultaneously, while maintaining the flame retardant properties of polyvinyl chloride alloy material, the wear resistance and flame retardant smoke property of product are improved, and the prepared polyvinyl chloride alloy material has excellent wear resistance and flame-retardant low smoke performance.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a polyvinyl chloride alloy material, its preparation method, and its application. Background Technology

[0002] Polyvinyl chloride (PVC) is widely used in various industries in China due to its high cost-effectiveness, low price, flame retardancy, and weather resistance. Domestic apparent consumption exceeds 20 million tons. However, PVC resin has drawbacks such as poor toughness and abrasion resistance. To promote its wider application, performance improvements are needed. While PVC resin contains 56% chlorine, a flame-retardant element, and pure PVC has an oxygen index of 56, exhibiting excellent flame-retardant properties, PVC produces high smoke regardless of whether it is burning with a flame or smoldering. This is because during combustion, the PVC molecular chain breaks down, leading to the removal of HCl, chain cyclization, and the generation of low-density particles with benzene ring structures, resulting in visible black smoke composed of carbon particles.

[0003] Patent CN201410130799 discloses a weather-resistant and flame-retardant PVC / ASA alloy material and its preparation method. It primarily addresses the weathering defects of PVC / ABS alloy materials by replacing ABS with ASA, utilizing the high weather resistance and non-brittle properties of ASA to provide a weather-resistant and flame-retardant PVC / ASA alloy material. Patent CN201210572001 discloses a PVC / ASA alloy material and its preparation method, also primarily addressing the heat resistance defects of PVC / ABS alloy materials by replacing ABS with ASA and adding heat-resistant additives such as SMA to provide a heat-resistant PVC / ASA alloy material.

[0004] However, the introduction of ASA into PVC materials reduces the material's wear resistance and reduces its smoke suppression effect. Therefore, it is of great significance to develop a PVC alloy material that combines weather resistance, heat resistance, wear resistance, and low smoke effect. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems existing in the prior art and to provide a polyvinyl chloride alloy material, its preparation method, and its application.

[0006] This invention is achieved through the following technical solution:

[0007] The polyvinyl chloride alloy material provided by the present invention comprises, by weight, the following components: 59-81 parts of polyvinyl chloride resin, 18-42 parts of styrene-acrylonitrile-acrylic rubber terpolymer, 4-21 parts of pure monomer resin, 2-16 parts of inorganic rigid material, 0.5-5.5 parts of stabilizer, and 1-5 parts of acrylate processing aid.

[0008] This invention introduces an (ASA) styrene-acrylonitrile-acrylic rubber terpolymer into PVC resin to improve the toughness of PVC materials. However, because ASA contains a rubber phase, the wear resistance of the material decreases. The essence of polymer wear lies in the slippage or breakage of molecular chain segments under the friction of external forces, causing the material to transfer in sheets to the surface of the mating parts, resulting in adhesive wear. Based on this, this invention further introduces a certain amount of pure monomer resin. During processing, the pure monomer resin can promote material plasticization, improve the surface gloss, and make the surface smoother and more delicate. Simultaneously, the pure monomer resin has a low melting point, allowing a thin protective layer to form on the material surface when the material generates heat through friction. Combining these two factors, the wear resistance of the PVC / ASA system is improved. Furthermore, this invention introduces a certain amount of inorganic rigid material to replace traditional chlorinated polyethylene for toughening. The inorganic rigid material is nanoscale, can tightly bond with the material matrix, and can also play a good toughening role under impact. At the same time, compared with organic toughening systems, this inorganic rigid material can maintain a higher modulus and prevent molecular chain segment slippage, which helps to improve the wear resistance of PVC / ASA system.

[0009] Preferably, the polyvinyl chloride alloy material comprises, by weight, the following components: 60-80 parts of polyvinyl chloride resin, 20-40 parts of styrene-acrylonitrile-acrylic rubber terpolymer, 5-20 parts of pure monomer resin, 3-15 parts of inorganic rigid material, 1-5 parts of stabilizer, and 2-4 parts of acrylate processing aid.

[0010] In a preferred embodiment of the polyvinyl chloride alloy material of the present invention, the pure monomer resin is polymerized from pure aromatic monomers.

[0011] The pure monomer resin described in this invention is an aromatic petroleum resin, which is polymerized from pure aromatic petroleum monomers, namely α-methylstyrene monomer.

[0012] As a preferred embodiment of the polyvinyl chloride alloy material of the present invention, the softening point of the pure monomer resin is 75℃-125℃; the softening point is measured with reference to GB / T15332-94 softening point of hot melt adhesives.

[0013] Preferably, the softening point of the pure monomer resin is within the range of any one or both of 75℃, 80℃, 90℃, 100℃, 110℃, 120℃, and 125℃. More preferably, the softening point of the pure monomer resin is 80℃-120℃.

[0014] Through experiments, this invention has verified that the pure monomer resin with the above-mentioned softening point can enable the polyvinyl chloride alloy material of this invention to have good processing performance.

[0015] As a preferred embodiment of the polyvinyl chloride alloy material of the present invention, the inorganic rigid material includes at least one of nano-calcium carbonate, nano-silica, and tubular nanomaterials.

[0016] Preferably, the particle size D90 of the nano-calcium carbonate and nano-silica is less than 400 nm; the particle size is tested by laser particle size analyzer.

[0017] Preferably, the inorganic rigid material is a tubular nanomaterial; the tubular nanomaterial includes at least one of carbon nanotubes and halloysite; preferably halloysite.

[0018] In a preferred embodiment of the polyvinyl chloride alloy material of the present invention, the stabilizer is at least one of calcium-zinc stabilizer, lead salt stabilizer, organotin stabilizer, and barium-zinc stabilizer.

[0019] As a preferred embodiment of the polyvinyl chloride alloy material of the present invention, the tubular nanomaterial has an inner diameter of 10nm-100nm and a tube length of 15nm-1500nm.

[0020] Preferably, the tubular nanomaterial has an inner diameter of 10nm-20nm and a length of 100nm-1500nm.

[0021] This invention has discovered through research that when tubular nanomaterials are used as inorganic rigid materials, the presence of the tubular structure not only provides a good toughening effect but also enhances the flame retardant properties of the material, while simultaneously improving its wear resistance and flame retardant effect.

[0022] Furthermore, since halloysite nanotubes contain water of crystallization, which acts as a barrier, they also have an adsorption effect on free radicals and a good carbonization effect, resulting in better toughening, flame retardant and smoke suppression effects.

[0023] In a preferred embodiment of the polyvinyl chloride alloy material of the present invention, the degree of polymerization of the polyvinyl chloride resin is 800-1300. The degree of polymerization is determined and calculated using a capillary viscometer with a dilute solution of polyvinyl chloride resin as the test sample, according to GB / T3401-2007.

[0024] Preferably, the degree of polymerization of the polyvinyl chloride resin is any one or a combination of 800, 1000, and 1300.

[0025] In a preferred embodiment of the polyvinyl chloride alloy material of the present invention, the weight ratio of the inorganic rigid material to the pure monomer resin is 1:(0.75-2.5).

[0026] Preferably, the weight ratio of the inorganic rigid material to the pure monomer resin is any one or a combination of 1:0.75, 1:1, 1:1.5, 1:2, and 1:2.5; more preferably, the weight ratio of the inorganic rigid material to the pure monomer resin is 1:(1-2).

[0027] This invention has found that when the inorganic rigid material and the pure monomer resin are within the above-mentioned mass ratio range, the material has better overall performance.

[0028] Preferably, in the polyvinyl chloride alloy material, the sum of the mass percentages of the polyvinyl chloride resin and the styrene-acrylonitrile-acrylic rubber terpolymer is not less than 60%.

[0029] Another object of the present invention is to provide a method for preparing the polyvinyl chloride alloy material, comprising the following steps:

[0030] (1) Mix polyvinyl chloride resin and stabilizer evenly, then add styrene-acrylonitrile-acrylic rubber terpolymer, pure monomer resin, acrylate processing aids and inorganic rigid materials and mix evenly to obtain premix;

[0031] (2) The premix obtained in step (1) is added to a twin-screw extruder for extrusion granulation to obtain the polyvinyl chloride alloy material.

[0032] The preparation method of the polyvinyl chloride alloy material described in this invention is simple and can be industrialized on a large scale.

[0033] Preferably, the extrusion granulation temperature is: Zone 1 110℃-120℃, Zone 2 120℃-130℃, Zone 3 130℃-140℃, Zone 4 140℃-150℃, Zone 5 145℃-155℃, Zone 6 150℃-160℃, Zone 7 155℃-165℃, Zone 8 160℃-170℃, Zone 9 150℃-160℃; and the screw speed is 350-450 rpm.

[0034] Another object of the present invention is to provide the application of the polyvinyl chloride alloy material in transportation profiles and electronic and electrical profiles.

[0035] The polyvinyl chloride alloy material of this invention has excellent wear resistance and flame retardant and low smoke properties, and can be used in transportation, electronics and electrical engineering, building materials and other fields, such as luggage racks for public buses, bus door and window profiles, and profiles for electronic and electrical guide rails.

[0036] The beneficial effects of this invention are that it provides a polyvinyl chloride alloy material. This product improves the toughness of PVC material by adding a styrene-acrylonitrile-acrylic rubber terpolymer, and further introduces pure monomer resin and inorganic rigid material at the same time. While maintaining the flame retardant properties of the polyvinyl chloride alloy material, it improves the wear resistance and flame retardant smoke emission of the product. The resulting polyvinyl chloride alloy material has the characteristics of wear resistance, flame retardancy and low smoke emission, and the application scenarios of the product are further expanded. Detailed Implementation

[0037] To better illustrate the objectives, technical solutions, and advantages of this invention, the invention will be further described below with reference to specific embodiments. Those skilled in the art should understand that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions comprised of the listed features and open-ended technical solutions that include the listed features. All other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this invention.

[0038] Unless otherwise specified, the experimental methods used in the examples are conventional methods; the materials and reagents used are commercially available unless otherwise specified.

[0039] Examples 1-13

[0040] The composition of the polyvinyl chloride alloy material described in this embodiment of the invention is shown in Table 1.

[0041] The method for preparing the polyvinyl chloride alloy material includes the following steps:

[0042] (1) Mix the polyvinyl chloride resin and stabilizer evenly according to the weight parts, then add the styrene-acrylonitrile-acrylic rubber terpolymer, pure monomer resin, acrylate processing aids and inorganic rigid materials and mix evenly to obtain a premix.

[0043] (2) The premix obtained in step (1) is added to a twin-screw extruder for extrusion granulation to obtain the granulation material. The extrusion granulation temperature is: 115℃ in zone 1, 125℃ in zone 2, 135℃ in zone 3, 145℃ in zone 4, 150℃ in zone 5, 155℃ in zone 6, 160℃ in zone 7, 165℃ in zone 8, and 155℃ in zone 9. The screw speed is 400 rpm.

[0044] Comparative Examples 1-5

[0045] The only difference between each comparative example and the embodiment is the type and ratio of components, as shown in Table 2.

[0046] In the components described in each embodiment and comparative example,

[0047] The polyvinyl chloride resin 1 is TG-800, manufactured by Tosoh Corporation of Japan, with a degree of polymerization of 800.

[0048] The polyvinyl chloride resin 2 is TL-1000, manufactured by LG Korea, with a degree of polymerization of 1000.

[0049] The polyvinyl chloride resin 3 is TG-1300, manufactured by Tosoh Corporation of Japan, with a degree of polymerization of 1300.

[0050] The styrene-acrylonitrile-acrylic rubber terpolymer (ASA) is XC-180, Kumho;

[0051] The pure monomer resin 1 is TS3080, produced by Tengshun Chemical, with a softening point of 80℃.

[0052] The pure monomer resin 2 is 3100, Eastman, with a softening point of 100°C;

[0053] The pure monomer resin 3 is 1120, Eastman, with a softening point of 120°C;

[0054] The inorganic rigid material 1 is nano-silica, A200, Evonik Aerosil.

[0055] The inorganic rigid material 2 is a carbon nanotube, CP1002M, manufactured by LG in South Korea, with an inner diameter of 15nm.

[0056] The inorganic rigid material 3 is halloysite HNT200, also known as nanomaterials, with an inner diameter of 15nm.

[0057] The stabilizer is an organotin stabilizer, TM-181, or Yunnan Tin.

[0058] The acrylate processing aid PA20 is from Zhongyuan.

[0059] Unless otherwise specified, all components and raw materials used in the embodiments and comparative examples of this invention are commercially available, and the same type of components and raw materials are used in each parallel experiment.

[0060] Table 1. Content of each component (parts) in the materials of Examples 1-13

[0061]

[0062]

[0063] Table 2 shows the content (parts) of each component in the materials of Comparative Examples 1-5.

[0064]

[0065] To verify the performance of the polyvinyl chloride alloy material described in this invention, the products prepared in each embodiment and comparative example were subjected to the following performance tests, as detailed below:

[0066] 1. Wear resistance test: The sample is placed vertically on a vertical universal friction and wear testing machine. The sample size is 7mm × 6mm × 30mm, the rotation speed is 200r / min, the load is 50N, and the loading time is 30min. The wear value is less than 30g / m. 2 It is excellent.

[0067] 2. Total smoke release test: Cone calorimeter test, thermal radiation: 50KW, sample thickness: 3mm; smoke release of less than 300 is preferred.

[0068] 3. Flame retardant performance test: The test shall be conducted in accordance with GB-T 2406; Test method for burning performance of plastics, oxygen index method; an oxygen index greater than 27 is preferred.

[0069] The test results are shown in Tables 3 and 4.

[0070] Table 3. Material property test results of Examples 1-13

[0071]

[0072] Table 4. Material property test results for Comparative Examples 1-5

[0073] Test Project Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 <![CDATA[Total amount of smoke released (m 2 / m 2 )]]> 966 350 365 850 320 <![CDATA[Wear value (g / m 2 )]]> 65 58 53 62 50 Oxygen Index 27 28.5 28.3 27.5 28

[0074] As shown in Tables 3 and 4, the polyvinyl chloride alloy materials of Examples 1-13 of the present invention have excellent flame retardant, wear-resistant, and smoke-suppressing effects, with wear values ​​not exceeding 20 g / m². 2 It releases relatively little smoke and has good flame-retardant properties.

[0075] The test results of Examples 1 and Comparative Examples 2-3 show that neither excessively high nor low amounts of pure monomeric resin can give the material excellent overall performance. Comparing Examples 1 and Comparative Examples 1 and 4-5, it is evident that without the introduction of inorganic rigid materials, the wear resistance and smoke suppression effect of the material significantly decrease. Furthermore, only when the amount of inorganic rigid materials added is within the range specified in this application can the material exhibit excellent wear resistance, flame retardancy, and smoke suppression effects. A comparison of Examples 1 and Examples 6 and 7 shows that the introduction of halloysite can provide superior smoke suppression effects while ensuring the material's wear resistance and flame retardancy.

[0076] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polyvinyl chloride alloy material, characterized in that, By weight, it includes the following components: 59-81 parts of polyvinyl chloride resin, 18-42 parts of styrene-acrylonitrile-acrylic rubber terpolymer, 4-21 parts of pure monomer resin, 2-16 parts of inorganic rigid material, 0.5-5.5 parts of stabilizer and 1-5 parts of acrylate processing aids. The pure monomer resin is polymerized from pure aromatic monomers; The inorganic rigid material includes at least one of nano-calcium carbonate, nano-silica, and tubular nanomaterials; the weight ratio of the inorganic rigid material to the pure monomer resin is 1:(0.75-2.5).

2. The polyvinyl chloride alloy material according to claim 1, characterized in that, The softening point of the pure monomer resin is 75℃-125℃.

3. The polyvinyl chloride alloy material according to claim 1, characterized in that, The stabilizer is at least one of calcium-zinc stabilizers, lead salt stabilizers, organotin stabilizers, and barium-zinc stabilizers.

4. The polyvinyl chloride alloy material according to claim 1, characterized in that, The tubular nanomaterials include at least one of carbon nanotubes and halloysite.

5. The polyvinyl chloride alloy material according to claim 4, characterized in that, The tubular nanomaterial is halloysite.

6. The polyvinyl chloride alloy material according to claim 1, characterized in that, The degree of polymerization of the polyvinyl chloride resin is 800-1300.

7. The polyvinyl chloride alloy material according to claim 1, characterized in that, The weight ratio of the inorganic rigid material to the pure monomer resin is 1:(1-2).

8. The method for preparing the polyvinyl chloride alloy material according to any one of claims 1-7, characterized in that, Includes the following steps: (1) Mix polyvinyl chloride resin and stabilizer evenly, then add styrene-acrylonitrile-acrylic rubber terpolymer, pure monomer resin, acrylate processing aids and inorganic rigid materials and mix evenly to obtain premix; (2) The premix obtained in step (1) is added to a twin-screw extruder for extrusion granulation to obtain the polyvinyl chloride alloy material.

9. The application of the polyvinyl chloride alloy material according to any one of claims 1-7 in transportation and electronic / electrical profiles.

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