Chlorinated polyvinyl chloride composite material, preparation method and application thereof

Abstract

The application discloses a chlorinated polyvinyl chloride composite material and a preparation method and application thereof, and relates to the technical field of chlorinated polyvinyl chloride composite materials. The application provides a chlorinated polyvinyl chloride composite material, which comprises the following components in parts by weight: chlorinated polyvinyl chloride resin 50-70 parts, ABS resin 30-50 parts, polyvinyl chloride resin 8-15 parts, heat stabilizer 3-6 parts, lubricant 1-5 parts, inorganic filler 1-5 parts, and other additives 0-3 parts; and the polymerization degree of the chlorinated polyvinyl chloride resin is 500-700. According to the selection of the specific parts by weight of the chlorinated polyvinyl chloride composite material, the flame-retardant grade of 5VA can be reached without adding a flame retardant, the carbonization performance is good, and the chlorinated polyvinyl chloride composite material has good processing flow performance and cantilever beam notched impact strength.

Description

Technical Field

[0001] The present invention relates to the technical field of chlorinated polyvinyl chloride composite materials, in particular to a chlorinated polyvinyl chloride composite material and a preparation method and application thereof. Background Art

[0002] Chlorinated polyvinyl chloride (CPVC) is a new type of engineering plastic made by chlorinating and modifying polyvinyl chloride (PVC) resin. Its heat deformation temperature is over 10 degrees Celsius higher than that of PVC, allowing its application in harsh environments where many other materials cannot be used. However, pure CPVC is more difficult to thermally stabilize and process than PVC, and its impact strength is relatively low, limiting its commercial application. ABS, a terpolymer of acrylonitrile-butadiene-styrene, exhibits excellent processability and impact resistance, but ABS itself has a low oxygen index and is extremely flammable. Therefore, blending CPVC with ABS to prepare an alloy can, on the one hand, compensate for the poor flame retardancy of ABS, and on the other hand, reduce the processing difficulty of the CPVC system and improve its impact resistance.

[0003] Chinese patent CN103374191A discloses a flame-retardant CPVC / ABS alloy material and its preparation method. This patent requires the addition of a flame retardant, such as 1-10 parts antimony trioxide or sodium antimonate, to the PVC / ABS alloy material to achieve a V-0 flame retardancy, and its impact resistance is also not particularly ideal. Chinese patent CN106189046A discloses a CPVC / ABS composition and its preparation method. This patent reports the use of a core-shell ABS grafted powder as an impact modifier for alloying and blending with CPVC. This system exhibits good impact resistance, but the ABS used is not commercially sourced but rather obtained through a special preparation process. Furthermore, the patent does not report the processing flow properties and flame retardancy of this system.

[0004] In summary, developing a chlorinated polyvinyl chloride composite material with good processing flowability, Izod notched impact strength, combustion charring performance, and flame retardancy has high application value. Summary of the Invention

[0005] Based on this, the purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a chlorinated polyvinyl chloride composite material with good processing flowability, Izod notched impact strength, combustion charring performance and flame retardancy.

[0006] To achieve the above-mentioned purpose, the technical solution adopted by the present invention is: a chlorinated polyvinyl chloride composite material, comprising the following components in parts by weight: 50-70 parts of chlorinated polyvinyl chloride resin, 30-50 parts of ABS resin, 8-15 parts of polyvinyl chloride resin, 3-6 parts of heat stabilizer, 1-5 parts of lubricant, 1-5 parts of inorganic filler, and 0-3 parts of other additives; the degree of polymerization of the chlorinated polyvinyl chloride resin is 500-700.

[0007] The introduction of PVC in the present invention can weaken the interaction between CPVC molecular weights, improving CPVC's processing flow properties to a certain extent. PVC also increases entanglement with CPVC and ABS molecular chains, ensuring physical bonding between alloy phases, thereby ensuring the flame retardancy of the entire CPVC alloy. During combustion, it is difficult to burn through and forms a char layer with a certain strength. By selecting specific weight proportions of CPVC, ABS, and PVC, the chlorinated polyvinyl chloride composite material prepared in the present invention exhibits excellent processing flow properties, notched Izod impact strength, combustion char formation properties, and flame retardancy. The specific weight proportions selected in the present invention enable the chlorinated polyvinyl chloride composite material to achieve a 5VA flame retardancy rating without the addition of a flame retardant.

[0008] The degree of polymerization of PVC and CPVC of the present invention is measured by gel permeation chromatography (GPC).

[0009] Preferably, the weight portion of the chlorinated polyvinyl chloride resin is 55-60 parts, the weight portion of the ABS resin is 35-45 parts, and the weight portion of the polyvinyl chloride resin is 10-12 parts.

[0010] When the above components are used, the performance of the prepared chlorinated polyvinyl chloride composite material is better, MFI ≥ 29g / 10min, and the Izod notched impact strength ≥ 27kJ / m 2 , 1.0mm vertical combustion is V-0, 1.0mm 5V combustion is 5VA level, and the combustion carbonization property is excellent.

[0011] Preferably, the total mass of the chlorinated polyvinyl chloride resin, ABS resin and polyvinyl chloride resin is 90-95% of the mass of the chlorinated polyvinyl chloride composite material.

[0012] The inventors found in experiments that the total mass of chlorinated polyvinyl chloride resin, ABS resin and polyvinyl chloride resin in the chlorinated polyvinyl chloride composite material affects the performance of the chlorinated polyvinyl chloride composite material. If the total mass of chlorinated polyvinyl chloride resin, ABS resin and polyvinyl chloride resin is 90-95% of the mass of the chlorinated polyvinyl chloride composite material, the performance of the obtained chlorinated polyvinyl chloride composite material is better.

[0013] Preferably, the ABS resin satisfies at least any one of the following conditions: the weight percentage of acrylonitrile is 19-23%, the weight percentage of butadiene is 18-30%, and the weight percentage of styrene is 50-57%.

[0014] The percentage of the constituent units in the ABS resin of the present invention is determined by elemental analysis and FTIR.

[0015] The inventors found in actual experiments that the structural composition of ABS is very critical. Under the above-mentioned specific selection of the weight percentage of acrylonitrile, butadiene, and styrene in ABS resin, the compatibility with CPVC is better. The prepared chlorinated polyvinyl chloride composite material has a processing flowability MFI of more than 28g / 10min and an Izod notched impact strength of 27kJ / m 2 Above, the combustion and charring performance is excellent, 1.0mm vertical combustion V-0 grade, 1.0mm 5V combustion 5VA grade.

[0016] Preferably, the degree of polymerization of the polyvinyl chloride resin is 700-1500, preferably 1000-1300.

[0017] The inventors found in actual experiments that the degree of polymerization of PVC is very critical. When the degree of polymerization of PVC is too low, it cannot effectively increase the entanglement with the CPVC molecular chain and the ABS molecular chain. When the degree of polymerization of PVC is too high, the processing flowability deteriorates. Under the above specific selection, the chlorinated polyvinyl chloride composite material prepared has a processing flowability MFI of more than 28g / 10min and an Izod notched impact strength of 25kJ / m 2 Above, the combustion and charring performance is excellent, 1.0mm vertical combustion V-0 grade, 1.0mm 5V combustion 5VA grade.

[0018] Preferably, the heat stabilizer is at least one of an organic tin stabilizer and an organic antimony stabilizer; such as methyl, butyl, octyl alkyl tin, methyl, butyl, octyl mercaptan tin, methyl maleate, butyl, octyl tin, alkyl tin laurate and other organic tin stabilizers, tri(dodecyl mercaptan) antimony, tri(n-butyl mercaptoacetate) antimony, pentathiolate antimony, tri(isooctyl mercaptoacetate) antimony and other organic antimony stabilizers; the lubricant is at least one of polyethylene wax, oxidized polyethylene wax, Fischer-Tropsch wax, paraffin wax, and calcium stearate; the inorganic filler is at least one of calcium carbonate, talc, barium sulfate, and titanium dioxide; the other additives are at least one of a toughening agent, a flow modifier, an antioxidant, and a weathering agent, wherein the toughening agent includes ACR, MBS, and CPE, the flow modifier includes pentaerythritol ester, silicone, etc., the antioxidant includes hindered phenol antioxidants, phosphite antioxidants, etc., and the weathering agent includes an anti-ultraviolet agent, etc.

[0019] Preferably, the lubricant is polyethylene wax and oxidized polyethylene wax; preferably, the weight ratio of the polyethylene wax to the oxidized polyethylene wax is 1-2:1-2.

[0020] Preferably, the inorganic filler is titanium dioxide and calcium carbonate; preferably, the weight ratio of titanium dioxide to calcium carbonate is 1-2:1-5.

[0021] In addition, the present invention provides a method for preparing the chlorinated polyvinyl chloride composite material, comprising the following steps:

[0022] (1) Weigh various components according to the ratio;

[0023] (2) uniformly mixing the components in step (1) to obtain a mixture A;

[0024] (3) The mixture A obtained in step (2) is conveyed to a twin-screw extruder for extrusion granulation to obtain the chlorinated polyvinyl chloride composite material.

[0025] Preferably, in step (2), the mixing temperature is 80-100°C; and in step (3), the temperature of each screw section of the twin-screw extruder is 150-170°C.

[0026] Furthermore, the present invention provides applications of the chlorinated polyvinyl chloride composite material in the fields of home appliances, electronic appliances, building materials and pipe fittings, and security.

[0027] Compared to existing technologies, the present invention provides the following advantages: by selecting specific weight proportions of CPVC, ABS, and PVC, the resulting chlorinated polyvinyl chloride composite material exhibits superior processing flowability, notched Izod impact strength, combustion charring performance, and flame retardancy. Furthermore, the chlorinated polyvinyl chloride composite material can achieve a 5VA flame retardancy rating without the addition of a flame retardant. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a comparison chart of charring properties during combustion (front and back after combustion). DETAILED DESCRIPTION

[0029] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0030] In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified; the heat stabilizers, lubricants, inorganic fillers, and other additives used in the examples of the present invention and the comparative examples are exactly the same and are all conventional commercially available products.

[0031] The raw materials used in the examples and comparative examples are described below, but are not limited to these materials:

[0032] Chlorinated polyvinyl chloride resin 1: degree of polymerization 500, Z-500, Shandong Gaoxin Chemical;

[0033] Chlorinated polyvinyl chloride resin 2: degree of polymerization 700, H727, Kaneka Chemical, Japan;

[0034] Chlorinated polyvinyl chloride resin 3: degree of polymerization 450, H305, Kaneka Chemical, Japan;

[0035] Chlorinated polyvinyl chloride resin 4: DP 1000, R327, Shandong Gaoxin Chemical;

[0036] ABS resin 1: acrylonitrile content 19-22%, butadiene content 20%-25%, styrene content 50-57%, ABS D-120A, Guoqiao Petrochemical;

[0037] ABS resin 2: acrylonitrile content 19-22%, butadiene content 20%-25%, styrene content 50-57%, ABS 750N SW, Kumho Petrochemical, South Korea;

[0038] ABS resin 3: acrylonitrile content 19-22%, butadiene content 16%-18%, styrene content 61-65%, ABS DG-MG94, Tianjin Dagu Chemical;

[0039] Polyvinyl chloride resin 1: degree of polymerization 1000, PVC TL-1000, Tianjin LG Bohai Chemical;

[0040] Polyvinyl chloride resin 2: degree of polymerization 1300, PVC HG-1300, Hanwha Chemical;

[0041] Polyvinyl chloride resin 3: degree of polymerization 700, PVC TL-700, Tianjin LG Bohai Chemical;

[0042] Polyvinyl chloride resin 4: degree of polymerization 1500, S-75, Formosa Plastics Corporation, Taiwan, China;

[0043] Thermal stabilizer: methyltin mercaptan, commercially available;

[0044] Lubricant: oxidized polyethylene wax, polyethylene wax, the weight ratio of oxidized polyethylene wax to polyethylene wax is 1:1, commercially available;

[0045] Inorganic fillers: titanium dioxide, calcium carbonate, the weight ratio of titanium dioxide to calcium carbonate is 2:1, commercially available;

[0046] Other additives: hindered phenol antioxidant - antioxidant 1010, commercially available;

[0047] Examples and Comparative Examples

[0048] The components and weight percentages of the chlorinated polyvinyl chloride composite materials of the embodiment and comparative example are shown in Table 1 and Table 2. The preparation method of the chlorinated polyvinyl chloride composite materials of the embodiment and comparative example comprises the following steps:

[0049] (1) Weigh various components according to the ratio;

[0050] (2) uniformly mixing the components in step (1) at a mixing temperature of 90° C. to obtain a mixture A;

[0051] (3) The mixture A obtained in step (2) is conveyed to a twin-screw extruder, the screw temperature of each section of the twin-screw extruder is 150-170° C., and extruded and granulated to obtain the chlorinated polyvinyl chloride composite material.

[0052] Table 1

[0053]

[0054]

[0055] Table 2

[0056]

[0057] Performance Testing

[0058] 1. Processing flowability (MFI): tested in accordance with ISO 1133-2012 at 220°C / 10kg;

[0059] 2. Izod notched impact strength: tested in accordance with ISO 180-2000 at 23°C;

[0060] 3. 5V level and vertical burning: according to UL94-2018, the sample thickness is 1.0mm;

[0061] 4. Combustion charring: Burning with a 500W flame, distinguished by visual inspection;

[0062] Visual inspection method for the appearance of carbonization of square plate after burning: injection mold 1.0mm square plate sheet and burn it under the same burning conditions (UL94 5V burning standard). Figure 1 As shown in the table, according to whether there is burn-through, carbonization degree and carbon layer strength, they are divided into: ● (excellent, no burn-through, good carbonization and certain strength), ○ (good, no burn-through, good carbonization), △ (average, with cracks of about 2mm), ╳ (poor, easily burned through);

[0063] The performance test results are shown in Table 3.

[0064] Table 3

[0065]

[0066] Table 4

[0067]

[0068] As can be seen from the table above, the chlorinated polyvinyl chloride composite material prepared in the embodiment of the present invention has an MFI of ≥25g / 10min and an Izod notched impact strength of ≥20kJ / m 2 , 1.0mm vertical combustion is V-0 grade, 1.0mm5V combustion is 5VA grade, and the combustion into carbonization is good.

[0069] From the comparison of Examples 1-4, it can be seen that when the weight parts of chlorinated polyvinyl chloride resin are 55-60 parts, the weight parts of ABS resin are 35-45 parts, and the weight parts of polyvinyl chloride resin are 10-12 parts, the performance of the prepared chlorinated polyvinyl chloride composite material is better, MFI ≥ 29g / 10min, and the Izod notched impact strength ≥ 27kJ / m 2 , 1.0mm vertical combustion is V-0 grade, 1.0mm 5V combustion is 5VA grade, and the combustion carbonization property is excellent.

[0070] From the comparison of Example 3, Example 5 and Comparative Examples 1-2, it can be seen that the polymerization degree of the chlorinated polyvinyl chloride resin of the present invention is 500-700, and the performance of the prepared chlorinated polyvinyl chloride composite material is better, MFI ≥ 28g / 10min, and Izod notched impact strength ≥ 27kJ / m 2 1.0mm vertical combustion is V-0 grade, 1.0mm5V combustion is 5VA grade, and combustion charring is excellent. When the degree of polymerization of CPVC is 450, the notched impact resistance is low and the combustion performance is poor; when the degree of polymerization of CPVC is 1000, the processing performance is poor (MFI value is less than 10), and the combustion performance can only reach the 5VB level.

[0071] From the comparison between Example 3 and Examples 6-7, it can be seen that the structural composition of ABS is very critical. When the weight percentage of acrylonitrile in ABS resin is 19-23%, the weight percentage of butadiene is 18-30%, and the weight percentage of styrene is 50-57%, the processing flowability MFI is above 28g / 10min and the Izod notched impact strength is 27kJ / m 2 Above, the combustion and charring performance is excellent, 1.0mm vertical combustion V-0 grade, 1.0mm 5V combustion 5VA grade.

[0072] From the comparison between Example 3 and Examples 8-10, it can be seen that when the degree of polymerization of the polyvinyl chloride resin is 1000-1300, the inventors have found that the degree of polymerization of PVC is very critical. When the degree of polymerization of PVC is too low, it cannot effectively increase the entanglement effect with the CPVC molecular chain and the ABS molecular chain. When the degree of polymerization of PVC is too high, the processing flowability deteriorates. Under the above specific selection, the chlorinated polyvinyl chloride composite material prepared has a processing flowability MFI of more than 28g / 10min and an Izod notched impact strength of 25kJ / m 2 Above, the combustion and charring performance is excellent, 1.0mm vertical combustion V-0 grade, 1.0mm 5V combustion 5VA grade.

[0073] A comparison of Example 3 with Comparative Examples 6-7 demonstrates that the ABS resin and polyvinyl chloride resin of the present invention form a synergistic system, with neither component being indispensable. A comparison of Example 3 with Comparative Examples 3-5 and Comparative Example 7 demonstrates that the weight ratios of the chlorinated polyvinyl chloride resin, ABS resin, and polyvinyl chloride resin of the present invention must be within the specified ranges of the present invention. Slight deviations from the specified weight ratios result in significant deterioration in the processing flowability (MFI), notched Izod impact strength, and combustion performance of the resulting chlorinated polyvinyl chloride composite.

[0074] 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 the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A chlorinated polyvinyl chloride composite material, characterized in that: The invention comprises the following components in parts by weight: 50-70 parts of chlorinated polyvinyl chloride resin, 30-50 parts of ABS resin, 8-15 parts of polyvinyl chloride resin, 3-6 parts of heat stabilizer, 1-5 parts of lubricant, 1-5 parts of inorganic filler, and 0-3 parts of other additives; the degree of polymerization of the chlorinated polyvinyl chloride resin is 500-700; the degree of polymerization of the polyvinyl chloride resin is 700-1500; The ABS resin satisfies the following conditions: the weight percentage of acrylonitrile is 19-23%, the weight percentage of butadiene is 20-30%, and the weight percentage of styrene is 50-57%; or the weight percentage of acrylonitrile is 19-22%, the weight percentage of butadiene is 16-18%, and the weight percentage of styrene is 61-65%; The MFI of the chlorinated polyvinyl chloride composite material at 220°C / 10kg is ≥25g / 10min, and the test method is ISO1133-2012; The chlorinated polyvinyl chloride composite material has an Izod notched impact strength of ≥20 kJ / m 2 , the test method is ISO 180-2000; The chlorinated polyvinyl chloride composite material has a V-0 grade when burned vertically at 1.0 mm and a 5VA grade when burned at 1.0 mm at 5 V; the test method is UL94-2018.

2. The chlorinated polyvinyl chloride composite material according to claim 1, wherein The weight portion of the chlorinated polyvinyl chloride resin is 55-60 parts, the weight portion of the ABS resin is 35-45 parts, and the weight portion of the polyvinyl chloride resin is 10-12 parts.

3. The chlorinated polyvinyl chloride composite material according to claim 1, wherein: The total mass of the chlorinated polyvinyl chloride resin, ABS resin and polyvinyl chloride resin is 90-95% of the mass of the chlorinated polyvinyl chloride composite material.

4. The chlorinated polyvinyl chloride composite material according to claim 1, wherein The degree of polymerization of the polyvinyl chloride resin is 1000-1300.

5. The chlorinated polyvinyl chloride composite material according to claim 1, wherein: The heat stabilizer is at least one of an organic tin stabilizer and an organic antimony stabilizer; the lubricant is at least one of polyethylene wax, oxidized polyethylene wax, Fischer-Tropsch wax, paraffin wax and calcium stearate; the inorganic filler is at least one of calcium carbonate, talc, barium sulfate and titanium dioxide; and the other additives are at least one of a toughening agent, a flow modifier, an antioxidant and a weathering agent.

6. The chlorinated polyvinyl chloride composite material according to claim 1, wherein: The chlorinated polyvinyl chloride composite material does not contain a flame retardant.

7. A method for preparing the chlorinated polyvinyl chloride composite material according to any one of claims 1 to 6, characterized in that: The steps include: (1) Weigh various components according to the ratio; (2) uniformly mixing the components in step (1) to obtain a mixture A; (3) The mixture A obtained in step (2) is conveyed to a twin-screw extruder for extrusion granulation to obtain the chlorinated polyvinyl chloride composite material.

8. The method for preparing the chlorinated polyvinyl chloride composite material according to claim 7, wherein: In the step (2), the mixing temperature is 80-100°C; in the step (3), the temperature of each screw section of the twin-screw extruder is 150-170°C.

9. Use of the chlorinated polyvinyl chloride composite material according to any one of claims 1 to 6 in the fields of electronics and electrical engineering, building materials and pipe fittings, and security.

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