A cpvc alloy material and application thereof

Abstract

The application discloses a CPVC alloy material and application thereof, and belongs to the technical field of high polymer materials. The application effectively improves the processing fluidity, impact resistance and weather resistance of the material by adding a specific amount of SAN resin and ASA resin into the CPVC resin and limiting the acrylonitrile content in the SAN resin within a specific range, so that the obtained alloy material is suitable for preparing household appliances, building material pipe fittings, electronic and electrical products, security products, outdoor products and the like.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and particularly relates to a CPVC alloy material and application thereof. BACKGROUND

[0002] Chlorinated polyvinyl chloride (CPVC) resin is a product prepared by chlorination of polyvinyl chloride (PVC) resin, and the chlorine content thereof can be increased from 56.7 wt.% of the PVC resin to 60 wt.% or even more than 70 wt.%. The heat distortion temperature of the CPVC resin is increased by more than 10℃ than that of the PVC resin, and the specific increase in temperature is increased with the increase in chlorination degree, which enables the CPVC resin to be applied in harsh environments where many materials cannot be used. However, after the chlorination reaction of the PVC resin, the interaction between the molecular chains is enhanced, resulting in an increase in the processing difficulty of the CPVC resin; at the same time, the impact strength of the pure CPVC material is low, and the commercial application thereof is limited.

[0003] Therefore, it is necessary to develop a CPVC alloy material which is easy to process, has high impact strength and good weather resistance. SUMMARY

[0004] Based on the defects of the prior art, the purpose of the application is to provide a CPVC alloy material and application thereof, which is easy to process, has high impact strength and good weather resistance.

[0005] In order to achieve the above purpose, the application provides a CPVC alloy material, which comprises the following components in parts by weight: 29.5-60.5 parts of CPVC resin, 9.6-20.4 parts of ASA resin and 19.5-40.8 parts of SAN resin; wherein the content of acrylonitrile in the SAN resin is 24 wt.%-30.5 wt.%.

[0006] SAN resin, also known as AS resin, is a copolymer of styrene and acrylonitrile, which has good processing fluidity but poor impact resistance; the content of acrylonitrile in the SAN resin will affect the compatibility of the SAN resin with the CPVC resin, by controlling the content of acrylonitrile in the SAN resin in the range of 24wt.% to 30.5wt.%, the SAN resin has good compatibility with the CPVC resin without adding a compatibilizer, which is conducive to weakening the interaction between CPVC molecules, thereby improving the processing fluidity, and further reducing the frictional heat between the molecular chains of CPVC during processing, and slowing down the processing decomposition of CPVC. The ASA resin is a ternary graft copolymer with core-shell structure composed of acrylate (ACR), styrene (ST) and acrylonitrile (AN), which has strong weather resistance and excellent impact resistance. By adding a specific amount of SAN resin and ASA resin to the CPVC resin, and limiting the content of acrylonitrile in the SAN resin within a specific range, the processing fluidity, impact resistance and weather resistance of the material can be effectively improved.

[0007] The CPVC alloy material not only is easy to process, but also has high impact strength and good weather resistance under the joint action of the components in a specific content.

[0008] The content of acrylonitrile in the SAN resin is 24wt.% to 30.5wt.%, such as 25wt.%, 26wt.%, 27wt.%, 28wt.%, 29wt.%, 30wt.% or a range formed by any two of the above values. The content of acrylonitrile in the SAN resin can be measured by elemental analysis method, such as using high temperature combustion method to determine the content of conventional organic elements in the sample, and the elements measured are carbon (C), hydrogen (H) and nitrogen (N). The test conditions can be selected as follows: sample weighing: 2mg, decomposition temperature: 950-1200℃, analysis time: 6-9 minutes for simultaneous determination of C, H and N.

[0009] The CPVC resin is 29.5-60.5 parts by weight, such as 29.5 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 55 parts by weight, 60 parts by weight, 60.5 parts by weight or a range formed by any two of the above values.

[0010] The ASA resin is 9.6-20.4 parts by weight, such as 9.6 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 17 parts by weight, 20 parts by weight, 20.4 parts by weight or a range formed by any two of the above values.

[0011] The SAN resin is 19.5-40.8 parts by weight, such as 19.5 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 40.8 parts by weight or a range formed by any two of the above values.

[0012] The weight ratio of the ASA resin and the SAN resin will affect the processability, impact strength and weather resistance of the alloy material. When the SAN resin / ASA resin (w / w) ratio is too high, the impact strength and weather resistance of the alloy material will be weak due to the weak impact strength and weather resistance of the SAN resin compared with the ASA resin; when the SAN resin / ASA resin (w / w) ratio is too low, the CPVC will decompose more during the process due to the high viscosity during the process, which is not conducive to the impact strength and weather resistance. In order to obtain better processability, impact strength and weather resistance, in some embodiments, the weight ratio of the ASA resin and the SAN resin is 1:(1.2-3.1), such as 1:1.25, 1:1.3, 1:1.5, 1:1.8, 1:2, 1:2.3, 1:2.5, 1:2.8, 1:3 or a range formed by any two of the above values. In particular, in a specific embodiment, the weight ratio of the ASA resin and the SAN resin is 1:(1.45-2.35), such as 1:1.5, 1:1.7, 1:1.9, 1:2, 1:2.1, 1:2.3 or a range formed by any two of the above values, and the impact strength and weather resistance of the obtained alloy material are better.

[0013] The average polymerization degree of the CPVC resin will affect the viscosity, impact strength and weather resistance of the alloy material during the process. When the average polymerization degree of the CPVC resin is too low, its impact strength and weather resistance are weak; when the average polymerization degree of the CPVC resin is too high, the viscosity of the alloy material during the process is high, which causes the decomposition of the CPVC due to the friction between the molecular chains during the process, which adversely affects the impact strength and weather resistance. In some embodiments, the average polymerization degree of the CPVC resin is 350-750, such as 400, 500, 600, 700 or a range formed by any two of the above values, so that the process viscosity of the obtained CPVC alloy material is appropriate, which is conducive to injection molding, and the impact strength and weather resistance are better. In a specific embodiment, the average polymerization degree of the CPVC resin is 450-650, such as 500 or 600, so that the impact strength and weather resistance of the obtained CPVC alloy material are better.

[0014] The average polymerization degree of the CPVC resin can be measured by high-temperature gel permeation chromatography (GPC) test, using 1,2,4-trichlorobenzene as the eluent and styrene divinylbenzene copolymer as the gel powder, and measuring at 150°C.

[0015] In some embodiments, the ASA resin is an ASA powder. Adding the ASA resin in the form of a powder is more conducive to its dispersion in the matrix.

[0016] The smaller the bulk density of the ASA powder, the more beneficial it is to its dispersion in the matrix. In some embodiments, the bulk density of the ASA powder is ≤ 0.41 g / cm 3 , 0.4 g / cm 3 , 0.38 g / cm 3 , 0.35 g / cm 3 , 0.32 g / cm 3 , 0.3 g / cm 3 , 0.28 g / cm 3 , 0.25 g / cm 3 or a range formed by any two of the above values, so that it is better dispersed in the matrix, which is beneficial to improve the impact resistance and weather resistance of the CPVC alloy material, especially when the bulk density of the ASA powder is ≤ 0.36 g / cm 3 . In a specific embodiment, the bulk density of the ASA powder is 0.27-0.36 g / cm 3 , 0.28 g / cm 3 , 0.29 g / cm 3 , 0.30 g / cm 3 , 0.31 g / cm 3 , g / cm 3 , 0.32 g / cm 3 , 0.33 g / cm 3 , 0.34 g / cm 3 , 0.35 g / cm 3 or a range formed by any two of the above values.

[0017] The bulk density of the ASA resin can be measured according to GB / T 23771-2009 at 23°C, 50% RH.

[0018] In some embodiments, the CPVC alloy material further comprises the following components by weight: heat stabilizer 2.8-6.3 parts, lubricant 0.9-5.2 parts, inorganic filler 0.9-5.1 parts, and other additives 0-3.1 parts.

[0019] In some embodiments, the heat stabilizer includes at least one of an organotin-based stabilizer and an organoantimony-based stabilizer, but the selection thereof is not limited thereto. As an example, the organotin-based stabilizer includes at least one of alkyl tin, alkyl mercaptan tin, alkyl tin maleate, alkyl tin laurate, etc., wherein the alkyl tin includes at least one of methyl tin, butyl tin, octyl tin, etc., the alkyl mercaptan tin includes at least one of methyl mercaptan tin, butyl mercaptan tin, octyl mercaptan tin, etc., the alkyl tin maleate includes at least one of methyl tin maleate, butyl tin maleate, octyl tin maleate, etc., and the alkyl tin laurate includes at least one of methyl tin laurate, butyl tin laurate, octyl tin laurate, etc. As an example, the organoantimony-based stabilizer includes at least one of tris(dodecyl mercaptan) antimony, tris(n-butyl mercaptoacetate) antimony, penta-mercaptobenzimidazole antimony, tris(isooctyl mercaptoacetate) antimony, etc.

[0020] In some embodiments, the lubricant includes at least one of polyethylene wax, oxidized polyethylene wax, Fischer-Tropsch wax, paraffin wax, and polyester wax, but the selection thereof is not limited thereto.

[0021] In some embodiments, the inorganic filler includes at least one of calcium carbonate, talc, barium sulfate, and titanium dioxide, but the selection thereof is not limited thereto.

[0022] In some embodiments, the other auxiliary agent includes at least one of plasticization promoter, flow modifier, antioxidant, and weathering agent, but the selection thereof is not limited thereto. As an example, the plasticization promoter includes at least one of methyl methacrylate-acrylate copolymer, etc.; the flow modifier includes at least one of modified petroleum resin, etc.; the antioxidant includes at least one of hindered phenol and aniline, etc.; and the weathering agent includes at least one of benzotriazole and hindered amine, etc.

[0023] In some embodiments, the content of the CPVC resin in the CPVC alloy material is 28 wt.% or more, such as in a range formed by any two of 29 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 64 wt.% or more.

[0024] In some embodiments, the melt flow rate of the SAN resin at 200°C under a load of 5 kg according to ISO 1133-2012 is 3 g / 10 min or more, such as in a range formed by any two of 3 g / 10 min, 3.5 g / 10 min, 4 g / 10 min, 4.5 g / 10 min, 5 g / 10 min or more.

[0025] The CPVC alloy material described in the present application can contain common additives such as flame retardants and antistatic agents without impairing the effects of the present application.

[0026] In some embodiments, the method for preparing the CPVC alloy material comprises the following steps: mixing raw materials of each component, feeding into a screw extruder for melt extrusion and granulation, thereby obtaining the CPVC alloy material. In a specific embodiment, the mixing is carried out at 80-100℃. In a specific embodiment, the temperature of each section of the screw extruder is 150-170℃.

[0027] The present application also provides the use of the CPVC alloy material in the preparation of household appliances, building material pipe fittings, electronic and electrical products, security products or outdoor products. For example, junction box shell, connecting pipe fitting, power strip emergency lighting shell, tool shell, etc.

[0028] Compared with the prior art, the present application has the following advantages:

[0029] (1) The present application adds SAN resin with a specific acrylonitrile content to CPVC resin to weaken the interaction between CPVC molecules, effectively improve the processing fluidity, reduce the frictional heat between the molecular chains of CPVC during processing, and slow down the processing decomposition of CPVC; by adding ASA resin to CPVC resin, the impact resistance and weather resistance are effectively improved.

[0030] (2) The CPVC alloy material of the present application, under the combined action of specific contents of each component, is not only easy to process, but also has high impact strength and good weather resistance, and is suitable for the preparation of household appliances, building material pipe fittings, electronic and electrical products, security products, outdoor products, etc. DETAILED DESCRIPTION

[0031] In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in conjunction with specific examples and comparative examples, the purpose of which is to understand the content of the present application in detail, rather than to limit the present application. All other examples obtained by those of ordinary skill in the art without creative labor fall within the scope of the present application. The experimental reagents and instruments involved in the implementation of the present application are common ordinary reagents and instruments unless otherwise specified. In the present application, the open description of technical features includes both the closed technical solution consisting of the listed features and the open technical solution containing the listed features.

[0032] Examples and Comparative Examples

[0033] Each of the embodiments and the comparative examples provides a CPVC alloy material, the composition of which is shown in Tables 1 and 2, and the preparation method comprises the following steps: mixing raw materials of each component by a high-speed mixer device, continuously mixing at a temperature of 90°C for 10 minutes, and then feeding into a twin-screw extruder, the temperature of each section of the screw of the extruder being between 150-170°C, under the shearing, mixing and conveying of the screw, the material is fully melted and compounded, and finally the CPVC alloy material is obtained by extruding and granulating.

[0034] The component information used in each of the embodiments and the comparative examples is as follows:

[0035] CPVC Resin 1: average polymerization degree 450, H305, Japan Kao Corporation;

[0036] CPVC Resin 2: average polymerization degree 500, Z-500, Shandong Gaoxin Chemical;

[0037] CPVC Resin 3: average polymerization degree 600, H716S, Japan Kao Corporation;

[0038] CPVC Resin 4: average polymerization degree 700, H727, Japan Kao Corporation;

[0039] ASA Powder 1: bulk density 0.28 g / cm 3 , UMG AXS A600N, Japan Ube;

[0040] ASA Powder 2: bulk density 0.32 g / cm 3 , ASA POW XC640, South Korea Kumho Chemical;

[0041] ASA Powder 3: bulk density 0.35 g / cm 3 , ASA LP2065X, Guangzhou Enteng Innovative Materials;

[0042] ASA Powder 4: bulk density 0.40 g / cm 3 , ASA LI910, South Korea LG Chemical;

[0043] ASA Resin 5: Starex ASAWX-9700, South Korea Lotte;

[0044] ABS: ABS D-120A, Guojiao Petrochemical;

[0045] SAN Resin 1: acrylonitrile content 20 wt.%, styrene content 80 wt.%, SAN 310TR, MFI 3.0 g / 10 kg, South Korea Kumho Petrochemical;

[0046] SAN resin 2: acrylonitrile content of 25 wt.%, styrene content of 75 wt.%, SAN KFA-130, MFI of 3.5 g / 10 kg, Liaoning Jinfa;

[0047] SAN resin 3: acrylonitrile content of 27 wt.%, styrene content of 73 wt.%, SAN SA50, MFI of 3.8 g / 10 kg, LG Huizhou;

[0048] SAN resin 4: acrylonitrile content of 30 wt.%, styrene content of 70 wt.%, SAN 350, MFI of 3.3 g / 10 kg, South Korea Jinhu Petrochemical;

[0049] SAN resin 5: acrylonitrile content of 32 wt.%, styrene content of 68 wt.%, SAN 335T, MFI of 3.0 g / 10 kg, South Korea Jinhu Petrochemical;

[0050] Thermal stabilizer: thiol methyl tin stabilizer;

[0051] Lubricant: polyethylene wax, oxidized polyethylene wax and polyester wax, mass ratio of 1:1:1;

[0052] Inorganic filler: titanium dioxide;

[0053] Other auxiliary agents: methyl methacrylate-acrylate copolymer.

[0054] The components used in each embodiment and comparative example of the present application are commercially available unless otherwise specified, and the components used in each parallel experiment are the same.

[0055] The CPVC alloy material obtained in each embodiment and comparative example was first injection molded into a standard sample bar according to ASTM standard size for testing, and then each performance test was carried out according to the test standards shown in Table 3. The test results are shown in Table 4.

[0056] Table 1

[0057]

[0058] Table 2

[0059]

[0060]

[0061] Table 3

[0062]

[0063] Table 4

[0064]

[0065]

[0066] From Table 4, it can be seen that the CPVC alloy material obtained by each embodiment of the present application has good processing performance, impact resistance and weather resistance, wherein the melt flow rate is above 15 g / min (220℃ / 10kg), the Izod notched impact strength is above 200 J / m, and the impact retention rate after aging is above 80%.

[0067] The melt flow rate, Izod notched impact strength and impact retention rate after aging of Comparative Examples 1-2 are low, which may be because the content of acrylonitrile in the SAN resin is too high or too low, which is not conducive to the compatibility of the SAN resin with the CPVC resin, resulting in poor processing flowability, which is not conducive to processing, and the molecular chains are easy to generate heat by friction during processing, which is easy to decompose, and is not conducive to impact resistance and weather resistance.

[0068] The melt flow rate, Izod notched impact strength and impact retention rate after aging of Comparative Examples 3-4 are low, which shows that the content of the ASA resin or the SAN resin being too high or too low is not conducive to the processing performance, impact resistance and weather resistance.

[0069] It can be seen from the comparison of Example 2 and Examples 4-7 that as the weight ratio of the SAN resin / ASA resin (w / w) increases, the melt flow rate of the alloy material gradually increases, and the Izod notched impact strength and weather resistance show a trend of first increasing and then decreasing. When the weight ratio of the ASA resin and the SAN resin is in the range of 1:(1.45-2.55), not only is the melt flow rate of the CPVC alloy material high during processing, but also the processing performance is good, and the Izod notched impact strength and the impact retention rate after aging are higher.

[0070] It can be seen from the comparison of Example 2 and Examples 12-14 that as the average degree of polymerization of the CPVC resin increases, the melt flow rate of the alloy material gradually decreases, and the Izod notched impact strength and weather resistance show a trend of first increasing and then decreasing. When the average degree of polymerization of the CPVC resin is in the range of 450-650, not only is the melt flow rate of the CPVC alloy material high during processing, but also the processing performance is good, and the Izod notched impact strength and the impact retention rate after aging are higher.

[0071] It can be seen from the comparison of Examples 11, 15-18 that compared with the ASA resin, the use of ASA powder can make the impact strength of the CPVC alloy material higher, which is because the ASA powder is easier to disperse in the matrix; the lower the bulk density of the ASA powder, the more conducive to its dispersion in the matrix, which is conducive to improving the impact resistance and weather resistance of the alloy material. When the bulk density of the ASA powder is 0.27-0.36 g / cm 3At this time, the cantilever beam notched impact strength and impact retention rate after aging of the obtained CPVC alloy material are higher.

[0072] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and are not a limitation on the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A CPVC alloy material, characterized in that, The product comprises the following components in parts by weight: 30-60 parts CPVC resin, 9.6-20.4 parts ASA resin, and 19.5-40.8 parts SAN resin; wherein the acrylonitrile content in the SAN resin is 24 wt.%-30.5 wt.%, the weight ratio of the ASA resin to the SAN resin is 1:(1.2-3.1), the ASA resin is ASA adhesive powder, and the bulk density of the ASA adhesive powder is 0.27-0.36 g / cm³. 3 .

2. The CPVC alloy material as described in claim 1, characterized in that, The weight ratio of the ASA resin to the SAN resin is 1:(1.45~2.35).

3. The CPVC alloy material as described in claim 1, characterized in that, The average degree of polymerization of the CPVC resin is 400~750.

4. The CPVC alloy material as described in claim 3, characterized in that, The average degree of polymerization of the CPVC resin is 450~650.

5. The CPVC alloy material as described in claim 1, characterized in that, It also includes the following components in parts by weight: 2.8 to 6.3 parts heat stabilizer, 0.9 to 5.2 parts lubricant, 0.9 to 5.1 parts inorganic filler, and 0 to 3.1 parts other additives.

6. The application of the CPVC alloy material as described in any one of claims 1 to 5 in the manufacture of household appliances, building material pipe fittings, electronic and electrical products, security products or outdoor products.

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