PVC / ABS alloy material, preparation method and application thereof

Abstract

The application provides a PVC / ABS alloy material and a preparation method and application thereof, and belongs to the technical field of high polymer materials.The PVC / ABS alloy material comprises the following components in parts by weight: 38-62 parts of PVC resin, 27-53 parts of ABS resin, 8-28 parts of SMA resin, 1.5-5.5 parts of a heat stabilizer, 5-10 parts of a filler and 1-5 parts of a lubricant; wherein the content of maleic anhydride in the SMA resin is 10-32%. In the PVC / ABS alloy material, the SMA resin with a specific content of maleic anhydride is added, so that the resistance to baking deformation and the dimensional stability of the PVC / ABS alloy material are improved.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a PVC / ABS alloy material, its preparation method, and its application. Background Technology

[0002] Polyvinyl chloride (PVC) resin is one of the most produced and cost-effective general-purpose plastics. Due to the presence of polar chlorine atoms in its structure, PVC has a natural advantage in flame retardancy, making it suitable for many applications requiring high flame retardancy, such as the electronics and electrical industries. However, the glass transition temperature (Tg) of PVC is typically around 80°C, limiting its application in high-temperature environments. Furthermore, PVC has relatively poor impact strength, which restricts its use in commercial applications requiring high heat resistance.

[0003] ABS is a terpolymer of acrylonitrile, butadiene, and styrene, possessing good toughness and processability. However, its low oxygen index and high flammability are major drawbacks. Therefore, PVC / ABS alloying offers complementary advantages: PVC compensates for ABS's lack of flame retardancy, while ABS reduces the processing difficulty and improves PVC's impact resistance. However, PVC / ABS alloys have a high coefficient of linear expansion, generally poor dimensional stability, and are prone to deformation after baking, limiting their application range.

[0004] Therefore, improving the baking resistance and dimensional stability of PVC / ABS alloy materials is a current challenge. Summary of the Invention

[0005] The purpose of this disclosure is to overcome the shortcomings of the prior art and to provide a PVC / ABS alloy material, its preparation method, and its application.

[0006] To address the issues of poor bake resistance and dimensional stability of existing PVC / ABS alloy materials.

[0007] In a first aspect, the present invention provides a PVC / ABS alloy material comprising the following components in parts by weight: 38-62 parts PVC resin, 27-53 parts ABS resin, 8-28 parts SMA resin, 1.5-5.5 parts heat stabilizer, 5-10 parts filler, and 1-5 parts lubricant; wherein the maleic anhydride content in the SMA resin is 10-32%.

[0008] In different embodiments, the weight parts of the PVC resin may be, but are not limited to, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, or 62 parts.

[0009] In different embodiments, the weight parts of the ABS resin may be, but are not limited to, 27 parts, 30 parts, 33 parts, 35 parts, 37 parts, 40 parts, 43 parts, 45 parts, 48 ​​parts, 50 parts, or 53 parts;

[0010] In different embodiments, the weight parts of the SMA resin may be, but are not limited to, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 23 parts, 25 parts, or 28 parts.

[0011] In different embodiments, the heat stabilizer may be present in, but is not limited to, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or 5.5 parts by weight.

[0012] In different embodiments, the weight parts of the filler may be, but are not limited to, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, and 10 parts;

[0013] In different embodiments, the weight parts of the lubricant may be, but are not limited to, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts.

[0014] In different embodiments, the maleic anhydride content in the SMA resin can be, but is not limited to, 10%, 13%, 15%, 18%, 20%, 25%, 30%, or 32%; preferably 15-25%. The testing method is thermal pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS). The specific steps are as follows: take a small amount of sample, add it to the PY-GC-MS device, heat it rapidly in an inert atmosphere to generate pyrolysis products, directly introduce the pyrolysis products into the gas chromatography system for separation, and then enter the mass spectrometer for detection. The content of maleic anhydride is determined by qualitative and quantitative analysis of the characteristic fragment ions after high-temperature pyrolysis.

[0015] This invention improves the heat resistance, bake deformation resistance, and dimensional stability of PVC / ABS alloy materials by adding SMA resin (styrene-maleic anhydride copolymer) with a specific maleic anhydride content. By selecting an optimal SMA with a suitable maleic anhydride content, better compatibility between SMA, which has a low coefficient of linear expansion, and PVC / ABS is achieved, reducing molding shrinkage. Therefore, the resulting PVC / ABS alloy material, which is resistant to heat deformation and has excellent dimensional stability, can achieve minimal deformation after baking at 90°C. This has significant commercial value in applications with strict requirements for heat resistance and dimensional shrinkage. If the maleic anhydride content in the SMA resin is too low, it cannot improve the heat resistance, bake deformation resistance, and dimensional stability of the PVC / ABS alloy material; if the maleic anhydride content in the SMA resin is too high, the compatibility between SMA and PVC deteriorates, and the high melt processing temperature of SMA resin prevents it from being processed with PVC or ABS resins.

[0016] In some embodiments, the degree of polymerization of the PVC resin is 300-800, for example, but not limited to 300, 400, 450, 500, 550, 600, 650, 700, 800, preferably 500-600, and the test method is high-temperature gel permeation chromatography (GPC).

[0017] In this invention, the PVC resin with the above-mentioned degree of polymerization can effectively improve the uniformity of the distribution of each component, thereby improving the baking deformation resistance and dimensional stability of the PVC / ABS alloy material.

[0018] Specifically, the degree of polymerization of the PVC resin is obtained by testing using the following method, with the specific steps as follows:

[0019] The degree of polymerization of the polymer was determined by an Agilent Technologies PL-GPC 220 gel permeation chromatograph with 1,2,4-trichlorobenzene as the eluent at a high temperature of 150°C, using a standard narrow-distribution polystyrene calibration curve.

[0020] In some embodiments, the melt flow rate of the ABS resin is 15-45 g / 10 min (220℃, 10 kg), and the test method refers to the standard GB / T3682.1-2018; the notched impact strength of the ABS resin is 15-45 kJ / m. 2 The test method is based on the standard GB / T 1843-2008.

[0021] In some embodiments, the weight-average molecular weight of the SMA resin is 5-250 kDa, preferably 10-170 kDa, and the test method is high-temperature gel permeation chromatography (GPC).

[0022] In some embodiments, the heat stabilizer is at least one of organotin stabilizers and organoantimony stabilizers.

[0023] Specifically, examples of the organotin stabilizer may be at least one of methyltin maleate, butyltin maleate, octyltin maleate, methyltin mercaptan, butyltin mercaptan, octyltin mercaptan, and dibutyltin laurate.

[0024] Specifically, examples of the organic antimony stabilizer may be at least one of tris(dodecylthio)antimony, tris(n-butyl mercaptoacetate)antimony, pentathiolate antimony, and tris(isooctyl mercaptoacetate)antimony.

[0025] Heat stabilizers can improve the heat distortion temperature of PVC resin and further enhance the heat resistance of PVC / ABS alloy materials.

[0026] In some embodiments, the filler is at least one of calcium carbonate, talc, barium sulfate, and titanium dioxide.

[0027] In some embodiments, the lubricant is at least one of low-molecular-weight ester lubricants, metal soap lubricants, stearic acid complex ester lubricants, and amide lubricants.

[0028] Specifically, low-molecular-weight ester lubricants may be selected from at least one of solid paraffin, liquid paraffin, and low-molecular-weight polyolefin waxes; metal soap lubricants may be selected from at least one of calcium stearate, magnesium stearate, zinc stearate, and barium stearate; stearic acid complex ester lubricants may be selected from at least one of ethylene glycol stearate, glyceryl stearate, and pentaerythritol stearate; and amide lubricants may be selected from at least one of erucamide, methyl bis-stearamide, and N,N-ethylene bis-stearamide.

[0029] Lubricants can improve the fluidity and compatibilize the components of PVC / ABS alloy materials, thereby reducing friction between the components during actual operation and improving the baking deformation resistance and dimensional stability of PVC / ABS alloy materials.

[0030] In some embodiments, the PVC / ABS alloy material further includes 0.1-3 parts by weight of an antioxidant; the antioxidant is at least one of phenolic antioxidants, phosphite antioxidants, divalent sulfur antioxidants, or hindered amine antioxidants.

[0031] Specifically, the phenolic antioxidant may be selected from at least one of antioxidant 264, antioxidant 1010, antioxidant 1076, antioxidant SP, antioxidant 2246, antioxidant CA, antioxidant 330, Irganox 1890, and antioxidant 3114; the phosphite antioxidant may be selected from at least one of antioxidant TNP, antioxidant ODP, antioxidant 168, Irganox 1093, and Irganox 1222; the divalent sulfur antioxidant may be selected from at least one of dilaurate thiodipropionate (DLTP) and distearate thiodipropionate (DSTP); and the hindered amine antioxidant may be selected from at least one of LS-744, LS-770, GW-540, and Flamstab NOR116.

[0032] In the PVC / ABS alloy material of this invention, the total mass of PVC resin and ABS resin is not less than 75%.

[0033] Secondly, a method for preparing the aforementioned PVC / ABS alloy material is provided, comprising the following steps:

[0034] S1: After mixing SMA resin and ABS resin evenly, add them to a screw extruder and melt-extrude and granulate them at a temperature of 200-230℃ to obtain an ABS / SMA composite.

[0035] S2: After the ABS / SMA composite and the remaining components are mixed evenly, they are added to a screw extruder and melt-extruded and granulated at a temperature of 170-190℃ to obtain PVC / ABS alloy material.

[0036] In different embodiments, the temperature of melt extrusion granulation in step S1 can be, but is not limited to, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, or 230°C.

[0037] In different embodiments, the temperature of melt extrusion granulation in step S2 can be, but is not limited to, 170°C, 175°C, 180°C, 185°C, or 190°C.

[0038] The melt extrusion temperature in steps S1 and S2 ensures that all raw materials are in a molten state, facilitating the fusion of the raw materials.

[0039] In some embodiments, in step S2, the mixing temperature is 80-100°C, for example, but not limited to 80°C, 85°C, 90°C, 95°C, or 100°C; and the time is 5-10 minutes, for example, but not limited to 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, or 10 minutes.

[0040] Mixing the ABS / SMA composite and the remaining components at the above temperature and time can improve the mixing effect of the ABS / SMA composite and the remaining components, which is beneficial for subsequent melt extrusion granulation.

[0041] Thirdly, the application of the aforementioned PVC / ABS alloy material in the fields of home appliances, electronics, electrical engineering, and security is provided; for example, electrical control boxes, junction boxes, wall switches, smoke detectors, etc.

[0042] Compared with the prior art, the beneficial effects of this disclosure are as follows: In this invention, SAM resin (styrene-maleic anhydride copolymer) with a specific maleic anhydride content is added to PVC / ABS alloy materials, which improves the baking deformation resistance and dimensional stability of PVC / ABS alloy materials. Detailed Implementation

[0043] To facilitate understanding of this disclosure, a more complete description will be provided below. However, this disclosure may be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure.

[0044] As used in this article:

[0045] "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0046] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0047] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1-5” is disclosed, the described range should be interpreted as including ranges “1-4”, “1-3”, “1-2”, “1-2 and 4-5”, “1-3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0048] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0049] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (K is any number representing a multiplier). It is important to understand that, unlike the number of parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0050] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0051] The raw materials used in the embodiments and comparative examples are described below, but are not limited to these materials:

[0052] PVC Resin-1: Polymerization degree 500, PVC S-50, Ningbo Formosa Plastics Chemical Co., Ltd.

[0053] PVC Resin-2: Degree of polymerization 600, PVC B-57, Formosa Plastics Chemical Co., Ltd., Taiwan;

[0054] PVC Resin-3: Degree of polymerization 700, PVC TL-700, Tianjin LG Chemical;

[0055] PVC Resin-4: Degree of polymerization 400, PVC P400, Xinjiang Zhongtai Chemical;

[0056] ABS resin: ABS KF-730, Liaoning Kingfa Science & Technology Co., Ltd.

[0057] SMA resin-1: Maleic anhydride content is 10%. SZ10010, Polyscope, Netherlands;

[0058] SMA resin-2: Maleic anhydride content is 15%. SZ15170, Polyscope, Netherlands;

[0059] SMA resin-3: Maleic anhydride content is 23%. SZ23110, Polyscope, Netherlands;

[0060] SMA resin-4: Maleic anhydride content is 30%. SZ30010, Polyscope, Netherlands;

[0061] SMA resin-5: Maleic anhydride content is 8%. SZ08250, Polyscope, Netherlands;

[0062] SMA resin-6: Maleic anhydride content is 40%. SZ40005, Polyscope, Netherlands;

[0063] Heat stabilizer: Methyltin mercaptan, commercially available;

[0064] Lubricant: A compound of oxidized polyethylene wax and polyethylene wax in a 1:1 mass ratio, both of which are commercially available;

[0065] Filler: A mixture of titanium dioxide and calcium carbonate in a mass ratio of 2:1, both of which are commercially available;

[0066] Antioxidant: Antioxidant 1010, commercially available.

[0067] Examples and Comparative Examples

[0068] The composition and weight parts of the PVC / ABS alloy materials described in the examples and comparative examples are shown in Tables 1-2.

[0069] The preparation method of the PVC / ABS alloy material described in the examples and comparative examples includes the following steps:

[0070] S1: After mixing SMA resin and ABS resin evenly, add them to a twin-screw extruder and melt-extrude and granulate at a temperature of 200-230℃ to obtain an ABS / SMA composite.

[0071] S2: Mix the ABS / SMA composite and the remaining components at 90℃ and 800rpm for 10min. Add the resulting premix to a twin-screw extruder and melt-extrude and granulate at 170-190℃ to obtain PVC / ABS alloy material.

[0072] Table 1

[0073]

[0074] Table 2

[0075]

[0076]

[0077] Performance testing

[0078] The PVC / ABS alloy materials obtained in the examples and comparative examples were subjected to performance tests, and the test methods are as follows:

[0079] (1) Heat resistance: The Vicat softening point of PVC / ABS alloy materials was tested according to B50 in ISO 306-2022;

[0080] (2) Baking resistance to deformation: The PVC / ABS alloy materials obtained in the examples and comparative examples were injection molded into the same box parts. The cooled boxes were placed in an oven at 90°C for 24 hours. After natural cooling, the box parts were taken out and the maximum deformation in the horizontal and vertical directions of the box parts was measured and recorded as the 90°C baking deformation.

[0081] (3) Molding shrinkage rate: The molding shrinkage rate of PVC / ABS alloy materials at 23℃ was tested according to GB / T 15585-1995.

[0082] The test results are shown in Table 3.

[0083] Table 3

[0084]

[0085]

[0086] As shown in Table 3, the thermal deformation of the PVC / ABS alloy material of the present invention after baking at 90℃ for 24 hours is ≤5mm and the molding shrinkage rate is ≤0.4%, indicating that the PVC / ABS alloy material of the present invention has good resistance to baking deformation and dimensional stability.

[0087] As can be seen from Examples 1 and 4-6, when the degree of polymerization of PVC resin is 500-600, the heat deformation of the obtained PVC / ABS alloy material after baking at 90°C for 24 hours is ≤4.5mm, indicating that when the degree of polymerization of PVC resin is 500-600, the PVC / ABS alloy material has better resistance to baking deformation.

[0088] As can be seen from Examples 1, 7-9 and Comparative Examples 1-2, when the maleic anhydride content in the SMA resin is 15-25%, the heat deformation of the obtained PVC / ABS alloy material after baking at 90°C for 24 hours is ≤4.2mm, indicating that when the maleic anhydride content in the SMA resin is 15-25%, the PVC / ABS alloy material has better resistance to baking deformation.

[0089] As can be seen from Examples 1, 10-13 and Comparative Examples 3-5, when the weight part of SMA resin is 12-25, the heat deformation of the obtained PVC / ABS alloy material after baking at 90°C for 24 hours is ≤4.3mm, indicating that when the weight part of SMA resin is 12-25, the PVC / ABS alloy material has better resistance to baking deformation.

[0090] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of this disclosure and not to limit the scope of protection of this disclosure. Although this disclosure 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 this disclosure without departing from the substance and scope of the technical solutions of this disclosure.

Claims

1. A PVC / ABS alloy material, characterized in that, It includes the following components by weight: 38-60 parts PVC resin, 30-53 parts ABS resin, 8-28 parts SMA resin, 1.5-5.5 parts heat stabilizer, 5-10 parts filler, and 1-5 parts lubricant; wherein the maleic anhydride content in the SMA resin is 10-32%.

2. The PVC / ABS alloy material as described in claim 1, characterized in that, The maleic anhydride content in the SMA resin is 15-25%.

3. The PVC / ABS alloy material as described in claim 1, characterized in that, The degree of polymerization of the PVC resin is 300-800.

4. The PVC / ABS alloy material as described in claim 1, characterized in that, The heat stabilizer is at least one of organotin stabilizers and organoantimony stabilizers.

5. The PVC / ABS alloy material as described in claim 1, characterized in that, The filler is at least one of calcium carbonate, talc, barium sulfate, and titanium dioxide.

6. The PVC / ABS alloy material as described in claim 1, characterized in that, The lubricant is at least one of the following: low molecular weight ester lubricant, metal soap lubricant, stearic acid complex ester lubricant, and amide lubricant.

7. The PVC / ABS alloy material as described in claim 1, characterized in that, The PVC / ABS alloy material further includes 0.1-3 parts by weight of antioxidant; the antioxidant is at least one of phenolic antioxidants, phosphite antioxidants, divalent sulfur antioxidants or hindered amine antioxidants.

8. A method for preparing the PVC / ABS alloy material as described in any one of claims 1-7, characterized in that, Includes the following steps: S1: After mixing SMA resin and ABS resin evenly, add them to a screw extruder and melt-extrude and granulate them at a temperature of 200-230℃ to obtain an ABS / SMA composite. S2: After the ABS / SMA composite and the remaining components are mixed evenly, they are added to a screw extruder and melt-extruded and granulated at a temperature of 170-190℃ to obtain PVC / ABS alloy material.

9. The method for preparing the PVC / ABS alloy material as described in claim 8, characterized in that, In step S2, the mixing temperature is 80-100℃ and the time is 5-10 minutes.

10. The application of the PVC / ABS alloy material as described in any one of claims 1-7 in the fields of home appliances, electronic and electrical engineering, and security.

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