PVC / ABS (polyvinyl chloride / acrylonitrile-butadiene-styrene) alloy material as well as preparation method and application thereof

Abstract

The invention provides a PVC / ABS (polyvinyl chloride / acrylonitrile-butadiene-styrene) alloy material as well as a preparation method and application thereof, and belongs to the technical field of high polymer materials. The PVC / ABS alloy material is prepared from the following components in parts by weight: 38 to 62 parts of PVC resin, 27 to 53 parts of ABS resin, 8 to 28 parts of SMA resin, 1.5 to 5.5 parts of heat stabilizer, 5 to 10 parts of filler and 1 to 5 parts of lubricant, wherein the content of maleic anhydride in the SMA resin is 10-32%. According to the PVC / ABS alloy material, the SAM resin with specific maleic anhydride content is added into the PVC / ABS alloy material, so that the baking deformation resistance and the dimensional stability of the PVC / ABS alloy material are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to a PVC / ABS alloy material, a preparation method thereof and an application thereof. Background Art

[0002] Polyvinyl chloride (PVC) resin is one of the general plastics with a relatively high production volume and cost performance at present. Due to the presence of polar chlorine atoms in its structure, PVC has an inherent advantage in flame retardancy, and thus can be applied to many scenarios requiring high flame retardancy, such as the electronic and electrical industries. However, the glass transition temperature (Tg) of PVC material itself is usually around 80 °C, which limits its application in high-temperature environments, and the impact strength of PVC material is poor, which is restricted in commercial applications with high heat resistance requirements.

[0003] ABS is a terpolymer of acrylonitrile-butadiene-styrene, with good toughness and processability. However, the low oxygen index of ABS material itself and its extremely easy combustion are major drawbacks of ABS. Therefore, alloying of PVC / ABS can achieve complementary advantages. On the one hand, PVC can make up for the shortcoming of the flame retardancy of ABS material, and on the other hand, ABS can reduce the processing difficulty of PVC and improve the impact resistance of PVC. However, the linear expansion coefficient of PVC / ABS alloy is relatively large, the dimensional stability is general, and it is prone to deformation after baking, which hinders the application range of PVC / ABS alloy.

[0004] Therefore, how to improve the baking resistance and dimensional stability of PVC / ABS alloy materials is a difficult problem to be solved at present. Summary of the Invention

[0005] The purpose of the present disclosure is to overcome the deficiencies of the prior art and provide a PVC / ABS alloy material, a preparation method thereof and an application thereof.

[0006] In order to solve the problems of poor baking resistance and dimensional stability of PVC / ABS alloy materials in the prior art.

[0007] In the first aspect of the present invention, a PVC / ABS alloy material is provided, which 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 heat stabilizer, 5-10 parts of filler, 1-5 parts of lubricant; wherein, the maleic anhydride content in the SMA resin is 10-32%.

[0008] In different embodiments, the parts by weight of the PVC resin can 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, 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, 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, 28 parts;

[0011] In different embodiments, the weight parts of the heat stabilizer may be, but are not limited to, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts;

[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, 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, 5 parts.

[0014] In different embodiments, the maleic anhydride content in the SMA resin may be, but are not limited to, 10%, 13%, 15%, 18%, 20%, 25%, 30%, 32%; preferably 15 - 25%, and its test method is 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 equipment, quickly heat it 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] In the PVC / ABS alloy material of the present invention, an SMA resin (styrene-maleic anhydride copolymer) with a specific maleic anhydride content is added, which improves the baking deformation resistance and dimensional stability of the PVC / ABS alloy material. By preferably selecting an SMA with a suitable maleic anhydride content, the SMA with a lower linear expansion coefficient has better compatibility with PVC / ABS, reducing the molding shrinkage rate. Therefore, the PVC / ABS alloy material with baking deformation resistance and dimensional stability can achieve extremely small deformation after baking at 90 °C and relatively excellent dimensional stability. It has significant commercial value in application scenarios with strict requirements for heat-resistant baking deformation and dimensional shrinkage rate. If the maleic anhydride content in the SMA resin is low, it cannot play a role in improving the heat resistance, baking deformation resistance and dimensional stability of the PVC / ABS alloy material; if the maleic anhydride content in the SMA resin is high, it will lead to poor compatibility between SMA and PVC, and the melting processing temperature of the SMA resin is high, so it cannot be processed and formed with PVC resin and ABS resin.

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

[0017] In the present invention, the PVC resin with the above degree of polymerization can effectively improve the distribution uniformity 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 the following test method. The specific steps are as follows:

[0019] The degree of polymerization of the polymer is measured by an Agilent Technologies gel permeation chromatograph PL-GPC 220 using 1,2,4-trichlorobenzene as the eluent solvent at a high temperature of 150 °C, and calibrated with 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 °C, 10 kg), and its test method reference standard is GB / T3682.1-2018; the notched impact strength of the ABS resin is 15-45 kJ / m 2 , and its test method reference standard is 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 its test method is the high-temperature gel permeation chromatography (GPC) method.

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

[0023] Specifically, examples of the organotin stabilizer may be at least one of methyl tin maleate, butyl tin maleate, octyl tin maleate, methyl mercaptan tin, butyl mercaptan tin, octyl mercaptan tin, and dibutyl tin laurate.

[0024] Specifically, examples of the organoantimony stabilizer may be at least one of tris(dodecyl mercaptan)antimony, tris(n-butyl mercaptoacetate)antimony, pentathiol antimony, and tris(isooctyl mercaptoacetate)antimony.

[0025] The heat stabilizer can improve and increase the heat distortion temperature of the PVC resin, and further improve the heat resistance of the PVC / ABS alloy material.

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

[0027] In some embodiments, the lubricant is at least one of a low molecular weight lipid lubricant, a metal soap lubricant, a stearic acid composite ester lubricant, and an amide lubricant.

[0028] Specifically, the low molecular weight lipid lubricant may be selected from at least one of solid paraffin, liquid paraffin, and low molecular weight polyolefin wax; the metal soap lubricant may be selected from at least one of calcium stearate, magnesium stearate, zinc stearate, and barium stearate; the stearic acid composite ester lubricant may be selected from at least one of ethylene glycol stearate, glycerol stearate, and pentaerythritol stearate; and the amide lubricant may be selected from at least one of erucic acid amide, methylene bisstearic acid amide, and N,N-ethylene bisstearic acid amide.

[0029] The lubricant can improve the fluidity and compatibilizer between the components of the PVC / ABS alloy material, reduce the friction between the components during the actual operation process, and thus achieve the effect of improving the baking deformation resistance and dimensional stability of the PVC / ABS alloy material.

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

[0031] Specifically, the phenolic antioxidant can be selected from at least one of antioxidant 264, antioxidant 1010, antioxidant 1076, antioxidant SP, antioxidant 2246, antioxidant CA, antioxidant 330, Irganox1890, and antioxidant 3114; the phosphite antioxidant can be selected from at least one of antioxidant TNP, antioxidant ODP, antioxidant 168, Irganox1093, and Irganox1222; the divalent sulfur antioxidant can be selected from at least one of dilauryl thiodipropionate (DLTP) and distearyl thiodipropionate (DSTP); the hindered amine antioxidant can be selected from at least one of LS-744, LS-770, GW-540, and Flamstab NOR116.

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

[0033] In a second aspect, a method for preparing the PVC / ABS alloy material is provided, including the following steps:

[0034] S1: After uniformly mixing the SMA resin and the ABS resin, add them into a screw extruder and melt-extrude and pelletize at a temperature of 200 - 230 °C to obtain an ABS / SMA composite;

[0035] S2: After uniformly mixing the ABS / SMA composite and the remaining components, add them into a screw extruder and melt-extrude and pelletize at a temperature of 170 - 190 °C to obtain the PVC / ABS alloy material.

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

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

[0038] The melt-extrusion temperatures in step S1 and step S2 ensure that each raw material is in a molten state, facilitating the mutual fusion of the raw materials.

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

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

[0041] In a third aspect, there is provided an application of the described PVC / ABS alloy material in the fields of household appliances, electronics and electrical engineering, electronic and electrical engineering, and security; for example, electric control boxes, junction boxes, wall switches, smoke alarms, etc.

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

[0043] To facilitate the understanding of the present disclosure, the present disclosure will be described more comprehensively below. However, the present disclosure can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosed content of the present disclosure more thorough and comprehensive.

[0044] As used herein, the terms:

[0045] "Prepared from..." is synonymous with "comprising". As used herein, the terms "comprising", "including", "having", "containing" or any other variation thereof are intended to cover non-exclusive inclusion. For example, a composition, step, method, article or device containing 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 device.

[0046] The connecting word "consisting of" excludes any unstated element, step or component. If used in a claim, this phrase will render the claim closed, excluding materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the claim body rather than immediately following the subject, it only limits the elements described in that clause; other elements are not excluded from the claim as a whole.

[0047] When an equivalent, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values and lower preferred values, this should be understood to specifically disclose all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit 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 to include ranges such as "1-4", "1-3", "1-2", "1-2 and 4-5", "1-3 and 5", etc. When a numerical range is described herein, unless otherwise stated, the range is intended to include its end values and all integers and fractions within the range.

[0048] In these examples, unless otherwise specified, the parts and percentages are by mass.

[0049] "Parts by mass" refers to the basic measurement unit representing the mass ratio relationship of multiple components. 1 part can represent any unit mass, such as 1 g or 2.689 g, etc. If we say that the mass of component A is a parts by mass and the mass of component B is b parts by mass, it means the mass ratio of component A to component B is a:b. Or, it means the mass of component A is aK and the mass of component B is bK (K is any number representing a multiple factor). It should not be misunderstood that, different from the number of parts by mass, the sum of the parts by mass of all components is not limited to 100 parts.

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

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

[0052] PVC Resin - 1: Degree of polymerization 500, PVC S - 50, Ningbo Formosa Plastics Chemical Industry;

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

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

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

[0056] ABS Resin: ABS KF - 730, Liaoning Kingfa Technology;

[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: Mercaptomethyltin, commercially available;

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

[0065] Filler: A compound of titanium dioxide and calcium carbonate with a mass ratio of 2:1, both titanium dioxide and calcium carbonate 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 in the examples and comparative examples are shown in Table 1 - 2.

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

[0070] S1: After mixing the SMA resin and the ABS resin evenly, add them into a twin - screw extruder and melt - extrude and pelletize at a temperature of 200 - 230 °C to obtain an ABS / SMA composite;

[0071] S2: Mix the ABS / SMA composite and the remaining components for 10 min under the conditions of a temperature of 90 °C and a rotation speed of 800 rpm. Add the obtained premix into a twin - screw extruder and melt - extrude and pelletize at a temperature of 170 - 190 °C to obtain the PVC / ABS alloy material.

[0072] Table 1

[0073]

[0074] Table 2

[0075]

[0076]

[0077] Performance test

[0078] The PVC / ABS alloy materials obtained from 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 the PVC / ABS alloy material was tested according to B50 in ISO 306-2022;

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

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

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

[0083] Table 3

[0084]

[0085]

[0086] As can be seen from Table 3, the thermal deformation amount of the PVC / ABS alloy material of the present invention after baking at 90 °C for 24 h is ≤5 mm, 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 the PVC resin is 500-600, the thermal deformation amount of the obtained PVC / ABS alloy material after baking at 90 °C for 24 h is ≤4.5 mm, indicating that when the degree of polymerization of the PVC resin is 500-600, the PVC / ABS alloy material has better resistance to baking deformation.

[0088] It can be seen from Example 1, Examples 7-9 and Comparative Examples 1-2 that when the maleic anhydride content in the SMA resin is 15-25%, the thermal deformation of the obtained PVC / ABS alloy material after baking at 90°C for 24 h is ≤ 4.2 mm, 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] It can be seen from Example 1, Examples 10-13 and Comparative Examples 3-5 that when the weight part of the SMA resin is 12-25, the thermal deformation of the obtained PVC / ABS alloy material after baking at 90°C for 24 h is ≤ 4.3 mm, indicating that when the weight part of the 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 the present disclosure rather than to limit the protection scope of the present disclosure. Although the present disclosure has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present disclosure can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present disclosure.

Claims

1. A PVC / ABS alloy material, characterized in that: The invention 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 heat stabilizer, 5-10 parts of filler and 1-5 parts of lubricant; wherein the content of maleic anhydride in the SMA resin is 10-32%.

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

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

4. The PVC / ABS alloy material according to claim 1, characterized in that: The heat stabilizer is at least one of an organic tin stabilizer and an organic antimony stabilizer.

5. The PVC / ABS alloy material according to claim 1, characterized in that: The filler is at least one of calcium carbonate, talcum powder, barium sulfate and titanium dioxide.

6. The PVC / ABS alloy material according to claim 1, characterized in that: The lubricant is at least one of a low molecular weight lipid lubricant, a metal soap lubricant, a stearic acid complex ester lubricant, and an amide lubricant.

7. The PVC / ABS alloy material according to claim 1, characterized in that: The PVC / ABS alloy material further comprises 0.1-3 parts by weight of an antioxidant; the antioxidant is at least one of a phenolic antioxidant, a phosphite antioxidant, a divalent sulfur antioxidant or a hindered amine antioxidant.

8. A method for preparing the PVC / ABS alloy material according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1: After the SMA resin and the ABS resin are evenly mixed, they are added into a screw extruder, and melt-extruded and granulated at a temperature of 200-230°C to obtain an ABS / SMA composite; S2: After the ABS / SMA compound and the remaining components are uniformly mixed, they are added into a screw extruder, and melt-extruded and granulated at a temperature of 170-190° C. to obtain a PVC / ABS alloy material.

9. The method for preparing the PVC / ABS alloy material according to claim 8, characterized in that: In step S2, the mixing temperature is 80-100° C. and the mixing time is 5-10 min.

10. Application of the PVC / ABS alloy material according to any one of claims 1 to 7 in the fields of household appliances, electronic and electrical engineering, and security.

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