WO2022121330A1 - Pvc料及其制备方法 - Google Patents

Pvc料及其制备方法 Download PDF

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WO2022121330A1
WO2022121330A1 PCT/CN2021/108869 CN2021108869W WO2022121330A1 WO 2022121330 A1 WO2022121330 A1 WO 2022121330A1 CN 2021108869 W CN2021108869 W CN 2021108869W WO 2022121330 A1 WO2022121330 A1 WO 2022121330A1
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pvc material
parts
pvc
stabilizer
plasticizer
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PCT/CN2021/108869
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English (en)
French (fr)
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王超
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长春捷翼汽车零部件有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • the invention relates to the technical field of polymer materials, in particular to a high-performance, environment-friendly and low-temperature impact-resistant PVC material and a preparation method thereof.
  • PVC material is a kind of cable material prepared by using polyvinyl chloride as raw material, introducing various additives such as plasticizers, stabilizers, flame retardants, fillers, etc., through blending, extrusion granulation, etc.
  • various additives such as plasticizers, stabilizers, flame retardants, fillers, etc.
  • the requirements for cable performance are getting higher and higher, especially if it meets the requirements of EU ROHS and other requirements to enter, there are many additives in traditional cable materials, which not only leads to an increase in production processes, an increase in production costs, and a reduction in production costs.
  • Production efficiency the inclusion of harmful auxiliaries can also pose a hazard to the health of the producer.
  • the purpose of the present invention is to provide a PVC material and a preparation method thereof.
  • the PVC material has both excellent high temperature thermal stability and low temperature impact resistance.
  • the present invention provides a PVC material, in parts by weight, the raw materials of the PVC material include: 90-120 parts of PVC resin, 20-50 parts of plasticizer, 5-10 parts of stabilizer, flame retardant wherein, the plasticizer is trioctyl trimellitate, the filler is heavy calcium carbonate, and the stabilizer is calcium zinc stabilizer.
  • the PVC material can have good low-temperature impact resistance.
  • the plasticizer and stabilizer can improve the thermal stability of the PVC material, and by adding an appropriate stabilizer, the volatilization of the plasticizer can be slowed down and the stability of the prepared PVC material can be improved.
  • the mass ratio of the plasticizer to the stabilizer can be controlled to be (4-6):(1-2), for example, the mass ratio of the plasticizer to the stabilizer can be controlled to be 5:1.
  • the mass ratio of the plasticizer and the filler can be controlled to be 8:(1-3).
  • the plasticizer is preferably a trioctyl trimellitate (TOTM) environmentally friendly plasticizer, and the trioctyl trimellitate plasticizer is beneficial to improve the low-temperature impact resistance of the PVC material .
  • TOTM trioctyl trimellitate
  • the trioctyl trimellitate used in the present invention meets the EU standard, is environmentally friendly, has no pollution, and is conducive to the expansion of PVC sales and application range of the material.
  • the stabilizer plays an internal lubricating role in the PVC material.
  • the use of calcium-zinc stabilizer as the stabilizer can improve the low temperature impact resistance of the PVC material, and at the same time improve the processing performance and thermal stability of the PVC material.
  • the calcium-zinc stabilizer generally comprises a zinc stearate-type calcium-zinc stabilizer, and the mass content of zinc stearate in the zinc-stearate-type calcium-zinc stabilizer is at least 10%.
  • selecting heavy calcium carbonate as the filler can enhance the low-temperature impact resistance of the PVC material while enhancing the mechanical strength of the PVC material and reducing the material cost.
  • the particle size of the ground calcium carbonate may be 2500-3000 mesh (preferably 2800 mesh), and the mass proportion of calcium carbonate in the ground calcium carbonate is generally greater than 80%.
  • the raw materials of the PVC material may include: 90-120 parts of PVC resin, 20-50 parts of plasticizer (for example, 30-50 parts), 5-10 parts of stabilizer, 2-8 parts of flame retardant, and 5 parts of filler. share.
  • the average degree of polymerization of the PVC resin is 1250-1350.
  • the flame retardant is a Sb 2 O 3 type flame retardant, and the mass proportion of the active ingredients of the flame retardant is greater than 82%.
  • the flame retardant may be a flame retardant comprising Sb 2 O 3 , and the mass proportion of the Sb 2 O 3 is generally greater than 55%, and has good flame retardant performance.
  • the present invention also provides the preparation method of the above-mentioned PVC material, which comprises:
  • Step 1 blending PVC resin and plasticizer to obtain a first mixture
  • Step 2 adding stabilizer, flame retardant and filler to the first mixture for blending to obtain a second mixture;
  • Step 3 extruding and granulating the second mixture to obtain the PVC material.
  • the blending time is generally controlled to be 2min-6min (for example, 2min) to increase the compatibility between the PVC resin and the plasticizer.
  • the blending time in step 2, can also be controlled to 2min-6min (for example, 2min) to increase the compatibility between the raw materials.
  • the extrusion temperature can be controlled to be 140-180°C (for example, 140°C-170°C, 170°C-180°C, specifically 140°C, 170°C) °C, 180 °C, etc.), the device used for extrusion granulation can be a twin-screw extruder.
  • the third step may include cutting the molded PVC material into a standard test strip.
  • the preparation method of the above-mentioned PVC material can include:
  • Step 1 the PVC resin and the plasticizer are blended for 2min-6min to obtain the first mixture;
  • Step 2 adding stabilizer, flame retardant and filler to the first mixture and blending for 2min-6min to obtain a second mixture;
  • Step 3 put the second mixture into a twin-screw extruder, extrude and granulate at 140-180°C (eg, 140°C, 170°C, 180°C), and then obtain the PVC material; During the test, the molded PVC material was cut into standard experimental strips.
  • 140-180°C eg, 140°C, 170°C, 180°C
  • the preparation method provided by the present invention enables the prepared PVC material to have both excellent high temperature thermal stability and low temperature impact resistance by selecting suitable raw material components and controlling the proportions between the components, and the lowest low temperature impact resistance temperature can reach -70°C, far better than the low-temperature impact resistance of conventional PVC materials.
  • Figure 1 is a photo of the PVC material prepared in Example 1.
  • FIG. 2 is a photograph of the PVC material prepared in Comparative Example 8.
  • FIG. 2 is a photograph of the PVC material prepared in Comparative Example 8.
  • FIG. 3 is a photograph of the PVC material prepared in Comparative Example 9.
  • FIG. 3 is a photograph of the PVC material prepared in Comparative Example 9.
  • the manufacturer of the heavy calcium carbonate used in the following experiments is Guangzhou Bangyou Powder Co., Ltd.
  • the present embodiment provides a preparation method of PVC material, which comprises the following steps:
  • This embodiment provides a preparation method of PVC material, which is basically the same as the preparation method of Example 1, except that in this embodiment, the weight of 2 heavy calcium carbonate is increased to 15 parts, and the obtained PVC material is Denoted as sample B.
  • This embodiment provides a preparation method of PVC material, which is basically the same as the preparation method of Example 1, the only difference is that in this embodiment, the weight of heavy calcium carbonate is increased to 17 parts, and the obtained PVC material is recorded as for sample C.
  • This embodiment provides a preparation method of PVC material, which is basically the same as the preparation method of Example 1, except that in this embodiment, the weight of heavy calcium carbonate is increased to 20 parts, and the obtained PVC material is recorded as for sample D.
  • This comparative example provides a preparation method of PVC material, which is basically the same as the preparation method of Example 1, except that no filler is added in this comparative example, and the obtained PVC material is recorded as sample E.
  • This comparative example provides a preparation method of PVC material, which is basically the same as the preparation method of Example 1, except that this comparative example uses 5 parts of kaolin instead of 5 parts of heavy calcium carbonate as filler, and the obtained PVC material is recorded as for sample F.
  • This comparative example provides a preparation method of PVC material, which is basically the same as the preparation method of Example 1, except that in this comparative example, 5 parts of calcined kaolin is replaced by 5 parts of heavy calcium carbonate as filler, and the obtained PVC material is Denoted as sample G.
  • This comparative example provides a preparation method of PVC material, which is basically the same as the preparation method of Example 1, except that this comparative example uses 8 parts of barium-zinc stabilizer instead of 8 parts of calcium-zinc stabilizer as the stabilizer.
  • the PVC material is recorded as sample H.
  • This comparative example provides a preparation method of PVC material, which is basically the same as the preparation method of Example 4, the only difference is that this comparative example uses 8 parts of barium-zinc stabilizer instead of 8 parts of calcium-zinc stabilizer as the stabilizer.
  • the PVC material is recorded as sample I.
  • This comparative example provides a preparation method of PVC material, which is basically the same as the preparation method of Example 2, the only difference is that this comparative example uses 40 parts of epoxidized soybean oil instead of 40 parts of TOTM as a plasticizer, and the obtained PVC The material is recorded as sample J.
  • This comparative example provides a preparation method of PVC material, which is basically the same as the preparation method of Example 2, except that 25 parts of TOTM and 15 parts of epoxidized soybean oil are used in this comparative example to replace the 40 parts used in Example 2 TOTM was used as a plasticizer, and the obtained PVC material was recorded as sample K.
  • thermal stability test is carried out in accordance with ISO 182-1 standard, which includes: put 5mg granular sample in the test tube to the lower marked level, then put PH test paper with a width of 5mm in the test tube, and then plug the test tube with cotton . Put it into a beaker filled with 200°C silicone oil, and start timing, accurate to the minute.
  • the thermal stabilization time is the time elapsed when the lower edge of the test strip begins to change color.
  • the low temperature impact test is carried out according to the test method specified in GBT5470 "Determination of Embrittlement Temperature of Plastics by Impact Method", using the A instrument in GBT5470. Thermal stability and low temperature impact test results are summarized in Table 1.
  • Example 2 Comparing the performance results of Example 1 with Comparative Example 4, Example 4 and Comparative Example 5, it can be seen that compared with the barium-zinc stabilizer, the PVC material prepared with the calcium-zinc stabilizer has a lower low temperature resistance shock temperature. This result shows that the selection of specific types of calcium and zinc stabilizers is beneficial to improve the low temperature impact resistance of PVC materials.
  • the preparation method of the PVC material provided by the present invention can obtain both excellent thermal stability and low temperature resistance by controlling the type selection and dosage of each component in the raw material, and the low temperature impact resistance temperature of the PVC material can be It can reach -55°C to -70°C, which is far better than the low-temperature impact resistance of conventional PVC materials.
  • This comparative example provides a preparation method of PVC material, wherein, in parts by weight, the raw materials of PVC material include: 100 parts of PVC resin, 8 parts of calcium zinc stabilizer, 5 parts of flame retardant, TOTM plasticizer and heavyweight There are 45 parts of calcium carbonate in total, and the mass ratio of TOTM plasticizer and heavy calcium carbonate is 2:1.
  • the process of preparing and processing the PVC material with the above-mentioned raw materials is the same as that in Example 1, and the obtained PVC material is recorded as sample L.
  • sample L The thermal stability and low temperature impact tests were carried out on sample L, and the test methods were the same as those of samples A-K.
  • the thermal stability of sample L was finally measured to be 220 min, and the low-temperature impact resistance showed fracture at -40 °C.
  • This comparative example provides a preparation method of PVC material, wherein, in parts by weight, the raw materials of PVC material include: 100 parts of PVC resin, 8 parts of calcium zinc stabilizer, 5 parts of flame retardant, 5 parts of heavy calcium carbonate, TOTM plasticizer and calcium-zinc stabilizer totaled 48 parts, and the mass ratio of TOTM plasticizer and calcium-zinc stabilizer was 15:1.
  • the process of preparing the PVC material with the above-mentioned raw materials is the same as that in Example 1, and the obtained PVC material is recorded as sample M.
  • sample M The thermal stability and low temperature impact tests were carried out on sample M, and the test methods were the same as those of samples A-K.
  • the thermal stability of sample M was finally measured to be 37 min, and the low temperature impact resistance temperature was -45 °C.
  • Fig. 1-Fig. 3 are respectively the photos of the PVC material processed in Example 1, Comparative Example 8 and Comparative Example 9. It can be seen from the comparison that after the same processing process, the surface of Sample A processed in Example 1 is flat. , smooth, while the surface of sample L and sample M obtained by comparative example 8 and comparative example 9 have wrinkles and uneven distribution.
  • This comparison result shows that the present invention can improve the processing performance of the PVC material by controlling the composition and the effective ratio between the raw materials in the PVC material, and the obtained PVC material has a smooth and uniform surface, which is beneficial to the practical application of the PVC material. effective functioning.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

一种PVC料及其制备方法，该PVC料的原料包括：PVC树脂，增塑剂，稳定剂，阻燃剂，填料；其中，该增塑剂为偏苯三甲酸三辛酯，该填料为重质碳酸钙，该稳定剂为钙锌稳定剂。该PVC料环保、无污染，并且兼具优异的高温热稳定性和低温抗冲击性。

Description

PVC料及其制备方法 技术领域
本发明涉及高分子材料技术领域，尤其涉及一种高性能、环保且低温抗冲击的PVC料及其制备方法。
背景技术
PVC料随着通信产业的发展开辟了广阔的应用前景。PVC料是用聚氯乙烯作为原材料，引入增塑剂、稳定剂、阻燃剂、填料等各种助剂，经过共混、挤出造粒等工艺制备而成的一种线缆料，随着全球市场化的不断发展，对线缆性能要求越来越高，尤其是需要符合欧盟ROHS等要求才可以进入，传统线缆料内助剂繁多，不仅导致生产工序增加，生产成本增加，降低了生产效率，包含的有害助剂还会对生产者健康造成危害。
发明内容
为了解决上述问题，本发明的目的在于提供一种PVC料及其制备方法。该PVC料兼具优异的高温热稳定性和低温抗冲击性。
为了达到上述目的，本发明提供了一种PVC料，以重量份计，该PVC料的原料包括：PVC树脂90-120份，增塑剂20-50份，稳定剂5-10份，阻燃剂2-8份，填料5-30份；其中，所述增塑剂为偏苯三甲酸三辛酯，所述填料为重质碳酸钙，所述稳定剂为钙锌稳定剂。
在上述PVC料中，通过选择合适的增塑剂种类、稳定剂种类和填料种类，并控制原料中各成分的配比，能够使PVC料具有良好的低温抗冲击性能。
在上述PVC料中，所述增塑剂和稳定剂能够提高PVC料的热稳定性，通过加入适当稳定剂，可以减缓增塑剂的挥发，提高制备得到的PVC料的稳定性。所述增塑剂与所述稳定剂的质量比可以控制为(4-6)：(1-2)，例如可以将增塑剂与稳定剂的质量比控制为5:1。
在上述PVC料中，通过控制所述增塑剂和填料的有效配比，可以改善PVC料的硬度和流变性能，进而提高PVC料的低温抗冲击性。在一些实施方案中，所述增塑剂和填料的质量比可以控制为8:(1-3)。
在上述PVC料中，所述增塑剂优选采用偏苯三甲酸三辛酯类(TOTM)环保增塑剂，该偏苯三甲酸三辛酯增塑剂有利于提高PVC料的低温抗冲击性。此外，相比于目前常用但不符合欧盟标准的邻苯二甲酸二辛酯增塑剂，本发明采用的偏苯三甲酸三辛酯符合 欧盟标准，且对环境友好、无污染，利于扩大PVC料的销路和应用范围。
在上述PVC料中，所述稳定剂在所述PVC料中起到内润滑作用。选用钙锌稳定剂作为稳定剂可以提升所述PVC料的低温抗冲击性，同时还能提高所述PVC料的加工性能和热稳定性。所述钙锌稳定剂一般包含硬脂酸锌类钙锌稳定剂，所述硬脂酸锌类钙锌稳定剂中硬脂酸锌的质量含量至少是10％。
在上述PVC料中，选用重质碳酸钙作为填料可以在加强所述PVC料的机械强度且降低材料成本的同时、提升所述PVC料的低温抗冲击性。所述重质碳酸钙的粒径可以是2500-3000目(优选2800目)，所述重质碳酸钙中碳酸钙的质量占比一般大于80％。
在上述PVC料中，在原料的其他成分用量保持不变的情况下，适当降低重质碳酸钙在原料中的用量可以进一步提升所述PVC料的低温抗冲击性。例如，所述PVC料的原料可以包括：PVC树脂90-120份，增塑剂20-50份(例如30-50份)，稳定剂5-10份，阻燃剂2-8份，填料5份。
在上述PVC料中，优选地，所述PVC树脂的平均聚合度为1250-1350。
在上述PVC料中，优选地，所述阻燃剂为Sb 2O 3类阻燃剂，所述阻燃剂的有效成分的质量占比大于82％。在一些具体实施方案中，所述阻燃剂可以是包含Sb 2O 3的阻燃剂、所述Sb 2O 3的质量占比一般大于55％，具有较好的阻燃性能。
本发明还提供了上述PVC料的制备方法，其包括：
步骤一，将PVC树脂和增塑剂共混，得到第一混合物；
步骤二，向所述第一混合物中加入稳定剂、阻燃剂和填料共混，得到第二混合物；
步骤三，将所述第二混合物挤出造粒，得到所述PVC料。
在本发明的具体实施方案中，步骤一中，所述共混的时间一般控制为2min-6min(例如2min)，以增加所述PVC树脂和所述增塑剂之间的相容性。
在本发明的具体实施方案中，步骤二中，所述共混的时间也可以控制为2min-6min(例如2min)，以增加各原料之间的相容性。
在本发明的具体实施方案中，步骤三中，所述挤出的温度可以控制为140-180℃(例如控制为140℃-170℃、170℃-180℃，具体可以控制为140℃、170℃、180℃等)，挤出造粒采用的装置可以是双螺杆挤出机。
在本发明的具体实施方案中，当需要对所述PVC料进行性能测试时，所述步骤三可以包括将模压成型后的PVC料裁剪成标准的实验样条。
在本发明的具体实施方案中，上述PVC料的制备方法可以包括：
步骤一，将PVC树脂和所述增塑剂共混2min-6min，得到第一混合物；
步骤二，向所述第一混合物中加入稳定剂、阻燃剂和填料共混2min-6min，得到第二混合物；
步骤三，将所述第二混合物放入双螺杆挤出机中，在140-180℃(例如140℃、170℃、180℃)挤出造粒，然后得到所述PVC料；当需要进行性能测试时，将模压成型后的PVC料裁剪成标准的实验样条。
本发明的有益效果在于：
本发明提供的制备方法通过选择合适的原料成分、控制各成分之间的配比，使制备得到的PVC料兼具优异的高温热稳定性和低温抗冲击性，最低的低温抗冲击温度可达到-70℃，远远好于常规的PVC料的低温抗冲击性能。
附图说明
图1为实施例1制备的PVC料的照片。
图2为对比例8制备的PVC料的照片。
图3为对比例9制备的PVC料的照片。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
以下实验中采用的重质碳酸钙的生产厂家为广州邦友粉体有限公司。
实施例1
本实施例提供了一种PVC料的制备方法，其包括以下步骤：
1、以重量份计，称量以下原料：PVC树脂100份，TOTM增塑剂40份，钙锌稳定剂8份、5份阻燃剂，重质碳酸钙5份。
2、将PVC树脂和TOTM增塑剂加入高速混合机共混2min，然后加入钙锌稳定剂、阻燃剂和重质碳酸钙共混2min，得到混合物；
3、将混合物放入双螺杆挤出机中进行造粒，挤出温度为140-180℃(例如可以是170℃，该挤出温度得到的PVC料具有较佳的塑化效果)，得到PVC料。将PVC料样品用标准裁刀裁剪成标准实验样条以备测试使用，记为样品A。
实施例2
本实施例提供了一种PVC料的制备方法，其与实施例1的制备方法基本相同，区别仅在于本实施例中2重质碳酸钙的重量份数增加至15份，将得到的PVC料记为样品 B。
实施例3
本实施例提供了一种PVC料的制备方法，其与实施例1的制备方法基本相同，区别仅在于本实施例中重质碳酸钙的重量份数增加至17份，将得到的PVC料记为样品C。
实施例4
本实施例提供了一种PVC料的制备方法，其与实施例1的制备方法基本相同，区别仅在于本实施例中重质碳酸钙的重量份数增加至20份，将得到的PVC料记为样品D。
对比例1
本对比例提供了一种PVC料的制备方法，其与实施例1的制备方法基本相同，区别仅在于本对比例不添加填料，将得到的PVC料记为样品E。
对比例2
本对比例提供了一种PVC料的制备方法，其与实施例1的制备方法基本相同，区别仅在于本对比例采用5份高岭土代替5份重质碳酸钙作为填料，将得到的PVC料记为样品F。
对比例3
本对比例提供了一种PVC料的制备方法，其与实施例1的制备方法基本相同，区别仅在于本对比例以5份煅烧高岭土替代5份重质碳酸钙作为填料，将得到的PVC料记为样品G。
对比例4
本对比例提供了一种PVC料的制备方法，其与实施例1的制备方法基本相同，区别仅在于本对比例以8份钡锌稳定剂替代8份钙锌稳定剂作为稳定剂，将得到的PVC料记为样品H。
对比例5
本对比例提供了一种PVC料的制备方法，其与实施例4的制备方法基本相同，区别仅在于本对比例以8份钡锌稳定剂替代8份钙锌稳定剂作为稳定剂，将得到的PVC料记为样品I。
对比例6
本对比例提供了一种PVC料的制备方法，其与实施例2的制备方法基本相同，区别仅在于本对比例以40份环氧大豆油替代40份TOTM作为增塑剂，将得到的PVC料记为样品J。
对比例7
本对比例提供了一种PVC料的制备方法，其与实施例2的制备方法基本相同，区别仅在于本对比例以25份TOTM和15份环氧大豆油替代实施例2中所用的40份TOTM作为增塑剂，将得到的PVC料记为样品K。
实施例1-4和对比例1-7所用的PVC料的原料组成总结在表1中。
对以上所有PVC料样品进行热稳定性测试和低温冲击测试。其中，热稳定性测试按照ISO 182-1标准进行，具体包括；将5mg粒状试样放在试管内至下标记水平面处，再把宽5mm的PH试纸放在试管内，然后用棉花塞住试管。放入盛有200℃硅油的烧杯内，开始计时，精确到分。试纸下边缘开始变色时所经过的时间即为热稳定时间。
低温冲击测试按照GBT5470《塑料冲击法脆化温度的测定》规定的测试方法，采用GBT5470中的A仪器进行。热稳定性和低温冲击测试结果总结在表1中。
表1
Figure PCTCN2021108869-appb-000001
对表1的测试结果进行以下分析：
(1)将对比例1-3与实施例1的性能结果对比可以看出，相比于以高岭土、煅烧高岭土作为填料以及不加填料，在PVC料中添加重质碳酸钙作为填料能够使制备的PVC料具有优异的低温抗冲击性，其低温抗冲击温度可达-70℃；同时，添加重质碳酸钙也能够提高热稳定性，使PVC料热稳定性最高可达310℃。这一结果说明，选用特定种类的填料有利于提高PVC料的热稳定性和低温抗冲击性。
(2)将实施例1与对比例4、实施例4与对比例5的性能结果对比可以看出，相比 于钡锌稳定剂，以钙锌稳定剂制备的PVC料具有更低的低温抗冲击温度。这一结果说明，选用特定种类的钙锌稳定剂有利于提高PVC料的低温抗冲击性。
(3)将实施例2、对比例6、对比例7性能结果进行对比可以看出，相比于将环氧大豆油作为增塑剂、以及将环氧大豆油与TOTM的混合物作为增塑剂，单独采用TOTM作为增塑剂制备的PVC料具有更低的低温抗冲击温度。这一结果说明，选用特定种类的增塑剂有利于提高PVC料的低温抗冲击性。
(4)比较实施例1-4的性能结果可以看出，随着重质碳酸钙在原料中的比重由5份逐渐增加至20份，PVC料的低温抗冲击性能表现出明显的下降。这一结果说明，在维持PVC料其他基本性能(例如机械性能)不明显下降的前提下，适当减少重质碳酸钙在PVC原料中的用量有利于提高PVC料的热稳定性和低温抗冲击性。
综合以上分析可以看出，本发明提供的PVC料的制备方法通过控制原料中各成分的种类选择和用量，能够获得兼具优异的热稳定性和耐低温性能，PVC料的低温抗冲击温度可以达到-55℃至-70℃，远远好于目前常规PVC料的低温抗冲击性。
对比例8
本对比例提供了一种PVC料的制备方法，其中，以重量份计，PVC料原料包括：PVC树脂100份，钙锌稳定剂8份、5份阻燃剂，TOTM增塑剂和重质碳酸钙共45份，TOTM增塑剂与重质碳酸钙的质量比为2：1。
以上述原料制备加工PVC料的过程与实施例1相同，得到PVC料记为样品L。
对样品L进行热稳定性和低温冲击性测试，测试方法与样品A-K的方法相同。最终测得样品L的热稳定性为220min，低温抗冲击表现为在-40℃时断裂。
将实施例1与对比例8的测试结果对比可以看出，当增塑剂与填料的质量比低于或超过8：(1-3)的范围时，PVC料的热稳定性和低温抗冲击性明显下降，这说明本发明通过控制增塑剂与填料的配比，能够提升PVC料的热稳定性和低温抗冲击性。
对比例9
本对比例提供了一种PVC料的制备方法，其中，以重量份计，PVC料原料包括：PVC树脂100份，钙锌稳定剂8份、阻燃剂5份，重质碳酸钙5份，TOTM增塑剂与钙锌稳定剂共48份，TOTM增塑剂与钙锌稳定剂的质量比为15：1。
以上述原料制备PVC料的过程与实施例1相同，得到PVC料记为样品M。
对样品M进行热稳定性和低温冲击性测试，测试方法与样品A-K的方法相同。最终测得样品M的热稳定性为37min，低温抗冲击温度为-45℃。
将实施例1与本对比例的测试结果对比可以看出，当增塑剂与钙锌稳定剂的质量比低于或超过5：1的范围时，PVC料的热稳定性和低温抗冲击性明显下降，这说明本发明通过控制增塑剂与钙锌稳定剂的配比，能够提升PVC料的热稳定性和低温抗冲击性。
图1-图3分别为实施例1、对比例8和对比例9加工得到的PVC料的照片，通过对比可以看出，在经过相同的加工过程后，实施例1加工得到的样品A表面平整、光滑，而对比例8和对比例9加工得到的样品L和样品M表面出现褶皱和分布不均的情况。这一对比结果说明：本发明通过控制PVC料中原料的组成和组成之间的有效配比，能够提高PVC料的加工性能，得到的PVC料表面平滑、均匀，有利于PVC料在实际应用中有效功能的发挥。

Claims (15)

  1. 一种PVC料，以重量份计，该PVC料的原料包括：PVC树脂90-120份，增塑剂20-50份，稳定剂5-10份，阻燃剂2-8份，填料5-30份；
    其中，所述增塑剂为偏苯三甲酸三辛酯，所述填料为重质碳酸钙，所述稳定剂为钙锌稳定剂。
  2. 根据权利要求1所述的PVC料，其中，所述增塑剂和稳定剂的质量比为(4-6)：(1-2)，所述增塑剂和填料的质量比为8:(1-3)。
  3. 根据权利要求1或2所述的PVC料，其中，所述增塑剂和稳定剂的质量比为5:1。
  4. 根据权利要求1-3任一项所述的PVC料，其中，以重量份计，所述PVC料的原料包括：PVC树脂90-120份，增塑剂20-50份，稳定剂5-10份，阻燃剂2-8份，填料5份。
  5. 根据权利要求1-4任一项所述的PVC料，其中，所述钙锌稳定剂包括硬脂酸锌类钙锌稳定剂。
  6. 根据权利要求5所述的PVC料，其中，所述硬脂酸锌类钙锌稳定剂中硬脂酸锌的质量含量大于等于10％。
  7. 根据权利要求1-4任一项所述的PVC料，其中，所述重质碳酸钙的粒径为2500-3000目，所述重质碳酸钙中碳酸钙的质量占比大于80％。
  8. 根据权利要求1-4、7任一项所述的PVC料，其中，所述重质碳酸钙的粒径为2800目。
  9. 根据权利要求1或4所述的PVC料，其中，所述PVC树脂的平均聚合度为1250-1350。
  10. 根据权利要求1或4所述的PVC料，其中，所述阻燃剂包括Sb 2O 3类阻燃剂，所述阻燃剂中有效成分的质量占比大于82％。
  11. 根据权利要求1、4、10任一项所述的PVC料，其中，所述阻燃剂包含Sb 2O 3，所述阻燃剂中Sb 2O 3的质量占比大于55％。
  12. 权利要求1-11任一项所述的PVC料的制备方法，其包括：
    步骤一，将PVC树脂和所述增塑剂共混，得到第一混合物；
    步骤二，向所述第一混合物中加入稳定剂、阻燃剂和填料共混，得到第二混合物；
    步骤三，将第二混合物挤出造粒，得到所述PVC料。
  13. 根据权利要求12所述的制备方法，其中，步骤一中，所述共混的时间为 2min-6min；步骤二中，所述共混的时间为2min-6min。
  14. 根据权利要求13所述的制备方法，其中，步骤一中，所述共混的时间为2min；步骤二中，所述共混的时间为2min。
  15. 根据权利要求12-14任一项所述的制备方法，其中，步骤三中，所述挤出的温度为140-180℃。
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