WO2020024308A1 - 一种pvc用稀土复合热稳定剂及其制备方法 - Google Patents

一种pvc用稀土复合热稳定剂及其制备方法 Download PDF

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WO2020024308A1
WO2020024308A1 PCT/CN2018/099092 CN2018099092W WO2020024308A1 WO 2020024308 A1 WO2020024308 A1 WO 2020024308A1 CN 2018099092 W CN2018099092 W CN 2018099092W WO 2020024308 A1 WO2020024308 A1 WO 2020024308A1
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parts
rare earth
acid
pvc
fatty acid
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PCT/CN2018/099092
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French (fr)
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严一丰
严晴
周国庆
高金奎
蒋设
肖阳生
杨光
范修强
龙喜香
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深圳市志海实业股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • the invention belongs to the technical field of organic synthesis and material preparation, and particularly relates to a rare earth composite heat stabilizer for PVC and a preparation method thereof.
  • Polyvinyl chloride is a thermoplastic produced by the polymerization of vinyl chloride monomers.
  • Polyvinyl chloride resin is also a heat-sensitive resin. Processing at high temperature and high shear strength can easily remove the HCl on the molecule and cause degradation, which will reduce the product's discoloration and mechanical properties. Therefore, a certain amount of stabilizer must be added during PVC processing to increase the decomposition temperature of PVC. With the widespread application of rigid polyvinyl chloride resins in the construction industry, the total production and consumption of polyvinyl chloride resins will further increase. Thermal stabilizers are essential additives for the processing of polyvinyl chloride resins, so the production of thermal stabilizers And consumption will also gradually increase, so the development and application of PVC heat stabilizers have important economic and social benefits.
  • the main types of stabilizers are lead salts, metal soaps, organic tin, organic antimony, organic compounds and rare earths.
  • the widely used thermal stabilizers are lead salts and composite metal soaps.
  • organotin stabilizers are widely used due to their good thermal stability and low price, but the toxicity of lead salt stabilizers also limits their application.
  • Metal soap stabilizers are mainly calcium-zinc composite heat stabilizers. Calcium-zinc heat stabilizers are widely recognized as non-toxic stabilizers, and their use is gradually increasing. An obstacle. Organotin stabilizers have good thermal stability, but they are expensive and the current output is small. From the perspective of environmental protection and human health, the development direction of PVC heat stabilizers should be non-toxic and efficient compounding.
  • Rare earth compound heat stabilizer is a new type of PVC heat stabilizer. Rare earth stabilizer is suitable for a variety of PVC products because of its non-toxic, high efficiency, multi-function, and affordable price. China has abundant rare earth resources. It is of great practical significance to make full use of the advantages of our country's rare earth resources to develop a PVC heat stabilizer suitable for China's national conditions.
  • the technical problem to be solved by the present invention is to provide a rare earth composite PVC thermal stabilizer with environmental protection and outstanding thermal stability in view of the shortcomings in the prior art.
  • the present invention is implemented by the following technical solutions.
  • a rare earth composite heat stabilizer for PVC composed of the following raw materials by weight:
  • the rare earth salt is 20 to 55 parts.
  • the zinc stearate is 15-50 parts.
  • the zeolite is 2 to 5 parts.
  • the calcium perchlorate is 2 to 5 parts.
  • the mixed fatty acid is 2-7 parts.
  • the epoxy fatty acid is 8 to 15 parts.
  • the paraffin is selected from the group consisting of ethylene homopolymerization product, cracked wax, and secondary brand wax.
  • the mixed fatty acid and the naphthenic acid may be replaced by one or more of stearic acid, oleic acid, dilauric acid, malic acid, citric acid, adipic acid, and triacetic acid.
  • the mixed fatty acid is a mixture of one or more of an aliphatic monocarboxylic acid and an aliphatic dicarboxylic acid.
  • the aliphatic dicarboxylic acid is an aliphatic dicarboxylic acid containing 6 to 20 carbon atoms and having a linear structure.
  • the trimethylolpropane and the sorbitol may be replaced by one or a mixture of pentaerythritol, dipentaerythritol, phosphite, and octyl epoxy stearate.
  • the rare earth salt is rare earth nitrate, rare earth sulfate, or rare earth chloride.
  • the antioxidant is any one of antioxidant 689, antioxidant 264, and antioxidant 1010.
  • the invention also discloses a method for preparing the rare earth composite heat stabilizer for PVC as described above, including the following steps:
  • SS1 0 to 10 parts of fatty acid, 1 to 5 parts of naphthenic acid, and 5 to 20 parts of epoxy fatty acid are mixed into a reaction kettle with a stirrer, stirred, and heated at 80 to 150 ° C for 1 to 3 hour;
  • SS2 Add 10 to 70 parts of rare earth salts to the reaction kettle, control the ratio of rare earth salts to the acid added to SS1 to 3: 2 to 2: 1, stir and continue heating at 80-150 ° C for 0.5 to 2 hours;
  • SS3 Add 3 to 70 parts of zinc stearate, 1 to 10 parts of zeolite, 1 to 10 parts of calcium perchlorate, and dropwise add 0.2 to 5 kg of the catalyst, and keep it for 1 to 3 hours with stirring to make it uniformly dispersed;
  • the step SS1 specifically refers to: adding the fatty acid, naphthenic acid, and epoxy fatty acid to a three-necked flask, installing a reflux condenser and a heating device, and heating the reaction under the action of magnetic stirring.
  • the catalyst is any one of glacial acetic acid, hydrogen peroxide, and ammonia.
  • the invention adopts a direct melting synthesis method.
  • the direct melting synthesis method is simple, easy to operate, non-polluting, environmentally friendly, low cost of raw materials, can reduce production costs, and has obvious market competitive advantages.
  • the proportion of the rare earth salt is excessive, because the excessive rare earth salt can improve the dispersibility of the thermal stabilizer, and the rare earth ion can surface modify the inorganic powder, and play a certain coupling agent and plasticizer.
  • the present invention has the following advantages:
  • Rare earth composite thermal stabilizers have good thermal stability properties, and their combined thermal stabilizers are often superior to traditional lead salts and barium / zinc, barium / pickle / zinc stabilizers.
  • rare earth composite stabilizers Agents can partially or completely replace organotin.
  • the refractive index of the rare-earth composite heat stabilizer is very close to that of the PVC resin, and can replace the traditionally used organotin for products with higher transparency requirements.
  • rare earth elements can absorb ultraviolet rays of 230-320nm (aging factors: ultraviolet rays, oxygen, humidity, etc.). Therefore, rare earth composite thermal stabilizers have the anti-light aging properties rare in other thermal stabilizers, and are suitable for PVC corrugated boards, window materials, etc Outdoor products.
  • Rare earth elements are low-toxic elements and have no toxic effect on the human body during their production, processing, transportation and storage.
  • Rare earth compound stabilizers are non-toxic products and can be used for food and pharmaceutical product packaging.
  • Examples 1-2 are examples of specific formulations and preparation methods of rare-earth composite heat stabilizers for PVC.
  • the components and proportions of the raw materials in the examples are shown in Table 1.
  • the content of each raw material component in the table is parts by weight. .
  • a comparative example was also added during the test. In the comparative example 1, no rare earth salt was added and in the comparative example 2, zinc stearate was not added.
  • the specific formula is shown in Table 1.
  • the content of each raw material component in the table is parts by weight.
  • a method for preparing a rare earth composite heat stabilizer for PVC includes the following steps:
  • a method for preparing a rare earth composite heat stabilizer for PVC includes the following steps:
  • a method for preparing a rare earth composite heat stabilizer for PVC includes the following steps:
  • a method for preparing a rare earth composite heat stabilizer for PVC includes the following steps:
  • SS1 7 parts of fatty acid, 4 parts of naphthenic acid, 15 parts of epoxy fatty acid are mixed into a reaction kettle with a stirrer, stirred, and heated at 140 ° C for 2.5 hours;
  • SS3 Add 5 parts of zeolite, 5 parts of calcium perchlorate, and dropwise add 4kg of catalyst, and keep it for 2.5 hours with stirring to make it uniformly dispersed;
  • Test condition 1 is a static thermal stabilization time test at 180 ° C
  • test condition 2 is at The temperature is 180 ° C, and the discoloration time is visually checked.
  • Table 2 The specific test results are shown in Table 2:
  • the rare earth salt and zinc stearate have a significant synergistic effect. Adding a mixture of rare earth salt and zinc stearate to PVC to do Congo red static and dynamic tests, the stabilization time is significantly longer than using rare earth salts alone. In the long, 180 ° C static Congo red experiment, the stabilization time of the rare earth salt alone is about 10 minutes less than that of the composite stabilizer.
  • the rare earth composite thermal stabilizer for PVC prepared according to the above-mentioned group distribution ratio and formulation method has excellent stability, the rare earth thermal stabilizer has good thermal stability performance, and the comprehensive performance of the compound thermal stabilizer Often superior to traditional lead salts and barium / zinc, barium / hop / zinc stabilizers.
  • rare earth compound stabilizers can partially or completely replace organotin.
  • Rare earth salts and zinc stearate have obvious synergistic effects. When they are used in a certain proportion, their long-term thermal stability is significantly improved. At the same time, this stabilizer is environmentally friendly, non-toxic and pollution-free.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PVC用稀土复合热稳定剂及其制备方法，稀土复合热稳定剂包括以下原料组分及重量份：稀土盐10～70份；硬脂酸锌3～70份；抗氧化剂1～15份；沸石1～10份；高氯酸钙1～10份；混合脂肪酸0～10份；环烷酸1～5份；环氧脂肪酸5～20份；石蜡10～15份；三羟甲基丙烷1～3份；山梨醇2～4份；邻苯二甲酸二异壬酯3.5～20份。该稀土复合热稳定剂是环保、稳定性高、价格便宜的稳定剂。

Description

一种PVC用稀土复合热稳定剂及其制备方法 技术领域
本发明属于有机合成与材料制备技术领域，具体涉及一种PVC用稀土复合热稳定剂及其制备方法。
背景技术
聚氯乙烯(polyvinyl chloride，PVC)是以氯乙烯单体聚合生产的热塑性塑料。聚氯乙烯树脂也是一种热敏性树脂，在高温和高剪切强度下进行加工容易脱去分子上的HCl而导致降解，使其产品变色和机械性能等下降。因此在PVC加工过程中必需加入一定量的稳定剂，以提高PVC的分解温度。随着硬质聚氯乙烯树脂在建筑行业的广泛应用，聚氯乙烯树脂的生产和消费总量将进一步增加，热稳定剂是聚氯乙烯树脂加工必不可少的添加剂，因此热稳定剂的生产和消费量也将逐渐增加，因此PVC热稳定剂的开发和应用具有重要的经济和社会效益。
近年来PVC行业得到迅速发展，因而PVC热稳定剂也成为重要产业。为防止PVC在加工过程中分解，热稳定剂是必不可少的添加剂。目前，铅盐类稳定剂在我国占主导地位。随着人们环保意识的逐渐增强，铅盐等重金属盐类稳定剂逐步被淘汰，无毒高效复合的稳定剂成为研究的热点。
根据聚氯乙烯的热分解机理，目前人们主要开发的稳定剂种类有铅盐、金属皂、有机锡、有机锑、有机化合物和稀土等，被广泛使用的热稳定剂有铅盐、复合金属皂和有机锡稳定剂。铅盐类热稳定剂具有良好的热稳定性和低廉的价格而被广泛应用，但铅盐类稳定剂的毒性同样限制了其应用范围。金属皂稳定剂主要是钙锌的复合热稳定剂，钙锌热稳定剂被公认为无毒稳定剂，其使用范围正在逐步增加，但钙锌热稳定剂的“锌烧”问题是其广泛应用的一个障碍。有机锡稳定剂的热稳定性良好，但其价格昂贵，目前产量较少。从环境保护和人类健康的角度看，聚氯乙烯热稳定剂的发展方向应该为无毒化和高效复合化。
稀土化合物热稳定剂是一种新型的PVC热稳定剂，稀土稳定剂因其具有无毒、高效、多功能、价格适宜等优点，适用于多种PVC制品。我国稀土资源丰富，充分利用我国的稀土资源优势，开发适合我国国情的PVC热稳定剂具有很大的现实意义。
稀土化合物作为聚氯乙烯热稳定剂的研究得到进一步加深。虽然其具有出色的热稳定性和耐光耐候性，但是其自身的热稳定性还需要进一步提高，而添加辅助稳定剂之后，稀土复合热稳定剂的稳定性得到了很大的改善，因此，开发一种环保、稳定性高、价格便宜的稀土复合热稳定剂具有重大的意义。
发明内容
本发明所要解决的技术问题在于针对上述现有技术中的不足，提供一种具有环保、热稳定性突出的稀土复合PVC热稳定剂。
为解决上述问题，本发明是通过以下技术方案实现的；
一种PVC用稀土复合热稳定剂，由以下重量份的原料组成：
Figure PCTCN2018099092-appb-000001
优选地，所述稀土盐为20～55份。
优选地，所述硬脂酸锌为15～50份。
优选地，所述沸石为2～5份。
优选地，所述高氯酸钙为2～5份。
优选地，所述混合脂肪酸为2～7份。
优选地，所述环氧脂肪酸为8～15份。
优选地，所述石蜡选择为乙烯均聚合产物、裂解蜡、副牌蜡。
优选地，所述混合脂肪酸和所述环烷酸可以由硬脂酸、油酸、双月桂酸、苹果酸、柠檬酸、己二酸、氨三乙酸中的一种或者几种混合物代替。
优选地，所述混合脂肪酸为脂肪族一元羧酸、脂肪族二元羧酸中的一种或几种的混合物。
优选地，所述脂肪族二元羧酸为含碳原子个数为6～20的而且具有直链结构的脂肪族二元羧酸。
优选地，所述的三羟甲基丙烷和所述山梨醇可以由季戊四醇、双季戊四醇、亚磷酸酯、环氧硬脂酸辛酯醇中的一种或者几种的混合物代替。
优选地，所述稀土盐为硝酸稀土、硫酸稀土、氯化稀土。
优选地，所述抗氧化剂为抗氧剂689、抗氧剂264、抗氧剂1010中的任意一种。
本发明还公开了制备如上述PVC用稀土复合热稳定剂的方法，包括以下步骤：
SS1：将0～10份的脂肪酸、1～5份的环烷酸、5～20份的环氧脂肪酸混合加入带有搅拌器的反应釜中，搅拌，在80-150℃下加热1～3小时；
SS2：向反应釜中加入10～70份的稀土盐，控制稀土盐与SS1中加入的酸的比例为3：2～2：1，搅拌并持续在80-150℃下加热0.5～2小时；
SS3：加入3～70份的硬脂酸锌，1～10份的沸石、1～10份高氯酸钙，并滴加催化剂0.2～5kg，搅拌下保温1～3小时使之分散均匀；
SS4：继续向反应釜中加入1～15份的抗氧化剂，并加入10～15份的石蜡作为润滑剂，加入1～3份的三羟甲基丙烷、2～4份的山梨醇，以及3.5～20份的邻苯二甲酸二异壬酯，持续搅拌0.5～1小时；
SS5：停止加热，继续搅拌反应釜，使产物自然降温，降温至80℃，出料，彻底冷却后，研磨、过筛、包装。
优选地，所述步骤SS1具体是指：将脂肪酸、环烷酸、环氧脂肪酸分别加入三口烧瓶中，安装回流冷凝管和加热装置，在磁石搅拌作用下，加热反应。
优选地，所述的催化剂为冰乙酸、双氧水、氨水中的任意一种。
本发明采用直接熔融法合成工艺，直接熔融法合成工艺简单，操作简便，无三非污染，绿色环保，原料成本低，可降低生产成本，市场竞争优势明显。本发明的配方中，稀土盐的比例过量，原因是过量的稀土盐可以提高热稳定剂的分散性，并且稀土离子能够对无机粉体进行表面改性，发挥一定的偶联剂、增塑剂、润滑剂的作用，提高PVC复合材料的力学性能。
本发明与现有技术相比具有以下优点：
(1)优异的热稳定性
稀土复合热稳定剂具有良好的热稳定性能，其复配型热稳定剂的综合性能常优于传统铅盐及钡/锌、钡/镐/锌类稳定剂在某些应用中，稀土复合稳定剂可部分或全部代替有机锡。
(2)透明性好
稀土复合热稳定剂的折光率与PVC树脂非常接近，可替代传统使用的有机锡，用于较高透明性要求的制品中。
(3)优良的耐候性
稀土元素可吸收230-320nm的紫外线(老化因素:紫外线、氧、潮湿等)，因此，稀土复合热稳定剂具有其他热稳定剂少有的抗光老化性能，适合于PVC波纹板、窗材等户外制品。
(4)无毒、安全卫生
稀土元素为低毒元素，在其生产、加工、运输、储存中对人体均无毒害作用。稀土复合稳定剂为无毒产品，可用于食品和医药产品包装。
(5)协同效应
稀土热稳定剂与硬脂酸锌之间有显著的协同效应，当它们按一定比例配合使用时，其长期热稳定性显著提高。
具体实施方式
下面结合实施例进一步阐述本发明。应理解，实施例仅用于说明本发明，而非限制本发明的范围。
实施例1-2是PVC用稀土复合热稳定剂具体配方以及制备方法的实施例，实施例中的各原料的组分和配比分别参见表1，表中各原料组分的含量为重量份。为了说明发明中的配方具有优异的效果，在试验过程中还增加了对比例，其中对比例1中，没有添加稀土盐，对比例2中没有添加硬脂酸锌，具体配方如表1所示，表中各原料组分的含量为重量份。
表1 实施例1～2和对比例1～2中各原料组分的重量配比
Figure PCTCN2018099092-appb-000002
Figure PCTCN2018099092-appb-000003
实施例1
一种PVC用稀土复合热稳定剂的制备方法，包括以下步骤：
SS1：将2份的混合脂肪酸、将2份的环烷酸、8份的环氧脂肪酸混合加入带有搅拌器的反应釜中，搅拌，在140℃下加热1.5小时；
SS2：向反应釜中加入20份的稀土盐，搅拌并持续在140℃下加热1小时；
SS3：加入15份的硬脂酸锌，2份的沸石、2份高氯酸钙，并滴加催化剂2kg，搅拌下保温1.5小时使之分散均匀；
SS4：继续向反应釜中加入5份的抗氧化剂，并加入12份的石蜡作为润滑剂，加入1份的三羟甲基丙烷、3份的山梨醇，以及5份的邻苯二甲酸二异壬酯，持续搅拌0.5小时；
SS5：停止加热，继续搅拌反应釜，使产物自然降温，降温至80℃，出料，彻底冷却后，研磨、过筛、包装。
实施例2
一种PVC用稀土复合热稳定剂的制备方法，包括以下步骤：
SS1：将7份的混合脂肪酸、4份的环烷酸、15份的环氧脂肪酸混合加入带有搅拌器的反应釜中，搅拌，在140℃下加热2.5小时；
SS2：向反应釜中加入55份的稀土盐，搅拌并持续在140℃下加热2小时；
SS3：加入50份的硬脂酸锌，5份的沸石、5份高氯酸钙，并滴加催化剂4kg，搅拌下保温2.5小时使之分散均匀；
SS4：继续向反应釜中加入12份的抗氧化剂，并加入14份的石蜡作为润滑剂，加入2份的三羟甲基丙烷、4份的山梨醇，以及15份的邻苯二甲酸二异壬酯，持续搅拌1小时；
SS5：停止加热，继续搅拌反应釜，使产物自然降温，降温至80℃，出料，彻底冷却后，研磨、过筛、包装。
对比例1
一种PVC用稀土复合热稳定剂的制备方法，包括以下步骤：
SS1：将2份的混合脂肪酸、2份的环烷酸、8份的环氧脂肪酸混合加入带有搅拌器的反应釜中，搅拌，在140℃下加热1.5小时；
SS2：加入15份的硬脂酸锌，2份的沸石、2份高氯酸钙，并滴加催化剂2kg，搅拌下保温1.5小时使之分散均匀；
SS3：继续向反应釜中加入5份的抗氧化剂，并加入12份的石蜡作为润滑剂，加入1份的三羟甲基丙烷、3份的山梨醇，以及5份的邻苯二甲酸二异壬酯，持续搅拌0.5小时；
SS4：停止加热，继续搅拌反应釜，使产物自然降温，降温至80℃，出料，彻底冷却后，研磨、过筛、包装。
对比例2
一种PVC用稀土复合热稳定剂的制备方法，包括以下步骤：
SS1：将7份的脂肪酸、4份的环烷酸、15份的环氧脂肪酸混合加入带有搅拌器的反应釜中，搅拌，在140℃下加热2.5小时；
SS2：向反应釜中加入55份的稀土盐，搅拌并持续在140℃下加热2小时；
SS3：加入5份的沸石、5份高氯酸钙，并滴加催化剂4kg，搅拌下保温2.5小时使之分散均匀；
SS4：继续向反应釜中加入12份的抗氧化剂，并加入14份的石蜡作为润滑剂，加入2份的三羟甲基丙烷、4份的山梨醇，以及15份的邻苯二甲酸二异壬酯，持续搅拌1小时；
SS5：停止加热，继续搅拌反应釜，使产物自然降温，降温至80℃，出料，彻底冷却后，研磨、过筛、包装。
性能测试
将实施例1-2以及对比例1-2中的稀土复合热稳定剂进行性能测试，采用刚果红实验的测试方法，测试条件1是在180℃的静态热稳定时间测试，测试条件2是在180℃的温度下热烘，目测变色的时间，具体测试结果如表2所示：
表2 测试结果
Figure PCTCN2018099092-appb-000004
由表2可以看出，稀土盐与硬脂酸锌具有明显的协同效应，将稀土盐与硬脂酸锌的混合物添加到PVC中做刚果红静态和动态测试，稳定时间明显比单独使用稀土盐的长，180℃的静态刚果红实验中，单独使用稀土盐的稳定时间比复合稳定剂的稳定时间少10min左右。
依据本发明以上所述组分配比及配制方法所制备的PVC用稀土复合热稳定剂，具有优异的稳定性，稀土热稳定剂具有良好的热稳定性能，其复配型热稳定剂的综合性能常优于传统铅盐及钡/锌、钡/镐/锌类稳定剂在某些应用中，稀土复合稳定剂可部分或全部代替有机锡。稀土盐与硬脂酸锌具有明显的协同效应，当它们按一定比例配合使用时，其长期热稳定性显著提高。同时，此稳定剂为环保材料，无毒无污染。
以上所述只是本发明的优选实施例，故凡依据本发明专利申请范围所述工艺原理所做同等修改，均包括于本发明专利所申请范围内。

Claims (10)

  1. 一种PVC用稀土复合热稳定剂，其特征在于，所述稀土复合热稳定剂包括以下原料组分及重量份：
    Figure PCTCN2018099092-appb-100001
  2. 根据权利要求1所述的PVC用稀土复合热稳定剂，其特征在于：所述稀土盐为20～55份；所述硬脂酸锌为15～50份；所述沸石为2～5份；所述高氯酸钙为2～5份；所述混合脂肪酸为2～7份；所述环氧脂肪酸为8～15份。
  3. 根据权利要求2所述的PVC用稀土复合热稳定剂，其特征在于：所述石蜡选择为乙烯均聚合产物、裂解蜡、副牌蜡。
  4. 根据权利要求2所述的PVC用稀土复合热稳定剂，其特征在于：用硬脂酸、油酸、双月桂酸、苹果酸、柠檬酸、己二酸、氨三乙酸中的一种或者几种的混合物替换所述混合脂肪酸和所述环烷酸。
  5. 根据权利要求2所述的PVC用稀土复合热稳定剂，其特征在于：用季戊四醇、双季戊四醇、亚磷酸酯、环氧硬脂酸辛酯中的一种或者几种的混合物替换所述的三羟甲基丙烷和所述山梨醇。
  6. 根据权利要求2所述的PVC用稀土复合热稳定剂，其特征在于：所述稀土盐为硝酸稀土、硫酸稀土、氯化稀土。
  7. 根据权利要求2所述的PVC用稀土复合热稳定剂，其特征在于：所述抗氧化剂为抗氧剂689、抗氧剂264、抗氧剂1010中的任意一种。
  8. 一种制备如权利要求1～7任一所述的PVC用稀土复合热稳定剂的方法，其特征在于，包括以下步骤：
    SS1：将0～10份的混合脂肪酸、1～5份的环烷酸、5～20份的环氧脂肪酸混合加入带有搅拌器的反应釜中，搅拌，在80-150℃下加热反应；
    SS2：向反应釜中加入10～70分的稀土盐，控制稀土盐与SS1中加入的酸的比例为3：2～2：1，搅拌并持续在80-150℃下加热反应；
    SS3：加入3～70份的硬脂酸锌，1～10份的沸石、1～10份高氯酸钙，并滴加催化剂0.2～5kg，搅拌下保温1～3小时使之分散均匀；
    SS4：继续向反应釜中加入1～15份的抗氧化剂，并加入10～15份的石蜡作为润滑剂，加入1～3份的三羟甲基丙烷、2～4份的山梨醇，以及3.5～20份的邻苯二甲酸二异壬酯，持续搅拌0.5～1小时；
    SS5：停止加热，继续搅拌反应釜，使产物自然降温，降温至80℃，出料，彻底冷却后，研磨、过筛、包装。
  9. 根据权利要求8所述的制备方法，其特征在于，所述步骤SS1具体是指：将混合脂肪酸、环烷酸、环氧脂肪酸分别加入三口烧瓶中，安装回流冷凝管和加热装置，在磁石搅拌作用下，加热反应。
  10. 根据权利要求8所述的制备方法，其特征在于：所述的催化剂为冰乙酸、双氧水、氨水中的任意一种。
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