WO2016192292A1 - 一种环保耐寒聚氯乙烯弹性体组合物及其制备方法 - Google Patents

一种环保耐寒聚氯乙烯弹性体组合物及其制备方法 Download PDF

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WO2016192292A1
WO2016192292A1 PCT/CN2015/093269 CN2015093269W WO2016192292A1 WO 2016192292 A1 WO2016192292 A1 WO 2016192292A1 CN 2015093269 W CN2015093269 W CN 2015093269W WO 2016192292 A1 WO2016192292 A1 WO 2016192292A1
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parts
polyvinyl chloride
elastomer composition
environmentally
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French (fr)
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王庚超
魏伟
黄近都
毛亮
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江苏兴华胶带股份有限公司
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    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • C08K2201/00—Specific properties of additives
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    • C08K2201/003—Additives being defined by their diameter
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    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

Definitions

  • the invention relates to the field of materials, in particular to an environmentally friendly cold-resistant polyvinyl chloride elastomer composition and a preparation method thereof.
  • Polyvinyl chloride elastomer has the characteristics of low price, adjustable mechanical properties and good flame retardancy. It is suitable for the preparation of elevator balance compensation chain sheath, wire and cable insulation cover, door and window and window seals. However, polyvinyl chloride elastomers have certain defects in environmental protection and low temperature toughness.
  • the toughening agent used in the application No. CN201310473887.1 is a silicone rubber, which has poor compatibility with the polyvinyl chloride body, which causes the normal temperature toughness and low temperature toughness of the elastomer to be affected, and the low temperature resistance is not satisfactory.
  • the application number is CN201210161975.3, which discloses a cold-resistant and environmentally-friendly polyvinyl chloride special cable material.
  • the raw material cost of the diethylene glycol dibenzoate plasticizer used is high, which limits its application in the civil range. Therefore, it is particularly important to develop a polyvinyl chloride elastomer with excellent comprehensive properties such as environmental protection, non-toxicity, cold resistance and high mechanical strength.
  • the object of the present invention is to provide an environmentally-friendly and cold-resistant polyvinyl chloride elastomer composition, which has the advantages of safety, environmental protection, cold resistance, heat resistance, aging resistance, high mechanical strength, etc., and can be maintained in a low temperature working environment. High toughness.
  • an environmentally friendly cold-resistant polyvinyl chloride elastomer composition including a polyvinyl chloride resin, an environmentally friendly composite plasticizing system, a toughening agent, a calcium-zinc composite stabilizer, and a lubricant.
  • An antioxidant and a pigment the environmentally friendly composite plasticizing system comprising a dialkyl terephthalate and a synthetic vegetable oil ester, the toughening agent comprising a polar rubber and a nano-active calcium carbonate, the elastomer composition being The Shore hardness is less than 80 at -5 ° C, and the alkyl group in the dialkyl terephthalate includes 7 to 12 carbon atoms.
  • each component of the elastomer composition comprises, by weight: 100 parts by weight of a polyvinyl chloride resin, 50 to 90 parts by weight of a dialkyl terephthalate, and 10 to 40 parts by weight of a synthetic vegetable oil ester. 5 to 20 parts by weight of polar rubber, 5 to 30 parts by weight of nano-active calcium carbonate, 4 to 8 parts by weight of calcium-zinc composite stabilizer, 1 to 2 parts by weight of lubricant, and 0.2 to 1 part by weight of anti-drug Oxygen agent and 0.5 to 3 parts by weight of the pigment.
  • the synthetic vegetable oil ester is modified by epoxidation or epoxy esterification of a vegetable oil
  • the vegetable oil is one or more of soybean oil, linseed oil, castor oil, safflower oil and sunflower oil. composition.
  • the polar rubber is one of ethylene-vinyl acetate copolymer rubber, urethane rubber, and polyacrylate rubber.
  • the ethylene-vinyl acetate copolymer rubber has a vinyl acetate content of 40 to 70% by weight.
  • the nano-active calcium carbonate has an average diameter of between 60 and 100 nm.
  • the lubricant is one of zinc stearate, stearic acid and polyethylene wax.
  • the antioxidant is tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 2,2'-methylene-bis(4-methyl- One or two of 6-tert-butylphenol), tris[2.4-di-tert-butylphenyl]phosphite, and triphenyl phosphite.
  • the pigment is one of high pigment carbon black and rutile type titanium dioxide.
  • the invention also provides a preparation method of the above environmentally-friendly cold-resistant polyvinyl chloride elastomer composition, comprising the following steps:
  • Step 1 Mix and mix the components uniformly in a kneader, and increase the temperature of the mixture by using the frictional heat generated by the stirring;
  • Step 2 the temperature of each component in the kneading machine rises to 90-100 ° C and discharges, and is sent to a cooling stirrer to cool to below 45 ° C;
  • Step 3 The cooled mixture is placed on a double-stage screw extruder, which comprises a twin-screw extruder and a single-screw extruder, and the twin-screw extruder has four
  • the temperature of the heating zone of the single screw extruder and the extrusion die were controlled at 110 to 130 ° C and 120 to 140 ° C, respectively, to obtain a polyvinyl chloride elastomer composition having a Shore hardness of less than 80 at -5 °C.
  • the polyvinyl chloride elastomer prepared by the invention has the advantages of excellent low temperature toughness, high mechanical strength, good heat aging resistance, environmental protection and non-toxicity, and excellent comprehensive performance, and is particularly suitable for preparing elevator balance compensation chain sheath, doors and windows and windows Seals and insulation coverings for wires and cables.
  • Dialkyl terephthalate has the same excellent plasticizing effect as phthalate plasticizers. Excellent cold resistance, no deactivation under low temperature conditions; synthetic vegetable oil has low volatility and can also be used as a heat stabilizer; two plasticizers can be used in a reasonable combination to give their respective performance advantages More excellent plasticizing effect of vinyl chloride;
  • the elastomer can still maintain good toughness under low temperature conditions; nano-active calcium carbonate as a toughening agent and filler in polyvinyl chloride
  • the matrix can be fully dispersed, greatly improving the toughness and strength of the elastomer, and has the dual effects of toughening and strengthening.
  • the combination of the two toughening agents produces a synergistic effect, which has a significant effect on improving the normal temperature toughness of the elastomer and maintaining the low temperature toughness;
  • the invention relates to an environmentally-friendly cold-resistant polyvinyl chloride elastomer composition, comprising a polyvinyl chloride resin, an environmentally friendly composite plasticizing system, a toughening agent, a calcium-zinc composite stabilizer, a lubricant, an antioxidant and a pigment
  • the environmentally friendly composite plasticizing system comprises a dialkyl terephthalate and a synthetic vegetable oil ester, the toughening agent package
  • the polar rubber and the nano-active calcium carbonate are used, the elastomer composition has a Shore hardness of less than 80 at -5 ° C, and the alkyl group of the dialkyl terephthalate comprises 7 to 12 carbon atoms.
  • the components of the elastomer composition are calculated by weight: 100 parts by weight of polyvinyl chloride resin, 50 to 90 parts by weight of dialkyl terephthalate, 10 to 40 parts by weight of synthetic vegetable oil ester, 5 to 20 parts by weight. Parts by weight of polar rubber, 5 to 30 parts by weight of nano-active calcium carbonate, 4 to 8 parts by weight of calcium-zinc composite stabilizer, 1 to 2 parts by weight of a lubricant, 0.2 to 1 part by weight of an antioxidant, and 0.5 ⁇ 3 parts by weight of pigment.
  • Synthetic vegetable oil esters are modified from vegetable oils by epoxidation or epoxy esterification, the vegetable oil being one or more of soybean oil, linseed oil, castor oil, safflower oil and sunflower oil;
  • the polar rubber is one of ethylene-vinyl acetate copolymer rubber, urethane rubber and polyacrylate rubber; the ethylene-vinyl acetate copolymer rubber has a vinyl acetate content of 40% to 70% by weight;
  • the nano-active calcium carbonate has an average diameter of between 60 and 100 nm;
  • the lubricant is one of zinc stearate, stearic acid and polyethylene wax;
  • the antioxidant is four [ ⁇ -(3,5) -di-tert-butyl-4-hydroxyphenyl)propanoic acid]pentaerythritol ester, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), tris[2.4-di-tert-butyl One or
  • the invention also provides a preparation method of the above environmentally-friendly cold-resistant polyvinyl chloride elastomer composition, comprising the following steps:
  • Step 1 Mix and mix the components uniformly in a kneader, and increase the temperature of the mixture by using the frictional heat generated by the stirring;
  • Step 2 the temperature of each component in the kneading machine rises to 90-100 ° C and discharges, and is sent to a cooling stirrer to cool to below 45 ° C;
  • Step 3 The cooled mixture is placed on a double-stage screw extruder, which comprises a twin-screw extruder and a single-screw extruder, and the twin-screw extruder has four
  • the temperature of the heating zone of the single screw extruder and the extrusion die were controlled at 110 to 130 ° C and 120 to 140 ° C, respectively, to obtain a polyvinyl chloride elastomer composition having a Shore hardness of less than 80 at -5 °C.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • the extruded pellets were hot pressed into a 2 mm or 6 mm sample on a flat vulcanizer and cut into the desired splines.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the extruded pellets were hot pressed into a 2 mm or 6 mm sample on a flat vulcanizer and cut into the desired splines.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • the temperature of the heating zone of the single screw extruder and the extrusion die are controlled at 110 to 130 ° C and 120 to 140 ° C, respectively.
  • the extruded pellets were hot pressed into a 2 mm or 6 mm sample on a flat vulcanizer and cut into the desired splines.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • the extruded pellets were hot pressed into a 2 mm or 6 mm sample on a flat vulcanizer and cut into the desired splines.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • the extruded pellets were hot pressed into a 2 mm or 6 mm sample on a flat vulcanizer and cut into the desired splines.
  • the extruded pellets were hot pressed into a 2 mm or 6 mm sample on a flat vulcanizer and cut into the desired splines.
  • the extruded pellets were hot pressed into a 2 mm or 6 mm sample on a flat vulcanizer and cut into the desired splines.
  • the extruded pellets were hot pressed into a 2 mm or 6 mm sample on a flat vulcanizer and cut into the desired splines.
  • the extruded pellets were hot pressed into a 2 mm or 6 mm sample on a flat vulcanizer and cut into the desired splines.

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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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)

Abstract

本发明公开了一种环保耐寒聚氯乙烯弹性体组合物及其制备方法，将聚氯乙烯树脂、对苯二甲酸二烷基酯、合成植物油酯、极性橡胶、纳米活性碳酸钙、钙锌系复合稳定剂、润滑剂、抗氧剂和颜料在捏合机中混合，待混合物料温达到90-100℃后出料冷却，再将冷却后的混合物置于双阶螺杆挤出机上挤出造粒而成，弹性体组合物在-5℃时邵氏硬度低于80。本发明的有益效果是具有低温韧性优异，力学强度高、耐热老化性好、环保无毒等优点，综合性能优异，特别适用于制备电梯平衡补偿链护套、门窗和车窗封条以及电线电缆的绝缘护层等。

Description

一种环保耐寒聚氯乙烯弹性体组合物及其制备方法 技术领域
本发明涉及材料领域，尤其涉及一种环保耐寒聚氯乙烯弹性体组合物及其制备方法。
背景技术
聚氯乙烯弹性体具有价格低廉、力学性能可调和阻燃性好等特点，适用于制备电梯平衡补偿链护套、电线电缆的绝缘护层以及门窗和车窗封条等众多场合。但聚氯乙烯弹性体在环保性和低温韧性等方面存在一定缺陷。
迄今，已有诸多专利报道了耐低温或耐寒性聚氯乙烯弹性体材料的组成和制备方法。如申请号为CN201210569416.6、CN201410284632.5、CN200810023863.5等中国专利。上述专利所描述的聚氯乙烯弹性体材料虽然具有一定的耐低温性能，低温韧性良好，然而其所用的主增塑剂为邻苯二甲酸酯类增塑剂，这类增塑剂会危害人体健康，达不到环保要求。
为了达到环保要求，已有专利报道了环境友好型的聚氯乙烯弹性体。申请号为CN200910102369.2、CN201310464355.1、CN201010508484.2、CN201310754691.X、CN201110199511.7、CN201310242694.5和CN201210106293.2等专利均公开了环保型聚氯乙烯弹性体的组成和制备方法，所制备的弹性体具有优良的环保性，对人体和环境污染甚少，然而其所使用的增韧剂与增塑剂低温性能较差，使得弹性体在低温(-40℃以下)条件下会脆化，严重影响弹性体在极寒环境下的使用寿命。同时，也有一些专利公开了环保耐寒的聚氯乙烯弹性体。如申请号为CN201310473887.1专利中所使用的增韧剂为硅橡胶，与聚氯乙烯基体中的相容性较差，造成弹性体的常温韧性和低温韧性均受到影响，耐低温性能不理想。申请号为CN201210161975.3公开了一种耐严寒环保聚氯乙烯基特种电缆料，所使用的二乙二醇二苯甲酸酯增塑剂原料成本高，限制了其在民用范围内的应用。因此开发一种环保无毒、耐寒、力学强度高等综合性能优异的聚氯乙烯弹性体显得尤为重要。
发明内容
本发明的目的在于提供一种环保耐寒聚氯乙烯弹性体组合物，具有安全环保、耐寒耐热、抗老化、力学强度高等优点，其能够在低温作业环境下依然保 持较高的韧性。
为了解决上述问题，本发明的技术解决方案是：一种环保耐寒聚氯乙烯弹性体组合物，包括聚氯乙烯树脂、环保复合增塑体系、增韧剂、钙锌系复合稳定剂、润滑剂、抗氧剂和颜料，所述环保复合增塑体系包括对苯二甲酸二烷基酯和合成植物油酯，所述增韧剂包括极性橡胶与纳米活性碳酸钙，所述弹性体组合物在-5℃时邵氏硬度低于80，所述对苯二甲酸二烷基酯中烷基包括7～12个碳原子。
进一步，所述弹性体组合物各组份按重量份计算包括：100重量份的聚氯乙烯树脂、50～90重量份的对苯二甲酸二烷基酯、10～40重量份的合成植物油酯、5～20重量份的极性橡胶、5～30重量份的纳米活性碳酸钙、4～8重量份的钙锌复合稳定剂、1～2重量份的润滑剂、0.2～1重量份的抗氧剂和0.5～3重量份的颜料。
进一步，所述合成植物油酯由植物油经环氧化或环氧基酯化改性而成，所述植物油为大豆油、亚麻油、蓖麻油、红花油和葵花油中的一种或多种组成。
进一步，所述极性橡胶为乙烯-醋酸乙烯酯共聚物橡胶、聚氨酯橡胶和聚丙烯酸酯橡胶中的一种。
进一步，所述乙烯-醋酸乙烯酯共聚物橡胶中醋酸乙烯酯重量百分比含量为40～70％。
进一步，所述纳米活性碳酸钙的平均直径在60～100nm之间。
进一步，所述润滑剂为硬脂酸锌、硬脂酸和聚乙烯蜡中的一种。
进一步，所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、2,2'-亚甲基-双(4-甲基-6-叔丁基苯酚)、三[2.4-二叔丁基苯基]亚磷酸酯、亚磷酸三苯酯中的一种或两种组成。
进一步，所述颜料为高色素炭黑和金红石型二氧化钛中的一种。
本发明还提供上述环保耐寒聚氯乙烯弹性体组合物的制备方法，包括如下步骤：
步骤一：将各组份在捏合机中搅拌混合均匀，利用搅拌产生的摩擦热使混合物温度升高；
步骤二：捏合机中各组份混合物温度上升到90-100℃后出料，送入冷却搅拌器冷却至45℃以下；
步骤三：将冷却后的混合物置于双阶螺杆挤出机上挤出造料，所述双阶螺杆挤出机包括双螺杆挤出机和单螺杆挤出机，所述双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；所述单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃，得到聚氯乙烯弹性体组合物，其在-5℃时邵氏硬度低于80。
本发明所制备的聚氯乙烯弹性体具有低温韧性优异，力学强度高、耐热老化性好、环保无毒等优点，综合性能优异，特别适用于制备电梯平衡补偿链护套、门窗和车窗封条以及电线电缆的绝缘护层等。
上述聚氯乙烯弹性组合物具有如下有益效果：
(1)通过采用安全环保型增塑剂，对环境和人体无安全隐患，符合环保要求，对苯二甲酸二烷基酯具有和邻苯二甲酸酯类增塑剂同样优异的增塑效果和优异的耐寒性能，在低温条件下不会失活；合成植物油脂具有低挥发性、亦可作为热稳定剂的特点；两种增塑剂通过合理的配合使用，发挥各自的性能优势可赋予聚氯乙烯更优异的增塑效果；
(2)采用具有耐寒性的极性橡胶和纳米活性碳酸钙作为增韧剂，使弹性体在低温条件下依然能够保持良好的韧性；纳米活性碳酸钙作为增韧剂和填充剂在聚氯乙烯基体中能够充分分散，极大的提高了弹性体的韧性和强度，起到增韧和增强的双重效应。两种增韧剂组合使用，产生协同效应，对提高弹性体的常温韧性、保持低温韧性有显著效果；
(3)使用环保型液态钙锌系复合稳定剂，对环境和人体对不存在危害隐患，符合环保要求。
具体实施方式
下面结合具体实施方式对本发明作进一步详细的说明。
为了本领域的技术人员能够更好地理解本发明所提供的技术方案，下面结合具体实施例进行阐述。
本发明涉及的一种环保耐寒聚氯乙烯弹性体组合物，包括聚氯乙烯树脂，环保复合增塑体系、增韧剂、钙锌系复合稳定剂、润滑剂、抗氧剂和颜料，所述环保复合增塑体系包括对苯二甲酸二烷基酯和合成植物油酯，所述增韧剂包 括极性橡胶与纳米活性碳酸钙，所述弹性体组合物在-5℃时邵氏硬度低于80，所述对苯二甲酸二烷基酯中烷基包括7～12个碳原子。
弹性体组合物各组份按重量份计算包括：100重量份的聚氯乙烯树脂、50～90重量份的对苯二甲酸二烷基酯、10～40重量份的合成植物油酯、5～20重量份的极性橡胶、5～30重量份的纳米活性碳酸钙、4～8重量份的钙锌复合稳定剂、1～2重量份的润滑剂、0.2～1重量份的抗氧剂和0.5～3重量份的颜料。
合成植物油酯由植物油经环氧化或环氧基酯化改性而成，所述植物油为大豆油、亚麻油、蓖麻油、红花油和葵花油中的一种或多种组成；所述极性橡胶为乙烯-醋酸乙烯酯共聚物橡胶、聚氨酯橡胶和聚丙烯酸酯橡胶中的一种；所述乙烯-醋酸乙烯酯共聚物橡胶中醋酸乙烯酯重量百分比含量为40～70％；所述纳米活性碳酸钙的平均直径在60～100nm之间；所述润滑剂为硬脂酸锌、硬脂酸和聚乙烯蜡中的一种；所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、2,2'-亚甲基-双(4-甲基-6-叔丁基苯酚)、三[2.4-二叔丁基苯基]亚磷酸酯、亚磷酸三苯酯中的一种或两种组成；所述颜料为高色素炭黑和金红石型二氧化钛中的一种。
本发明还提供上述环保耐寒聚氯乙烯弹性体组合物的制备方法，包括如下步骤：
步骤一：将各组份在捏合机中搅拌混合均匀，利用搅拌产生的摩擦热使混合物温度升高；
步骤二：捏合机中各组份混合物温度上升到90-100℃后出料，送入冷却搅拌器冷却至45℃以下；
步骤三：将冷却后的混合物置于双阶螺杆挤出机上挤出造料，所述双阶螺杆挤出机包括双螺杆挤出机和单螺杆挤出机，所述双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；所述单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃，得到聚氯乙烯弹性体组合物，其在-5℃时邵氏硬度低于80。
实施例一：
将100重量份的聚氯乙烯树脂、75重量份的对苯二甲酸二辛酯、25重量份的环氧大豆油、10重量份的聚氨酯橡胶、15重量份的纳米活性碳酸钙、5重量 份的钙锌复合稳定剂、1.5重量份的硬脂酸锌、0.6重量份的四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和1重量份的高色素炭黑在捏合机中高速搅拌混合，搅拌产生的摩擦热使混合物料温度升至90-100℃后出料，混合物料送入冷却搅拌器冷却至45℃以下，再将冷却后的混合物料置于双阶螺杆挤出机上挤出造粒，其中双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃。将挤出的粒料在平板硫化机上热压成厚度为2mm或6mm样片，并裁切成符合要求的样条。
实施例二：
将100重量份的聚氯乙烯树脂、90重量份的对苯二甲酸二庚酯、10重量份的环氧基酯化亚麻油、20重量份的乙烯-醋酸乙烯酯共聚物(醋酸乙烯重量百分比为40％)、5重量份的纳米活性碳酸钙、8重量份的钙锌复合稳定剂、1重量份的聚乙烯蜡、0.2重量份的四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和3重量份的金红石型二氧化钛在捏合机中高速搅拌混合，搅拌产生的摩擦热使混合物料温度升至90-100℃后出料，混合物料送入冷却搅拌器冷却至45℃以下，再将冷却后的混合物料置于双阶螺杆挤出机上挤出造粒，其中双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃。将挤出的粒料在平板硫化机上热压成厚度为2mm或6mm样片，并裁切成符合要求的样条。
实施例三：
将100重量份的聚氯乙烯树脂、70重量份的对苯二甲酸二(十二烷基)酯、40重量份的环氧红花油、5重量份的聚丙烯酸酯橡胶、30重量份的纳米活性碳酸钙、8重量份的钙锌复合稳定剂、2重量份的硬脂酸锌、0.5重量份的四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、0.2重量份的三[2.4-二叔丁基苯基]亚磷酸酯和1.5重量份的高色素炭黑在捏合机中高速搅拌混合，搅拌产生的摩擦热使混合物料温度升至90-100℃后出料，混合物料送入冷却搅拌器冷却至45℃以下，再将冷却后的混合物料置于双阶螺杆挤出机上挤出造粒，其中双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃， T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃。将挤出的粒料在平板硫化机上热压成厚度为2mm或6mm样片，并裁切成符合要求的样条。
实施例四：
将100重量份的聚氯乙烯树脂、70重量份的对苯二甲酸二辛酯、30重量份的环氧蓖麻油、20重量份的聚氨酯橡胶、20重量份的纳米活性碳酸钙、6重量份的钙锌复合稳定剂、1重量份的硬脂酸锌、0.6重量份的三[2.4-二叔丁基苯基]亚磷酸酯、0.2重量份的亚磷酸三苯酯和1重量份的高色素炭黑在捏合机中高速搅拌混合，搅拌产生的摩擦热使混合物料温度升至90-100℃后出料，混合物料送入冷却搅拌器冷却至45℃以下，再将冷却后的混合物料置于双阶螺杆挤出机上挤出造粒，其中双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃。将挤出的粒料在平板硫化机上热压成厚度为2mm或6mm样片，并裁切成符合要求的样条。
实施例五：
将100重量份的聚氯乙烯树脂、75重量份的对苯二甲酸二(十二烷基)酯、20重量份的环氧葵花油、15重量份的乙烯-醋酸乙烯共聚物(醋酸乙烯重量百分比为70％)、10重量份的纳米活性碳酸钙、5重量份的钙锌复合稳定剂、1重量份的聚乙烯蜡、0.6重量份的三[2.4-二叔丁基苯基]亚磷酸酯和0.5重量份的高色素炭黑在捏合机中高速搅拌混合，搅拌产生的摩擦热使混合物料温度升至90-100℃后出料，混合物料送入冷却搅拌器冷却至45℃以下，再将冷却后的混合物料置于双阶螺杆挤出机上挤出造粒，其中双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃。将挤出的粒料在平板硫化机上热压成厚度为2mm或6mm样片，并裁切成符合要求的样条。
对比例一：
将100重量份的聚氯乙烯树脂、75重量份的对苯二甲酸二辛酯、25重量份的环氧大豆油、10重量份的氯化聚乙烯、15重量份目数为1200的轻质碳酸 钙、5重量份的钙锌复合稳定剂、1.5重量份的润滑剂、0.6重量份的三[2.4-二叔丁基苯基]亚磷酸酯和1重量份的高色素炭黑在捏合机中高速搅拌混合，搅拌产生的摩擦热使混合物料温度升至90-100℃后出料，混合物料送入冷却搅拌器冷却至45℃以下，再将冷却后的混合物料置于双阶螺杆挤出机上挤出造粒，其中双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃。将挤出的粒料在平板硫化机上热压成厚度为2mm或6mm样片，并裁切成符合要求的样条。
对比例二：
将100重量份的聚氯乙烯树脂、75重量份的对苯二甲酸二辛酯、25重量份的环氧大豆油、10重量份的聚氨酯橡胶、15重量份目数为1200的轻质碳酸钙、5重量份的钙锌复合稳定剂、1.5重量份的润滑剂、0.6重量份的三[2.4-二叔丁基苯基]亚磷酸酯和1重量份的高色素炭黑在捏合机中高速搅拌混合，搅拌产生的摩擦热使混合物料温度升至90-100℃后出料，混合物料送入冷却搅拌器冷却至45℃以下，再将冷却后的混合物料置于双阶螺杆挤出机上挤出造粒，其中双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃。将挤出的粒料在平板硫化机上热压成厚度为2mm或6mm样片，并裁切成符合要求的样条。
对比例三：
将100重量份的聚氯乙烯树脂、75重量份的对苯二甲酸二(十二烷基)酯、20重量份的环氧葵花油、3重量份的乙烯-醋酸乙烯共聚物(醋酸乙烯重量百分比为50％)、10重量份的纳米活性碳酸钙、5重量份的钙锌复合稳定剂、1重量份的润滑剂、0.6重量份的三[2.4-二叔丁基苯基]亚磷酸酯和0.5重量份的高色素炭黑在捏合机中高速搅拌混合，搅拌产生的摩擦热使混合物料温度升至90-100℃后出料，混合物料送入冷却搅拌器冷却至45℃以下，再将冷却后的混合物料置于双阶螺杆挤出机上挤出造粒，其中双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃。将挤出的粒料在平板硫化机上热压成厚度为2mm 或6mm样片，并裁切成符合要求的样条。
对比例四：
将100重量份的聚氯乙烯树脂、75重量份的对苯二甲酸二(十二烷基)酯、20重量份的环氧葵花油、25重量份的聚氨酯橡胶、10重量份的纳米活性碳酸钙、5重量份的钙锌复合稳定剂、1重量份的润滑剂、0.6重量份的三[2.4-二叔丁基苯基]亚磷酸酯和0.5重量份的高色素炭黑在捏合机中高速搅拌混合，搅拌产生的摩擦热使混合物料温度升至90-100℃后出料，混合物料送入冷却搅拌器冷却至45℃以下，再将冷却后的混合物料置于双阶螺杆挤出机上挤出造粒，其中双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃。将挤出的粒料在平板硫化机上热压成厚度为2mm或6mm样片，并裁切成符合要求的样条。
对比例五：
将100重量份的聚氯乙烯树脂、75重量份的对苯二甲酸二(十二烷基)酯、20重量份的环氧葵花油、15重量份的聚丙烯酸酯橡胶、3重量份的纳米活性碳酸钙、5重量份的钙锌复合稳定剂、1重量份的润滑剂、0.6重量份的三[2.4-二叔丁基苯基]亚磷酸酯和0.5重量份的高色素炭黑在捏合机中高速搅拌混合，搅拌产生的摩擦热使混合物料温度升至90-100℃后出料，混合物料送入冷却搅拌器冷却至45℃以下，再将冷却后的混合物料置于双阶螺杆挤出机上挤出造粒，其中双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃。将挤出的粒料在平板硫化机上热压成厚度为2mm或6mm样片，并裁切成符合要求的样条。
对比例六：
将100重量份的聚氯乙烯树脂、75重量份的对苯二甲酸二(十二烷基)酯、20重量份的环氧葵花油、15重量份的乙烯-醋酸乙烯共聚物(醋酸乙烯重量百分比为60％)、35重量份的纳米活性碳酸钙、5重量份的钙锌复合稳定剂、1重量份的润滑剂、0.6重量份的三[2.4-二叔丁基苯基]亚磷酸酯和0.5重 量份的高色素炭黑在捏合机中高速搅拌混合，搅拌产生的摩擦热使混合物料温度升至90-100℃后出料，混合物料送入冷却搅拌器冷却至45℃以下，再将冷却后的混合物料置于双阶螺杆挤出机上挤出造粒，其中双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃。将挤出的粒料在平板硫化机上热压成厚度为2mm或6mm样片，并裁切成符合要求的样条。
将上述实施例和对比例中的样条进行拉伸强度、断裂伸长率、热老化、低温瞬时硬度和冲击法脆化温度测试，得到出如下结果：
Figure PCTCN2015093269-appb-000001
从测试结果可以看出，对比例在-5℃时的邵氏硬度均在80以上，耐寒、抗热老化、力学强度等均比实施例差。
上述说明示出并描述了本发明的优选实施例，如前所述，应当理解本发明并非局限于本文所披露的形式，不应看作是对其他实施例的排除，而可用于各种其他组合、修改和环境，并能够在本文所述发明构想范围内，通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围，则都应在本发明所附权利要求的保护范围内。

Claims (10)

  1. 一种环保耐寒聚氯乙烯弹性体组合物，其特征在于，包括聚氯乙烯树脂、环保复合增塑体系、增韧剂、钙锌系复合稳定剂、润滑剂、抗氧剂和颜料，所述环保复合增塑体系包括对苯二甲酸二烷基酯和合成植物油酯，所述增韧剂包括极性橡胶与纳米活性碳酸钙，所述弹性体组合物在-5℃时邵氏硬度低于80，所述对苯二甲酸二烷基酯中烷基包括7～12个碳原子。
  2. 如权利要求1所述的环保耐寒聚氯乙烯弹性体组合物，其特征在于，所述弹性体组合物各组份按重量份计算包括：100重量份的聚氯乙烯树脂、50～90重量份的对苯二甲酸二烷基酯、10～40重量份的合成植物油酯、5～20重量份的极性橡胶、5～30重量份的纳米活性碳酸钙、4～8重量份的钙锌复合稳定剂、1～2重量份的润滑剂、0.2～1重量份的抗氧剂和0.5～3重量份的颜料。
  3. 如权利要求1或2所述的环保耐寒聚氯乙烯弹性体组合物，其特征在于，所述合成植物油酯由植物油经环氧化或环氧基酯化改性而成，所述植物油为大豆油、亚麻油、蓖麻油、红花油和葵花油中的一种或多种组成。
  4. 如权利要求1或2所述的环保耐寒聚氯乙烯弹性体组合物，其特征在于，所述极性橡胶为乙烯-醋酸乙烯酯共聚物橡胶、聚氨酯橡胶和聚丙烯酸酯橡胶中的一种。
  5. 如权利要求4所述的环保耐寒聚氯乙烯弹性体组合物，其特征在于，所述乙烯-醋酸乙烯酯共聚物橡胶中醋酸乙烯酯重量百分比含量为40～70％。
  6. 如权利要求1或2所述的环保耐寒聚氯乙烯弹性体组合物，其特征在于，所述纳米活性碳酸钙的平均直径在60～100nm之间。
  7. 如权利要求1或2所述的环保耐寒聚氯乙烯弹性体组合物，其特征在于，所述润滑剂为硬脂酸锌、硬脂酸和聚乙烯蜡中的一种。
  8. 如权利要求1或2所述的环保耐寒聚氯乙烯弹性体组合物，其特征在于，所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、2,2'-亚甲基-双(4-甲基-6-叔丁基苯酚)、三[2.4-二叔丁基苯基]亚磷酸酯、亚磷酸三苯酯中的一种或两种组成。
  9. 如权利要求1或2所述的环保耐寒聚氯乙烯弹性体组合物，其特征在于，所述颜料为高色素炭黑和金红石型二氧化钛中的一种。
  10. 如权利要求1或2所述的环保耐寒聚氯乙烯弹性体组合物的制备方法，其特征在于，包括如下步骤：
    步骤一：将各组份在捏合机中搅拌混合均匀，利用搅拌产生的摩擦热使混合物温度升高；
    步骤二：捏合机中各组份混合物温度上升到90-100℃后出料，送入冷却搅拌器冷却至45℃以下；
    步骤三：将冷却后的混合物置于双阶螺杆挤出机上挤出造料，所述双阶螺杆挤出机包括双螺杆挤出机和单螺杆挤出机，所述双螺杆挤出机四个加热区和挤出模头的温度分别为：T1＝85～100℃，T2＝100～120℃，T3＝120～140℃，T4＝130～150℃，T模＝130～150℃；所述单螺杆挤出机加热区和挤出模头的温度分别控制在110～130℃和120～140℃，得到聚氯乙烯弹性体组合物，其在-5℃时邵氏硬度低于80。
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