CN1059685C - Polyurethane-containing thermoplastic ternary composition - Google Patents
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Abstract
本发明涉及一种含聚氨酯的热塑性三元组合物，该组合物含有40～90%(重量)的苯乙烯-丙烯腈的无规共聚物和5～30%(重量)的热塑性聚氨酯以及5～50%(重量)的乙烯-醋酸乙烯酯的共聚物。它具有耐老化性能好、生产工艺简单、生产成本低的特点。力学性能相当于通用级ABS，是一种新型的增韧塑料，可用于塑料工业中。The present invention relates to a thermoplastic ternary composition containing polyurethane, the composition contains 40-90% (weight) of styrene-acrylonitrile random copolymer and 5-30% (weight) of thermoplastic polyurethane and 5- 50% (by weight) of ethylene-vinyl acetate copolymer. It has the characteristics of good aging resistance, simple production process and low production cost. The mechanical properties are equivalent to general-purpose ABS, and it is a new type of toughened plastic that can be used in the plastics industry.
Description
本发明涉及增韧塑料，特别是关于含聚氨酯的三元增韧塑料。The present invention relates to toughened plastics, in particular to ternary toughened plastics containing polyurethane.
众所周知ABS塑料是典型的橡胶增韧塑料。它具有良好的综合力学性能，易加工成型，是目前用量大，使用广泛的通用型工程塑料。然而由于ABS组份中丁二烯含有双键，在紫外线作用下易氧化降解，耐候性较差，在室外暴露半年以后抗冲强度将下降45％。另外由于塑料相和橡胶相之间折光指数的悬殊，树脂透明性差，限制了它在某些方面的应用。为此在如何改善ABS性能方面，人们从共聚改性和共混改性方面做了大量的工作。文献昭57～34146报道了以苯乙烯-丙烯腈的无规共聚物(简称SAN)和热塑性聚氨酯(简称TPU)为原料制备透明性热塑性树脂组合物。该专利主要是在于使用聚酯型的聚氨酯为原料，通过两原料折光率的匹配，得到一种透明性的增韧塑料。但其增韧组合物的力学性能不够理想，同时使用大量的热塑性聚氨酯，其原料的成本也较高。为了克服上述技术存在的缺点，提供一种具有良好的屈服强度、断裂强度和断裂伸长率等力学性能，同时原料成本也较低廉的增韧塑料，本发明人发明了含聚氨酯的热塑性三元组合物。It is well known that ABS plastic is a typical rubber toughened plastic. It has good comprehensive mechanical properties and is easy to process and shape. It is a general-purpose engineering plastic that is currently used in large quantities and widely used. However, because the butadiene in the ABS component contains double bonds, it is easy to oxidize and degrade under the action of ultraviolet rays, and the weather resistance is poor. After half a year of outdoor exposure, the impact strength will drop by 45%. In addition, due to the great disparity in the refractive index between the plastic phase and the rubber phase, the resin has poor transparency, which limits its application in some aspects. For this reason, people have done a lot of work on how to improve the performance of ABS from the aspects of copolymerization modification and blending modification. Documents No. 57-34146 report the preparation of transparent thermoplastic resin compositions using styrene-acrylonitrile random copolymers (abbreviated as SAN) and thermoplastic polyurethane (abbreviated as TPU). The patent is mainly to use polyester-type polyurethane as a raw material, and obtain a transparent toughened plastic by matching the refractive index of the two raw materials. However, the mechanical properties of the toughened composition are not satisfactory, and a large amount of thermoplastic polyurethane is used, and the raw material cost is relatively high. In order to overcome the shortcomings of the above-mentioned technologies and provide a kind of toughened plastic with good mechanical properties such as yield strength, breaking strength and elongation at break, and the cost of raw materials is also relatively low, the inventor invented a thermoplastic ternary plastic containing polyurethane. combination.
本发明的目的是通过以下的技术方案来实现的：一种含聚氨酯的热塑性三元组合物，含40～90％(重量)的苯乙烯-丙烯腈的无规共聚物和5～30％(重量)的热塑性聚氨酯以及5～50％(重量)的乙烯-醋酸乙烯酯的共聚物。The object of the present invention is achieved by the following technical solutions: a polyurethane-containing thermoplastic ternary composition, containing 40-90% (weight) of styrene-acrylonitrile random copolymer and 5-30% ( weight) of thermoplastic polyurethane and 5-50% (weight) of ethylene-vinyl acetate copolymer.
上述技术方案中苯乙烯-丙烯腈无规共聚物中丙烯腈的含量为15～40％(重量)，其优选范围为20～30％(重量)。组合物中苯乙烯-丙烯腈无规共聚物的百分含量优选范围为60～80％(重量)。热塑性聚氨酯百分含量优选范围为5～20％(重量)，乙烯-醋酸乙烯酯共聚物百分含量优选范围为10～30％(重量)。所用的热塑性聚氨酯是由15～50％(重量)的二异氰酸酯和扩链剂构成硬段，50～85％(重量)的聚醚、聚酯或聚醚-聚酯构成软段。其中较好的热塑性聚氨酯由20～30％(重量)的二异氰酸酯和扩链剂构成硬段，70～80％(重量)的聚醚、聚酯或聚醚-聚酯构成软段。The content of acrylonitrile in the styrene-acrylonitrile random copolymer in the above technical solution is 15-40% by weight, and its preferred range is 20-30% by weight. The percentage content of the styrene-acrylonitrile random copolymer in the composition preferably ranges from 60 to 80% by weight. The preferred range of thermoplastic polyurethane percentage is 5-20% by weight, and the preferred range of ethylene-vinyl acetate copolymer percentage is 10-30% by weight. The thermoplastic polyurethane used is composed of 15-50% by weight of diisocyanate and chain extender as hard segment, and 50-85% by weight of polyether, polyester or polyether-polyester as soft segment. Among them, the preferred thermoplastic polyurethane consists of 20-30% (weight) of diisocyanate and chain extender to form the hard segment, and 70-80% (by weight) of polyether, polyester or polyether-polyester to form the soft segment.
本发明中所用的热塑性聚氨酯弹性体，它是由聚酯、聚醚或聚酯和聚醚的共聚物等低聚物多元醇和二异氰酸酯及扩链剂小分子二醇或二胺，通过逐步加成聚合制得由软、硬段交替组成的多嵌段共聚物。其中聚酯多元醇可以由不同的饱和脂肪酸或芳香酸和不同品种的二元醇缩聚而成。The thermoplastic polyurethane elastomer used among the present invention, it is by polyester, polyether or polyester and polyether copolymer etc. oligomer polyol and diisocyanate and chain extender small molecular diol or diamine, by adding step by step A multi-block copolymer composed of alternating soft and hard segments is obtained by synthesizing polymerization. Among them, polyester polyols can be formed by polycondensation of different saturated fatty acids or aromatic acids and diols of different varieties.
本发明组合物的制备可以用双辊炼胶机、静态混合器或双螺杆挤出。共混温度为160～190℃，共混时间为5～10分钟。样品力学性能的测试为：先将上述工艺共混制得的共混物在160～180℃、60Kg/cm2的平板硫化机中模压成1mm左右的薄片，然后裁切成亚铃试条，在DL-1000型电子拉力机上测定试样的应力～应变曲线，拉伸速度5mm/min。由此计算出组合物的屈服强度、断裂强度和断裂伸长率。The composition of the present invention can be prepared by twin-roll mill, static mixer or twin-screw extrusion. The blending temperature is 160-190° C., and the blending time is 5-10 minutes. The test of the mechanical properties of the sample is as follows: firstly, the blend prepared by the above process is molded into a thin sheet of about 1mm in a flat vulcanizing machine at 160-180°C and 60Kg/ cm2 , and then cut into Yaling test strips. The stress-strain curve of the sample was measured on a DL-1000 electronic tensile machine, and the tensile speed was 5mm/min. From this the yield strength, breaking strength and breaking elongation of the composition were calculated.
在本技术方案中，由于用饱和的含极性的热塑性橡胶和与之相匹配的高刚脆性塑料共混，通过调节热塑性橡胶的化学结构和组成，使橡胶相和塑料相之间建立起了适度的特殊相互作用，热塑性橡胶同时起着增韧与增容的双重作用。同时用乙烯-醋酸乙烯酯的共聚物代替部分聚氨酯组份，既保持了组合物的力学性能，同时降低了原料成本。最后通过简单的机械共混，毋需加入相溶剂，就得到了具有良好综合力学性能的新一代含聚氨酯三元增韧塑料。组合物的屈服强度，断裂强度和断裂伸长率等力学性能相当于通用级ABS树脂的指标。另外，由于不用含双键的聚丁二烯橡胶，使得热塑性组合物具有了较好的老化性能，取得了较好的效果。In this technical solution, since the saturated polar thermoplastic rubber is blended with the matched high rigidity and brittle plastic, by adjusting the chemical structure and composition of the thermoplastic rubber, a bond is established between the rubber phase and the plastic phase. Moderate special interaction, thermoplastic rubber plays a dual role of toughening and compatibilizing at the same time. At the same time, the ethylene-vinyl acetate copolymer is used to replace part of the polyurethane component, which not only maintains the mechanical properties of the composition, but also reduces the cost of raw materials. Finally, through simple mechanical blending without adding a phase solvent, a new generation of polyurethane-containing ternary toughened plastics with good comprehensive mechanical properties was obtained. The mechanical properties such as yield strength, breaking strength and breaking elongation of the composition are equivalent to the indexes of general-purpose ABS resin. In addition, because the polybutadiene rubber containing double bonds is not used, the thermoplastic composition has better aging properties and better results have been achieved.
【实施例1】【Example 1】
将80克苯乙烯-丙烯腈的无规共聚物，其中丙烯腈含量为15％(重量)、60克聚酯型热塑性聚氨酯，其中二异氰酸酯含量为15％(重量)、60克乙烯-醋酸乙烯酯的共聚物放入双辊炼胶机中共混，共混温度为170℃，时间15分钟。共混结束后，将制得的共混物在170℃、60Kg/cm2的平板硫化机中模压成1mm左右的薄片，然后裁切成哑铃试条，在DL-1000型电子拉力机上测定试样的应力～应变曲线，拉伸速度为5mm/min。由此计算得屈服应力为26.5MPa，断裂强度为34.5MPa，断裂伸长率为275％。【实施例2】80 grams of styrene-acrylonitrile random copolymer with acrylonitrile content of 15% by weight, 60 grams of polyester thermoplastic polyurethane with a diisocyanate content of 15% by weight, 60 grams of ethylene-vinyl acetate The ester copolymer was blended in a two-roll rubber mixer, the blending temperature was 170° C., and the blending time was 15 minutes. After the blending is completed, the prepared blend is molded into a thin sheet of about 1mm in a flat vulcanizing machine at 170°C and 60Kg/ cm2 , and then cut into dumbbell test strips, and tested on a DL-1000 electronic tensile machine. The stress-strain curve of the sample, the tensile speed is 5mm/min. The calculated yield stress is 26.5MPa, the breaking strength is 34.5MPa, and the breaking elongation is 275%. [Example 2]
按照实施例1的试验方法与测试计算方法。加入苯乙烯-丙烯腈的无规共聚物100克，其中丙烯腈含量为15％(重量)、80克聚醚型热塑性聚氨酯，其中二异氰酸酯含量为15％(重量)、20克乙烯-醋酸乙烯酯的共聚物。经测试计算结果：屈服应力为24.8MPa，断裂强度为37.1MPa-，断裂伸长率为285.6％。【实施例3】According to the test method and test calculation method of Example 1. Add 100 grams of random copolymers of styrene-acrylonitrile, wherein the content of acrylonitrile is 15% by weight, 80 grams of polyether thermoplastic polyurethane, wherein the content of diisocyanate is 15% by weight, 20 grams of ethylene-vinyl acetate ester copolymers. The calculation result of the test: the yield stress is 24.8MPa, the breaking strength is 37.1MPa-, and the breaking elongation is 285.6%. [Example 3]
按照实施例1的试验方法与测试计算方法。加入苯乙烯-丙烯腈的无规共聚物120克，其中丙烯腈含量为20％(重量)、44克聚醚-聚酯型的热塑性聚氨酯，其中二异氰酸酯含量为20％(重量)、36克乙烯-醋酸乙烯酯的共聚物。经测试计算结果：屈服应力为34.5MPa，断裂强度为31.8MPa，断裂伸长率为102.3％。【实施例4】According to the test method and test calculation method of Example 1. Add 120 grams of random copolymers of styrene-acrylonitrile, wherein the content of acrylonitrile is 20% (weight), 44 grams of thermoplastic polyurethane of polyether-polyester type, wherein the content of diisocyanate is 20% (weight), 36 grams Copolymer of ethylene-vinyl acetate. The calculation result of the test: the yield stress is 34.5MPa, the breaking strength is 31.8MPa, and the breaking elongation is 102.3%. 【Example 4】
按照实施例1的试验方法与测试计算方法。加入苯乙烯-丙烯腈的无规共聚物120克，其中丙烯腈含量为30％(重量)、56克聚酯型热塑性聚氨酯，其中二异氰酸酯含量为25％(重量)、24克乙烯-醋酸乙烯酯的共聚物。经测试计算结果：屈服应力为32.9MPa，断裂强度为32.4MPa，断裂伸长率为153.2％。【实施例5】According to the test method and test calculation method of Example 1. Add 120 grams of random copolymer of styrene-acrylonitrile, wherein the content of acrylonitrile is 30% by weight, 56 grams of polyester thermoplastic polyurethane, wherein the content of diisocyanate is 25% by weight, 24 grams of ethylene-vinyl acetate ester copolymers. The calculation result of the test: the yield stress is 32.9MPa, the breaking strength is 32.4MPa, and the breaking elongation is 153.2%. 【Example 5】
按照实施例1的试验方法与测试计算方法。加入苯乙烯-丙烯腈的无规共聚物140克，其中丙烯腈含量为25％(重量)、32克聚醚-聚酯型的热塑性聚氨酯，其中二异氰酸酯含量为30％(重量)、28克乙烯-醋酸乙烯酯的共聚物。经测试计算结果：屈服应力为39.8MPa，断裂强度为32.5MPa，断裂伸长率为37.2％。【实施例6】According to the test method and test calculation method of Example 1. Add 140 grams of random copolymers of styrene-acrylonitrile, wherein the content of acrylonitrile is 25% by weight, 32 grams of thermoplastic polyurethane of polyether-polyester type, wherein the content of diisocyanate is 30% by weight, 28 grams Copolymer of ethylene-vinyl acetate. The calculation result of the test: the yield stress is 39.8MPa, the breaking strength is 32.5MPa, and the breaking elongation is 37.2%. [Example 6]
按照实施例1的试验方法与测试计算方法。加入苯乙烯-丙烯腈的无规共聚物140克，其中丙烯腈含量为20％(重量)、40克聚醚型热塑性聚氨酯，其中二异氰酸酯含量为25％(重量)、20克乙烯-醋酸乙烯酯的共聚物。经测试计算结果：屈服应力为39.4MPa，断裂强度为31.0MPa，断裂伸长率为60.3％。【实施例7】According to the test method and test calculation method of Example 1. Add 140 grams of random copolymers of styrene-acrylonitrile, wherein the content of acrylonitrile is 20% by weight, 40 grams of polyether thermoplastic polyurethane, wherein the content of diisocyanate is 25% by weight, 20 grams of ethylene-vinyl acetate ester copolymers. The calculation result of the test: the yield stress is 39.4MPa, the breaking strength is 31.0MPa, and the breaking elongation is 60.3%. [Example 7]
按照实施例1的试验方法与测试计算方法。加入苯乙烯-丙烯腈的无规共聚物160克，其中丙烯腈含量为15％(重量)、8克聚酯型热塑性聚氨酯，其中二异氰酸酯含量为20％(重量)、32克乙烯-醋酸乙烯酯的共聚物。经测试计算结果：屈服应力为41.7MPa，断裂强度为38.1MPa，断裂伸长率为9.4％。【实施例8】According to the test method and test calculation method of Example 1. Add 160 grams of random copolymer of styrene-acrylonitrile, wherein the content of acrylonitrile is 15% by weight, 8 grams of polyester thermoplastic polyurethane, wherein the content of diisocyanate is 20% by weight, 32 grams of ethylene-vinyl acetate ester copolymers. The calculation result of the test: the yield stress is 41.7MPa, the breaking strength is 38.1MPa, and the breaking elongation is 9.4%. [Embodiment 8]
按照实施例1的试验方法与测试计算方法，加入苯乙烯-丙烯腈的无规共聚物180克，其中丙烯腈含量为40％(重量)、10克聚醚型热塑性聚氨酯，其中二异氰酸酯含量为40％(重量)、10克乙烯-醋酸乙烯酯的共聚物。经测试计算结果：屈服应力为59.8MPa，断裂强度为52.6MPa，断裂伸长率为8.9％。〖比较例1〗According to the test method and test calculation method of embodiment 1, add 180 grams of random copolymers of styrene-acrylonitrile, wherein acrylonitrile content is 40% (weight), 10 gram polyether type thermoplastic polyurethanes, wherein diisocyanate content is 40% by weight, 10 grams of ethylene-vinyl acetate copolymer. The calculation result of the test: the yield stress is 59.8MPa, the breaking strength is 52.6MPa, and the breaking elongation is 8.9%. 〖Comparative Example 1〗
将200克通用级ABS树脂放入双辊炼胶机中，加热树脂达温度170℃，然后在温度170℃、压力60Kg/cm2的平板硫化机中将ABS树脂模压成1mm左右的薄片，然后裁切成哑铃试条，在DL-1000型电子拉力机上测定试样的应力～应变典线，拉伸速度为5m/m。由此计算屈服应力为40MPa，断裂强度为32MPa，断裂伸长率为40％。Put 200 grams of general-purpose ABS resin into a double-roller rubber mixer, heat the resin to a temperature of 170°C, and then mold the ABS resin into a sheet of about 1mm in a flat vulcanizer at a temperature of 170°C and a pressure of 60Kg/ cm2 , and then Cut into dumbbell test strips, and measure the stress-strain typical line of the sample on a DL-1000 electronic tensile machine with a tensile speed of 5m/m. From this, the yield stress is calculated as 40MPa, the breaking strength is 32MPa, and the breaking elongation is 40%.
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| JPS5059243A (en) * | 1973-09-22 | 1975-05-22 | ||
| JPS5734146A (en) * | 1980-08-11 | 1982-02-24 | Asahi Chem Ind Co Ltd | Transparent impact-resistant thermoplastic resin composition |
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| JPS5059243A (en) * | 1973-09-22 | 1975-05-22 | ||
| JPS5734146A (en) * | 1980-08-11 | 1982-02-24 | Asahi Chem Ind Co Ltd | Transparent impact-resistant thermoplastic resin composition |
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