一种含有乙烯基双硬质酰胺的增刚成核剂组合物Increased nucleating agent composition containing vinyl bis-hard amide
技术领域Technical field
本发明涉及成核剂领域,具体涉及一种含有乙烯基双硬质酰胺的增刚成核剂组合物,同时涉及含有该成核剂组合物的热塑性塑料。The present invention relates to the field of nucleating agents, and in particular to a rigid nucleating agent composition containing vinyl bis-hard amide, and to a thermoplastic containing the nucleating agent composition.
技术背景technical background
热塑性塑料是指具有加热软化至于流动、冷却硬化特性的塑料,可以通过注射、挤出和吹塑加工成具有各种用途的注塑制品,如日用生活制品、医疗器具、电器、汽车以及管材管道等。本发明所涉及的热塑性聚合物包括但不限于聚烯烃(例如聚乙烯、聚丙烯、聚丁烯及其任何组合)、聚酰胺(例如尼龙)、聚氨基甲酸酯、聚酯(例如聚对苯二甲酸乙二酯)及其类似物。Thermoplastic refers to plastics with heat softening to flow and cooling hardening properties, which can be processed into various injection molded products by injection, extrusion and blow molding, such as daily life products, medical appliances, electrical appliances, automobiles and pipe pipes. Wait. Thermoplastic polymers to which the present invention relates include, but are not limited to, polyolefins (e.g., polyethylene, polypropylene, polybutylene, and any combination thereof), polyamides (e.g., nylon), polyurethanes, polyesters (e.g., poly-pairs). Ethylene phthalate) and its analogs.
目前通常所关注的在热塑性塑料例如聚烯烃、尼龙等中加入成核剂相关性能主要是以下方面:1、快的聚合物结晶速度和/或高结晶温度,聚合物熔体冷却固化结晶过程中,大分子长链由无序到有序的结晶状态,需较长的驰豫时间,结晶速率和结晶温度都低,而且会形成较大的球晶,球晶之间存在明显的界面引起不同的内应力,当受外力冲击时易产生裂纹而破裂,而在聚合物融体配制剂的冷却过程中加入成核剂后,利用成核剂化合物来提供晶体生长所用的成核点,使得结晶速度加快,从而使得在较高温度下进行结晶,而高的聚合物峰值结晶温度表示高的成核功效;其最终体现在制造部件上来说,高成核功效通常意味着快的加工周期和更理想的物理性能例如硬度、弹性模量、拉伸强度、冲击平衡等,一般来说,热塑性塑料的刚性由弯曲模量来表征,其韧性由冲击强度来表征;2、高透明度:目前需要热塑性塑料制品自身具有良好的透明度,在塑料中均匀分散的成核剂变小,晶体变得细微,微细化的晶体减少了结晶部分和非晶部分界面上的散射,当晶体尺寸小于1微米时,透明性急剧增加。At present, the related properties of adding a nucleating agent to thermoplastics such as polyolefins, nylons, etc. are mainly as follows: 1. Fast polymer crystallization rate and/or high crystallization temperature, during polymer melt cooling and solidification crystallization Long chain of macromolecules from disordered to ordered crystalline state requires longer relaxation time, low crystallization rate and crystallization temperature, and large spherulites are formed, and obvious interfaces between spherulites cause different The internal stress, when impacted by external force, is prone to cracking and cracking. After the nucleating agent is added during the cooling of the polymer melt formulation, the nucleating agent compound is used to provide the nucleation point for crystal growth, so that the crystallization Speed is increased, allowing crystallization to occur at higher temperatures, while high polymer peak crystallization temperatures indicate high nucleation efficiency; ultimately, in manufacturing parts, high nucleation efficiency usually means fast processing cycles and more Ideal physical properties such as hardness, modulus of elasticity, tensile strength, impact balance, etc. In general, the stiffness of a thermoplastic is characterized by a flexural modulus, Characterization is characterized by impact strength; 2. High transparency: It is currently required that the thermoplastic product itself has good transparency, the nucleating agent uniformly dispersed in the plastic becomes smaller, the crystal becomes fine, and the refined crystal reduces the crystal part and the non- Scattering at the interface of the crystal portion, when the crystal size is less than 1 μm, the transparency sharply increases.
此外,在热塑性塑料特别是尼龙的加工过程中,往往还存在难于脱模的困扰,目前市场上绝大部分尼龙在注塑过程中不易脱模,且流动性不强,给制造带来困扰,因此目前绝大部分的加工中采用添加脱模剂,然而脱模剂中含有多环芳氰,其属于环保
要求中严格限制的成分,为了确保安全,达到环保要求,最直接的办法就是原材料本身容易脱模,不需要用到脱模剂。In addition, in the processing of thermoplastics, especially nylon, there are often difficulties in demoulding. Most of the nylons on the market are not easily demolded during the injection molding process, and the fluidity is not strong, which causes troubles in manufacturing. At present, most of the processing uses the addition of a release agent, but the release agent contains polycyclic aryl cyanide, which is environmentally friendly.
In order to ensure safety and meet environmental protection requirements, the most direct method is to remove the mold itself without using a release agent.
现有技术中,乙烯基双硬质酰胺也称作乙撑双硬质酰胺,简称EBS,其是近年发展起来的新型塑料润滑剂,广泛应用于PVC制品、ABS、高抗冲聚苯乙烯、聚烯烃、橡胶、塑料制品的成型加工中。由于在其分子结构中含有二个酰胺基-C-NH-,因而,该产品加入塑料后,使塑料制品具有较好的防静电性,使塑料制品不易“吸尘”着脏。同时有零星的报道表明EBS尚可作为成核透明剂,在聚烯烃,聚甲醛和聚酰胺等化合物中能够缩短它的成核时间,促进树脂结构的变细,进而改善制品的机械性能和透明度。但是没有任何有关其与其它成核剂组合使用以提高其性能,特别是提高聚合物的刚性。In the prior art, vinyl bis-hard amide is also called ethylene bis-hard amide, referred to as EBS, which is a new type of plastic lubricant developed in recent years, widely used in PVC products, ABS, high impact polystyrene, In the molding process of polyolefin, rubber and plastic products. Since the molecular structure contains two amide groups -C-NH-, the plastic product has good antistatic property after being added to the plastic, so that the plastic product is not easy to "dust" and dirty. At the same time, there are sporadic reports that EBS can be used as a nucleating transparent agent, which can shorten its nucleation time in polyolefin, polyoxymethylene and polyamide compounds, promote the thinning of resin structure, and improve the mechanical properties and transparency of products. . However, there is nothing to do with its use in combination with other nucleating agents to improve its properties, especially to increase the rigidity of the polymer.
关于复合成核剂,已授权专利CN102219927B保护一种成核剂组合物,该组合物由一定比例的苯甲酸钠、对叔丁基苯甲酸羟基铝和双[2,2’-亚甲基-二(4,6-二叔丁基苯基)]磷酸铝组成,研究表明,所述成核剂组合物突破了原有单一成核剂不能同时提高聚丙烯冲击强度和弯曲模量的限制,不但可以提高聚丙烯制品的弯曲模量和热变形温度,而且还能显著提高冲击强度。CN102850578B公开了二芳基有机磷酸盐和芳香族羧酸金属盐的成核剂组合物,其对于聚烯烃的刚性、透明性和耐热性相比单独使用具有更好的效果。CN101065434A公开了包括两种成核剂的热塑性聚合物组合物,分别是将二羧酸盐和有机磷酸盐进行组合,结果表明,相比单独的,其透明性、韧性和刚性均增强。Regarding the composite nucleating agent, the patent CN102219927B has been protected by a nucleating agent composition consisting of a certain proportion of sodium benzoate, hydroxyaluminum p-tert-butylbenzoate and bis[2,2'-methylene-di- (4,6-di-tert-butylphenyl)]aluminum phosphate composition, studies have shown that the nucleating agent composition breaks through the original single nucleating agent can not simultaneously increase the polypropylene impact strength and flexural modulus limit, not only The flexural modulus and heat distortion temperature of the polypropylene article can be increased, and the impact strength can be remarkably improved. CN102850578B discloses a nucleating agent composition of a diaryl organophosphate and an aromatic carboxylic acid metal salt which has a better effect on the rigidity, transparency and heat resistance of the polyolefin than when used alone. CN101065434A discloses a thermoplastic polymer composition comprising two nucleating agents, respectively, which combines a dicarboxylate and an organophosphate, and the results show that the transparency, toughness and rigidity are enhanced compared to the individual.
由此可见,关于两种或多种成核剂配置成复合成核剂的研究逐渐成为热点。而将多种成核剂掺杂在一起使用在化学领域非常难以预测的区域,除非经过尝试、试验并完成相对大量的工作,否则通常无法知道哪种物质有效。It can be seen that research on the configuration of two or more nucleating agents into composite nucleating agents has gradually become a hot spot. The use of multiple nucleating agents is used in areas that are very difficult to predict in the chemical field, and unless a large amount of work is tried, tested, and done, it is often impossible to know which substance is effective.
目前需要提供一种针对热塑性塑料的成核剂,其能兼具快的聚合物结晶速度和/或高结晶温度的同时,还在脱模性能上有所改进。本发明申请人经过长时间的探索,开发出一种成核剂组合物,所述组合物相比其单独组分而言,在上述性能均有较大的改善。There is a need to provide a nucleating agent for thermoplastics that combines fast polymer crystallization rates and/or high crystallization temperatures while also providing improved release properties. The applicant of the present invention has developed a nucleating agent composition which has been greatly improved in the above properties as compared with its individual components after a long period of investigation.
发明内容Summary of the invention
本发明目的在于提供一种含有乙烯基双硬质酰胺的增刚成核剂组合物,所述成核
剂组合物,在目标热塑性塑料制品中同时产生高成核效率以及改善制品的脱模性能。所述高成核效率表现为快的聚合物结晶速度和/或高结晶温度,从而最终使得产品的弯曲模量以及热变形温度都得到显著提高。The object of the present invention is to provide a nucleating nucleating agent composition containing vinyl bis-hard amide, said nucleation
The composition of the composition simultaneously produces high nucleation efficiency in the target thermoplastic article and improves the release properties of the article. The high nucleation efficiency is manifested by a fast polymer crystallization rate and/or a high crystallization temperature, which ultimately results in a significant increase in the flexural modulus and heat distortion temperature of the product.
本发明的目的之二是提供将上述成核剂组合物在热塑性塑料中的应用。Another object of the present invention is to provide the use of the above nucleating agent composition in a thermoplastic.
本发明的目的之三是提供将上述成核剂组合物在聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)以及尼龙(PA6或PA66)中的应用。A third object of the present invention is to provide the above nucleating agent composition in polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and nylon (PA6 or PA66). application.
为了实现上述目的,本发明提供了一种含有乙烯基双硬质酰胺的增刚成核剂组合物,所述成核剂组合物含有二-[4-叔丁基苯甲酸]羟基铝和乙烯基双硬质酰胺,二者的重量比为5:1~1:5。In order to achieve the above object, the present invention provides a nucleating nucleating agent composition containing a vinyl bis-chamelamide containing bis-[4-tert-butylbenzoic acid] hydroxyaluminum and ethylene The base double hard amide has a weight ratio of 5:1 to 1:5.
优选地,二-[4-叔丁基苯甲酸]羟基铝和乙烯基双硬质酰胺的重量比为3:1~1:3;最优选地,二者的重量比为1:1。Preferably, the weight ratio of bis-[4-tert-butylbenzoic acid]hydroxyaluminum to vinyl bis-carbamide is from 3:1 to 1:3; most preferably, the weight ratio of the two is 1:1.
进一步地,还可以在上述增刚成核剂组合物的基础上额外加入水合硅酸镁,形成三元的含有乙烯基双硬质酰胺的增刚成核剂组合物,所述成核剂组合物含有二-[4-叔丁基苯甲酸]羟基铝、乙烯基双硬质酰胺和水合硅酸镁,三者的重量比为1-3:1-3:1-5;优选为1-2:1-2:1-4,最优选为1:1:2。Further, hydrated magnesium silicate may be additionally added to the above-mentioned nucleating nucleating agent composition to form a ternary addition nucleating nucleating agent composition containing vinyl bis-hard amide, the nucleating agent combination Containing bis-[4-tert-butylbenzoic acid]hydroxyaluminum, vinyl bis-hard amide and hydrated magnesium silicate, the weight ratio of the three is 1-3:1-3:1-5; preferably 1- 2:1-2:1-4, most preferably 1:1:2.
本发明进一步提供将上述成核剂组合物在热塑性塑料中的应用。The invention further provides for the use of the above nucleating agent composition in a thermoplastic.
本发明进一步提供将上述成核剂组合物在PET、PBT以及尼龙中的应用。The invention further provides for the use of the above nucleating agent compositions in PET, PBT and nylon.
本发明提供了上述成核剂组合物用于同时提高上述制品的弯曲模量以及脱模性。The present invention provides the above nucleating agent composition for simultaneously increasing the flexural modulus and mold release property of the above article.
本发明还提供了一种热塑性塑料,热塑性塑料包含上述的成核剂组合物和热塑性塑料,其中成核剂组合物的重量占热塑性塑料重量的0.01-2.00%;优选为0.05-1.00%;进一步优选为0.05-0.50%;特别优选为0.05-0.15%;所述热塑性塑料为PET、PBT或尼龙。The present invention also provides a thermoplastic comprising a nucleating agent composition and a thermoplastic as described above, wherein the weight of the nucleating agent composition is from 0.01 to 2.00% by weight of the thermoplastic; preferably from 0.05 to 1.00%; further It is preferably 0.05-0.50%; particularly preferably 0.05-0.15%; the thermoplastic is PET, PBT or nylon.
本发明所涉及的“热塑性塑料”是指暴露于足够的热量时会熔化,但是进行足够冷却时将保持固态但若不利用模子或类似物品不会保持原有形状的聚合物材料。具体来说,该术语也可仅包括以下宽范围定义的聚合物:在融体形成之后,通过冷却也可显示出结晶或半结晶形态的聚合物。本发明所涉及的热塑性聚合物包括但不限于聚烯烃(例如聚乙烯、聚丙烯、聚丁烯及其任何组合)、聚酰胺(例如尼龙)、聚氨基甲酸酯、聚酯(例如聚对苯二甲酸乙二酯)及其类似物。The term "thermoplastic" as used in the present invention refers to a polymeric material that will melt upon exposure to sufficient heat, but will remain solid when sufficiently cooled, but will not retain its original shape without the use of molds or the like. In particular, the term may also include only polymers defined in the broad range below: after formation of the melt, the polymer may also exhibit a crystalline or semi-crystalline form by cooling. Thermoplastic polymers to which the present invention relates include, but are not limited to, polyolefins (e.g., polyethylene, polypropylene, polybutylene, and any combination thereof), polyamides (e.g., nylon), polyurethanes, polyesters (e.g., poly-pairs). Ethylene phthalate) and its analogs.
除非另有说明,本申请中的“%”指重量百分比。
Unless otherwise stated, "%" in the present application refers to a percentage by weight.
本发明的上述成核剂组合物与PET、PBT或尼龙混合时,可以加入其它物质以提高制品的其他性能。When the above nucleating agent composition of the present invention is mixed with PET, PBT or nylon, other substances may be added to enhance other properties of the article.
本发明所提供的成核剂组合物弥补了单一成核剂在提高热塑性塑料制品刚性、脱模性等性能不佳的情况下,充分发挥成核剂组合物中各种成核剂的功能优势,使得最终产品能兼具上述多种性能。The nucleating agent composition provided by the invention makes up for the function advantage of various nucleating agents in the nucleating agent composition under the condition that the single nucleating agent improves the rigidity and the mold release property of the thermoplastic plastic product. So that the final product can combine the above various properties.
本发明的成核剂组合物中加入乙烯基双硬质酰胺后应用于热塑性塑料制品时,脱模性能得到显著的提高,同时制品的光泽度也得到改善。When a vinyl bis-carbamide is added to the nucleating agent composition of the present invention and applied to a thermoplastic article, the release property is remarkably improved, and the gloss of the article is also improved.
经本发明的成核剂组合物改性的热塑性塑料PET、PBT以及尼龙可以经受长时间的高温和机械应力,适合于日用生活制品、医疗器具、电器、汽车以及管材管道等户外专用料领域的应用。The thermoplastic PET, PBT and nylon modified by the nucleating agent composition of the invention can withstand high temperature and mechanical stress for a long time, and are suitable for outdoor special materials such as daily life products, medical appliances, electric appliances, automobiles and pipe pipes. Applications.
具体实施方式detailed description
本发明可由以下实施例进一步阐明,但这里提供的只是本发明的优选实施方式,本发明的范围并不受此限制。The invention is further clarified by the following examples, but the preferred embodiments of the invention are provided herein, and the scope of the invention is not limited thereto.
一、制备实施例:First, the preparation example:
原料来源:二-[4-叔丁基苯甲酸]羟基铝、乙烯基双硬质酰胺以及水合硅酸镁均为市售产品。Sources of raw materials: bis-[4-tert-butylbenzoic acid]hydroxyaluminum, vinyl bis-hard amide and hydrated magnesium silicate are all commercially available products.
PET、PBT以及尼龙(PA6)也均为市售产品(具体型号分别为PET-BG80,PBT-1100,PA6-M2000)PET, PBT and nylon (PA6) are also commercially available (specific models are PET-BG80, PBT-1100, PA6-M2000)
1、本发明成核剂组合物的制备1. Preparation of the nucleating agent composition of the present invention
实施例1:Example 1:
分别准确称取二-[4-叔丁基苯甲酸]羟基铝8.3g、乙烯基双硬质酰胺1.7g,然后在搅拌器中均匀混合,得到本发明成核剂1。8.3 g of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and 1.7 g of vinylbis-hard amide were accurately weighed and uniformly mixed in a stirrer to obtain a nucleating agent 1 of the present invention.
实施例2:Example 2:
分别准确称取二-[4-叔丁基苯甲酸]羟基铝1.7g、乙烯基双硬质酰胺8.3g,然后在搅拌器中均匀混合,得到本发明成核剂2。1.7 g of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and 8.3 g of vinylbis-hard amide were accurately weighed and uniformly mixed in a stirrer to obtain a nucleating agent 2 of the present invention.
实施例3:Example 3:
分别准确称取二-[4-叔丁基苯甲酸]羟基铝7.5g、乙烯基双硬质酰胺2.5g,然后在搅拌器中均匀混合,得到本发明成核剂3。
7.5 g of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and 2.5 g of vinylbis-hard amide were accurately weighed and uniformly mixed in a stirrer to obtain a nucleating agent 3 of the present invention.
实施例4:Example 4:
分别准确称取二-[4-叔丁基苯甲酸]羟基铝2.5g、乙烯基双硬质酰胺7.5g,然后在搅拌器中均匀混合,得到本发明成核剂4。2.5 g of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and 7.5 g of vinyl bis-hardamide were accurately weighed separately, and then uniformly mixed in a stirrer to obtain a nucleating agent 4 of the present invention.
实施例5:Example 5:
分别准确称取二-[4-叔丁基苯甲酸]羟基铝5g、乙烯基双硬质酰胺5g,然后在搅拌器中均匀混合,得到本发明成核剂5。5 g of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and 5 g of vinylbis-hard amide were accurately weighed and uniformly mixed in a stirrer to obtain a nucleating agent 5 of the present invention.
实施例6:Example 6
分别准确称取二-[4-叔丁基苯甲酸]羟基铝1.41g、乙烯基双硬质酰胺1.41g,以及水合硅酸镁7.18g,然后在搅拌器中均匀混合,得到本发明成核剂6。Accurately weighed 1.41 g of bis-[4-tert-butylbenzoic acid]hydroxyaluminum, 1.41 g of vinyl bis-hardamide, and 7.18 g of hydrated magnesium silicate, respectively, and then uniformly mixed in a stirrer to obtain the nucleation of the present invention. Agent 6.
实施例7:Example 7
分别准确称取二-[4-叔丁基苯甲酸]羟基铝2.5g、乙烯基双硬质酰胺2.5g,以及水合硅酸镁5g,然后在搅拌器中均匀混合,得到本发明成核剂7。Accurately weigh 2.5 g of bis-[4-tert-butylbenzoic acid]hydroxyaluminum, 2.5 g of vinylbis-hard amide, and 5 g of hydrated magnesium silicate, and then uniformly mix in a stirrer to obtain the nucleating agent of the present invention. 7.
2、应用实施例2. Application examples
(1)本发明成核剂在PA6中的应用(1) Application of the nucleating agent of the invention in PA6
将实施例1制备的成核剂1按照PA6质量的0.15%添加量用双螺杆挤出机挤出造粒、干燥,加工温度250℃,制得尼龙颗粒1。The nucleating agent 1 prepared in Example 1 was extruded and granulated in a twin-screw extruder according to a 0.15% addition amount of PA6 mass, and dried at a processing temperature of 250 ° C to obtain nylon particles 1.
基于相同的方法,分别将上述实施例2-7制备的成核剂2-7分别制得尼龙颗粒2-7。Based on the same method, the nucleating agents 2-7 prepared in the above Examples 2-7 were respectively obtained into nylon particles 2-7.
除成核剂的加入量为0.05%外,基于相同的方法,分别将上述实施例1-7制备的成核剂1-7分别制得尼龙颗粒8-14。The nucleating agents 1-7 prepared in the above Examples 1-7 were respectively obtained into nylon particles 8-14, except that the nucleating agent was added in an amount of 0.05%, based on the same method.
同样地,按照尼龙颗粒1制备的条件,不添加成核剂制备空白的尼龙颗粒对照样品。Similarly, blank nylon particle control samples were prepared without adding a nucleating agent under the conditions of nylon particle 1 preparation.
同样地,按照尼龙颗粒1制备的条件,分别添加目前市场上常用的尼龙成核剂P22和CAV102,加入量为0,15%,制得尼龙颗粒P22和尼龙颗粒CAV102。Similarly, nylon nucleating agents P22 and CAV102 which are currently used in the market were separately added in an amount of 0, 15% in accordance with the conditions for the preparation of the nylon particles 1, and nylon particles P22 and nylon particles CAV102 were obtained.
(2)本发明成核剂在PET中的应用(2) Application of the nucleating agent of the invention in PET
将实施例1制备的成核剂1按照PET质量的0.15%添加量用双螺杆挤出机挤出造粒、干燥,加工温度260℃,制得PET颗粒1。The nucleating agent 1 prepared in Example 1 was extruded and granulated in a twin-screw extruder according to the amount of 0.15% of the PET mass, and dried at a processing temperature of 260 ° C to obtain PET pellets 1.
基于相同的方法,分别将上述实施例2-7制备的成核剂2-7分别制得PET颗粒
2-7。Based on the same method, the nucleating agents 2-7 prepared in the above Examples 2-7 were respectively prepared into PET pellets.
2-7.
除成核剂的加入量为0.05%外,基于相同的方法,分别将上述实施例1-7制备的成核剂1-7分别制得PET颗粒8-14。The nucleating agents 1-7 prepared in the above Examples 1-7 were respectively prepared into PET particles 8-14, except that the amount of the nucleating agent added was 0.05%, based on the same method.
同样地,按照PET颗粒1制备的条件,不添加成核剂制备空白的PET颗粒对照样品。Similarly, blank PET particle control samples were prepared without adding a nucleating agent according to the conditions of PET particle 1 preparation.
(3)本发明成核剂在PBT中的应用(3) Application of the nucleating agent of the invention in PBT
将实施例1制备的成核剂1按照PBT质量的0.15%添加量用双螺杆挤出机挤出造粒、干燥,加工温度250℃,制得PBT颗粒1。The nucleating agent 1 prepared in Example 1 was extruded and granulated by a twin-screw extruder in an amount of 0.15% by mass of PBT, and dried at a processing temperature of 250 ° C to obtain PBT pellets 1.
基于相同的方法,分别将上述实施例2-7制备的成核剂2-7分别制得PBT颗粒2-7。Based on the same method, the nucleating agents 2-7 prepared in the above Examples 2-7 were respectively prepared to obtain PBT particles 2-7, respectively.
除成核剂的加入量为0.05%外,基于相同的方法,分别将上述实施例1-7制备的成核剂1-7分别制得PBT颗粒8-14。Except that the amount of the nucleating agent added was 0.05%, the nucleating agents 1-7 prepared in the above Examples 1-7 were respectively prepared to obtain PBT particles 8-14, respectively, based on the same method.
同样地,按照PBT颗粒1制备的条件,不添加成核剂制备空白的PBT颗粒对照样品。Similarly, blank PBT particle control samples were prepared without adding a nucleating agent according to the conditions of PBT particle 1 preparation.
二、性能测试实施例Second, performance test examples
1、测试结晶温度和脱模效果1. Test crystallization temperature and release effect
针对添加本发明成核剂组合物的尼龙(PA6)的结晶温度采用DSC测试,具体如下:在氮气条件下以10℃/min的升温速度升温至260℃,恒温3min,然后以10℃/min降温至25℃,然后再以10℃/min升温至260℃,记录降温曲线和第二次升温曲线。The crystallization temperature of the nylon (PA6) to which the nucleating agent composition of the present invention is added is tested by DSC, as follows: under nitrogen conditions, the temperature is raised to 260 ° C at a temperature increase rate of 10 ° C / min, the temperature is 3 min, and then 10 ° C / min. The temperature was lowered to 25 ° C, and then the temperature was raised to 260 ° C at 10 ° C / min, and the cooling curve and the second heating curve were recorded.
脱模性能根据完全脱模所需要的时间分为如下4个级别:The demolding performance is divided into the following four levels according to the time required for complete demolding:
(1)差——粘模;(1) poor - sticking mold;
(2)中——人工辅助脱模;(2) Medium - manual assisted demoulding;
(3)良好——基本能自动脱模,偶尔要人工辅助;(3) Good - basically capable of automatic demoulding, occasionally manual assist;
(4)优——完全自动脱模。(4) Excellent - completely automatic demoulding.
下表1-2示出了本发明的组合物以不同的用量和比例应用于尼龙中其相应的结晶温度和脱模效果。
Table 1-2 below shows the compositions of the present invention applied to nylon in their respective crystallization temperatures and release effects in varying amounts and ratios.
表1二-[4-叔丁基苯甲酸]羟基铝和乙烯基双硬质酰胺对PA6结晶温度及制品的脱模效果Table 1 Desiccation effect of bis-[4-tert-butylbenzoic acid] hydroxyaluminum and vinyl bis-carbamide on PA6 crystallization temperature and product
从表1可以看出,二-[4-叔丁基苯甲酸]羟基铝和乙烯基双硬质酰胺复合应用时,PA6的结晶温度明显高于单独添加的二-[4-叔丁基苯甲酸]羟基铝,二者在PA6的异相成核过程中,起到了明显的协同效应,同时脱模性能也得到显著改善;进一步地,结果表明,当二者的比例为1:1时,效果最佳。It can be seen from Table 1 that the crystallization temperature of PA6 is significantly higher than that of bis-[4-tert-butylbenzene added alone when the bis-[4-tert-butylbenzoic acid] hydroxyaluminum and vinyl bis-hard amide are combined. Formic acid] hydroxyaluminum, in the heterogeneous nucleation process of PA6, played a significant synergistic effect, and the release properties were also significantly improved; further, the results show that when the ratio of the two is 1:1, The best results.
表2二-[4-叔丁基苯甲酸]羟基铝、乙烯基双硬质酰胺和水合硅酸镁对PA6结晶温度及制品的脱模效果Table 2 bis-[4-tert-butylbenzoic acid] hydroxyaluminum, vinyl bis-hard amide and hydrated magnesium silicate on the crystallization temperature of PA6 and the release effect of the product
表2所示的三元组合物与表1的二元的测试条件相同,结果表明,在二-[4-叔丁基苯甲酸]羟基铝和乙烯基双硬质酰胺的基础上再添加水合硅酸镁后,其结晶温度进一步提高,相应地,所述制品的机械性能也会得到进一步提升。The ternary composition shown in Table 2 was identical to the binary test conditions of Table 1, and the results showed that hydration was further added on the basis of bis-[4-tert-butylbenzoic acid] hydroxyaluminum and vinyl bis-hard amide. After the magnesium silicate, the crystallization temperature is further increased, and accordingly, the mechanical properties of the article are further improved.
2、进行弯曲模量测试、冲击强度测试、热变形温度测试2. Perform bending modulus test, impact strength test, heat distortion temperature test
将上述应用实施例所制备的尼龙颗粒1—14、尼龙颗粒对照样品以及目前市场上的尼龙成核剂P22和CAV102分别注塑成标准样条,注塑温度为270℃。分别按照如下方法测试其弯曲模量、冲击强度以及热变形温度。The nylon particles 1-4 prepared in the above application examples, the nylon particle control sample, and the nylon nucleating agents P22 and CAV102 currently on the market were respectively injection molded into standard splines at an injection temperature of 270 °C. The flexural modulus, impact strength, and heat distortion temperature were tested as follows.
将上述应用实施例所制备的PET颗粒1—14、PET颗粒对照样品分别注塑成标准样条,注塑温度为280℃。按照如下方法测试其弯曲模量、冲击强度以及热变形温度。The PET particles 1-4 and the PET particle control samples prepared in the above application examples were respectively injection molded into standard splines at an injection temperature of 280 °C. The flexural modulus, impact strength, and heat distortion temperature were tested as follows.
将上述应用实施例所制备的PBT颗粒1—14、PBT颗粒对照样品分别注塑成标准样条,注塑温度为250℃。按照如下方法测试其弯曲模量、冲击强度以及热变形温度。The PBT particles 1-4 and the PBT particle control samples prepared in the above application examples were respectively injection molded into standard splines at an injection temperature of 250 °C. The flexural modulus, impact strength, and heat distortion temperature were tested as follows.
成核剂改性尼龙的测试按GB 2918—1998(塑料试样状态调节和试验的标准环境)规定,在(23±2)℃,相对湿度(RH)为(50±5)%的条件下进行,试样状态调节时间48h。物理性能测试分别按国家标准进行:悬臂梁缺口冲击强度执行标准GB/T 1843-1996,弯曲模量执行标准GB/T9341-2000,热变形温度执行标准GB/T 1634-2004。测试结果列于下表3-5:The nucleating agent modified nylon is tested according to GB 2918-1998 (standard environment for plastic sample state adjustment and testing), at (23 ± 2) ° C, relative humidity (RH) is (50 ± 5)% The sample state adjustment time was 48 h. Physical performance tests were carried out according to national standards: cantilever beam notched impact strength standard GB/T 1843-1996, flexural modulus implementation standard GB/T9341-2000, heat distortion temperature implementation standard GB/T 1634-2004. The test results are listed in Table 3-5 below:
表3本发明成核剂改性PA6(M2000)的多种性能Table 3 Various properties of the nucleating agent modified PA6 (M2000) of the present invention
样品sample
|
冲击强度/kJ/m2
Impact strength / kJ / m 2
|
弯曲模量/MPaFlexural modulus / MPa
|
热变形温度/℃(1.8MPa)Heat distortion temperature / ° C (1.8MPa)
|
尼龙颗粒1Nylon particles 1
|
6.586.58
|
2987.522987.52
|
60.360.3
|
尼龙颗粒2Nylon particles 2
|
6.526.52
|
2968.432968.43
|
60.160.1
|
尼龙颗粒3Nylon particles 3
|
6.566.56
|
2976.392976.39
|
60.260.2
|
尼龙颗粒4Nylon particles 4
|
6.536.53
|
2956.292956.29
|
60.060.0
|
尼龙颗粒5Nylon particles 5
|
6.706.70
|
2990.352990.35
|
60.560.5
|
尼龙颗粒6Nylon particles 6
|
6.696.69
|
3015.783015.78
|
62.162.1
|
尼龙颗粒7Nylon particles 7
|
6.716.71
|
3028.933028.93
|
62.562.5
|
尼龙颗粒8Nylon particles 8
|
6.646.64
|
2958.232958.23
|
59.959.9
|
尼龙颗粒9Nylon particles 9
|
6.606.60
|
2921.652921.65
|
59.759.7
|
尼龙颗粒10Nylon particles 10
|
6.486.48
|
2955.782955.78
|
59.859.8
|
尼龙颗粒11Nylon particles 11
|
6.506.50
|
2918.682918.68
|
59.659.6
|
尼龙颗粒12Nylon particles 12
|
6.596.59
|
2968.132968.13
|
60.160.1
|
尼龙颗粒13Nylon particles 13
|
6.636.63
|
2990.352990.35
|
61.561.5
|
尼龙颗粒14Nylon particles 14
|
6.686.68
|
3004.233004.23
|
61.961.9
|
尼龙颗粒对照样品Nylon particle control sample
|
6.486.48
|
2730.822730.82
|
54.154.1
|
尼龙颗粒P22Nylon particles P22
|
6.506.50
|
2965.212965.21
|
59.959.9
|
尼龙颗粒CAV102Nylon particle CAV102
|
6.506.50
|
2968.842,968.84
|
59.959.9
|
从表3中可以看出,与空白对照和市场上常规的P22和CAV102比较,采用本发明的成核剂1-7制备得到的尼龙颗粒1-14在弯曲模量、冲击强度、热变形温度方面明显效果更优,所述弯曲模量的改善,大大地提高了制品的刚性。就尼龙颗粒1-14本身来说,其中成核剂中二-[4-叔丁基苯甲酸]羟基铝和乙烯基双硬质酰胺的比例1:1的尼龙颗粒5和12,二-[4-叔丁基苯甲酸]羟基铝、乙烯基双硬质酰胺和水合硅酸镁的比例1:1:2的尼龙颗粒7和14的各性能又表现得最优;同时含有三元成核剂的尼龙颗粒6-7,13-14的各性能相比二元成核剂的PET颗粒1-5,8-12更佳。As can be seen from Table 3, compared with the blank control and the conventional P22 and CAV102 on the market, the nylon particles 1-14 prepared by using the nucleating agent 1-7 of the present invention have a flexural modulus, an impact strength, and a heat distortion temperature. The apparent effect is better, and the improvement of the flexural modulus greatly improves the rigidity of the product. In the case of nylon particles 1-14 itself, wherein the ratio of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and vinylbis-hard amide in the nucleating agent is 1:1 nylon particles 5 and 12, di-[ The ratio of 4-tert-butylbenzoic acid]hydroxyaluminum, vinylbis-hard amide and hydrated magnesium silicate in the ratio of 1:1:2 nylon particles 7 and 14 is optimal; and contains ternary nucleation The properties of the nylon particles 6-7, 13-14 of the agent are better than the PET particles 1-5, 8-12 of the binary nucleating agent.
表4本发明成核剂改性PET的多种性能Table 4 Various properties of the nucleating agent modified PET of the present invention
样品sample
|
冲击强度/kJ/m2
Impact strength / kJ / m 2
|
弯曲模量/MPaFlexural modulus / MPa
|
热变形温度/℃(0.45MPa)Heat distortion temperature / ° C (0.45MPa)
|
PET颗粒1PET pellet 1
|
4.364.36
|
2650.432650.43
|
77.277.2
|
PET颗粒2PET pellet 2
|
4.304.30
|
2693.252693.25
|
77.777.7
|
PET颗粒3PET particles 3
|
4.304.30
|
2681.282681.28
|
77.577.5
|
PET颗粒4PET particles 4
|
4.284.28
|
2691.912691.91
|
77.677.6
|
PET颗粒5PET particles 5
|
4.304.30
|
2696.062696.06
|
77.777.7
|
PET颗粒6PET particles 6
|
4.384.38
|
2801.192801.19
|
78.778.7
|
PET颗粒7PET particles 7
|
4.364.36
|
2894.032894.03
|
79.179.1
|
PET颗粒8PET particles 8
|
4.354.35
|
2625.132625.13
|
77.077.0
|
PET颗粒9PET particles 9
|
4.324.32
|
2648.342648.34
|
77.477.4
|
PET颗粒10PET particles 10
|
4.364.36
|
2633.612633.61
|
77.177.1
|
PET颗粒11PET particles 11
|
4.334.33
|
2652.382,652.38
|
77.677.6
|
PET颗粒12PET particles 12
|
4.314.31
|
2655.242655.24
|
77.777.7
|
PET颗粒13PET particles 13
|
4.324.32
|
2838.012838.01
|
78.978.9
|
PET颗粒14PET particles 14
|
4.384.38
|
2851.022851.02
|
78.978.9
|
PET颗粒对照样品PET particle control sample
|
4.064.06
|
2578.362578.36
|
75.875.8
|
从表4中可以看出,与空白对照比较,采用本发明的成核剂1-7制备得到的PET颗粒1-14在弯曲模量、冲击强度、热变形温度方面明显效果更优,所述弯曲模量的改善,大大地提高了制品的刚性。就PET颗粒1-14本身来说,其中成核剂中二-[4-叔丁基苯甲酸]羟基铝和乙烯基双硬质酰胺的比例1:1的PET颗粒5和12,二-[4-叔丁基苯甲酸]羟基铝、乙烯基双硬质酰胺和水合硅酸镁的比例1:1:2的PET颗粒7和14的各性能又表现得最优,同时含有三元成核剂的PET颗粒6-7,13-14的各性能相
比二元成核剂的PET颗粒1-5,8-12更佳。As can be seen from Table 4, the PET particles 1-14 prepared by using the nucleating agent 1-7 of the present invention have a markedly superior effect on the flexural modulus, the impact strength, and the heat distortion temperature as compared with the blank control. The improvement in flexural modulus greatly increases the rigidity of the article. In the case of PET particles 1-14 itself, wherein the ratio of bis-[4-tert-butylbenzoic acid]hydroxyaluminum and vinyl bis-carbamide in the nucleating agent is 1:1 PET particles 5 and 12, di-[ The ratio of 4-tert-butylbenzoic acid]hydroxyaluminum, vinyl bis-carbamide and hydrated magnesium silicate in the ratio of 1:1:2 PET particles 7 and 14 is optimal and contains ternary nucleation. Properties of PET particles 6-7, 13-14
More preferably, the PET particles 1-5, 8-12 than the binary nucleating agent.
表5本发明成核剂改性PBT的多种性能Table 5 Various properties of the nucleating agent modified PBT of the present invention
样品sample
|
冲击强度/kJ/m2
Impact strength / kJ / m 2
|
弯曲模量/MPaFlexural modulus / MPa
|
热变形温度/℃(1.8MPa)Heat distortion temperature / ° C (1.8MPa)
|
PBT颗粒1PBT particles 1
|
5.065.06
|
2726.642726.64
|
54.554.5
|
PBT颗粒2PBT particles 2
|
5.075.07
|
2776.592,776.59
|
54.954.9
|
PBT颗粒3PBT particles 3
|
5.035.03
|
2732.842732.84
|
54.654.6
|
PBT颗粒4PBT particles 4
|
5.025.02
|
2764.662764.66
|
54.854.8
|
PBT颗粒5PBT particles 5
|
5.095.09
|
2778.872778.87
|
54.954.9
|
PBT颗粒6PBT particles 6
|
5.075.07
|
2860.442860.44
|
56.056.0
|
PBT颗粒7PBT particles 7
|
5.125.12
|
2862.852862.85
|
56.256.2
|
PBT颗粒8PBT particles 8
|
5.005.00
|
2726.032726.03
|
54.554.5
|
PBT颗粒9PBT particles 9
|
5.125.12
|
2741.232,741.23
|
54.754.7
|
PBT颗粒10PBT particles 10
|
5.205.20
|
2736.072736.07
|
54.654.6
|
PBT颗粒11PBT particles 11
|
5.115.11
|
2775.222,775.22
|
55.055.0
|
PBT颗粒12PBT particles 12
|
5.135.13
|
2796.222,796.22
|
55.355.3
|
PBT颗粒13PBT particles 13
|
5.125.12
|
2826.612826.61
|
56.256.2
|
PBT颗粒14PBT particles 14
|
5.155.15
|
2832.652832.65
|
56.456.4
|
PBT颗粒对照样品PBT particle control sample
|
5.265.26
|
2699.062699.06
|
53.153.1
|
从表5中可以看出,与空白对照比较,采用本发明的成核剂1-7制备得到的PBT颗粒1-14在弯曲模量、冲击强度、热变形温度方面明显效果更优,所述弯曲模量的改善,大大地提高了制品的刚性。就PBT颗粒1-14本身来说,其中成核剂中二-[4-叔丁基苯甲酸]羟基铝和乙烯基双硬质酰胺的比例1:1的PBT颗粒5和12,二-[4-叔丁基苯甲酸]羟基铝、乙烯基双硬质酰胺和水合硅酸镁的比例1:1:2的PBT颗粒7和14的各性能又表现得最优,同时含有三元成核剂的PBT颗粒6-7,13-14的各性能相比二元成核剂的PET颗粒1-5,8-12更佳。As can be seen from Table 5, the PBT particles 1-14 prepared by using the nucleating agent 1-7 of the present invention have a markedly superior effect on the flexural modulus, the impact strength, and the heat distortion temperature as compared with the blank control. The improvement in flexural modulus greatly increases the rigidity of the article. In the case of PBT particles 1-14 itself, PBT particles 5 and 12, bis-[in which the ratio of bis-[4-tert-butylbenzoic acid] hydroxyaluminum and vinyl bis-carbamide in the nucleating agent is 1:1 The ratio of 4-tert-butylbenzoic acid]hydroxyaluminum, vinylbis-hard amide and hydrated magnesium silicate in the ratio of 1:1:2 PBT particles 7 and 14 is optimal and contains ternary nucleation. The performance of the PBT particles 6-7, 13-14 of the agent is better than that of the PET particles 1-5, 8-12 of the binary nucleating agent.
本发明的一种含有乙烯基双硬质酰胺的增刚成核剂组合物已经通过具体的实例进行了描述,本领域技术人员可借鉴本发明内容,适当改变原料、工艺条件等环节来实现相应的其它目的,其相关改变都没有脱离本发明的内容,所有类似的替换和改动对于本领域技术人员来说是显而易见的,都被视为包括在本发明的范围之内。
A rigid nucleating agent composition containing vinyl bis-hard amide of the present invention has been described by a specific example, and those skilled in the art can refer to the content of the present invention and appropriately change the raw materials, process conditions and the like to achieve corresponding It is to be understood that other changes and modifications may be made without departing from the scope of the invention.