WO2017092506A1 - 成核剂的制备方法 - Google Patents

成核剂的制备方法 Download PDF

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WO2017092506A1
WO2017092506A1 PCT/CN2016/101724 CN2016101724W WO2017092506A1 WO 2017092506 A1 WO2017092506 A1 WO 2017092506A1 CN 2016101724 W CN2016101724 W CN 2016101724W WO 2017092506 A1 WO2017092506 A1 WO 2017092506A1
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tert
reaction
butylbenzoic acid
preparation
aluminum
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赵文林
关方文
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呈和科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

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  • the invention relates to the technical field of preparation of polypropylene additives, in particular to a preparation method of a nucleating agent.
  • Nucleating agents are additives suitable for use in polymers, particularly incompletely crystalline polymers, such as polyethylene and polypropylene, and for modifying their crystallization behavior. Nucleating agents can shorten the molding cycle and improve product transparency, surface gloss, tensile strength, rigidity, heat distortion temperature, impact resistance and creep resistance by accelerating the crystallization rate, increasing the crystal density and promoting the grain size miniaturization. Denaturation and other properties.
  • CN102850578B discloses the preparation of such compounds, in particular by first dissolving 2,4-di-tert-butylbenzoic acid in a salt forming solvent (from acetone and water). In the composition), a metal hydroxide is subsequently added dropwise, and finally a salt forming agent aluminum chloride is added to carry out a salt formation reaction to obtain a final product of bis-[4-tert-butylbenzoic acid]hydroxyaluminum.
  • a salt forming solvent from acetone and water
  • the above conventional preparation method is characterized in that the reaction is carried out at a high temperature such as 80 ° C, and the saponification reaction is carried out first, followed by addition of an aluminum salt to form a salt formation reaction, and the heating step and the synthesis step are completed stepwise.
  • the preparation method is not only complicated in operation, but also requires the use of a large amount of an organic solvent and a water-soluble salt aluminum chloride, which causes troubles for subsequent rinsing, and has disadvantages such as environmental pollution and increased manufacturing cost.
  • the invention adopts a novel preparation process, and realizes a simple process and a short process.
  • the utility model overcomes the defects of causing environmental pollution, increasing manufacturing cost, and the like, and also realizes the advantages of better product yield and production cost.
  • the invention provides a preparation method of a polypropylene nucleating agent, which solves the problem that not only the process operation is complicated in the prior art, but also a large amount of organic solvent and water-soluble salt aluminum chloride must be used, which causes environmental pollution and increases manufacturing. Fees and other issues.
  • the present invention provides a process for preparing bis-[4-tert-butylbenzoic acid] hydroxyaluminum, which is characterized in that a substance is supplied from 4-tert-butylbenzoic acid, a metaaluminate, and an aluminum salt in water. Chemical reaction preparation to obtain di-[4-tertidine Benzoic acid] hydroxy aluminum.
  • reaction formula of the chemical reaction is as follows:
  • the solvent of the reaction system of this reaction is water.
  • the aluminum salt is one or more of aluminum nitrate, aluminum sulfate or aluminum chloride;
  • the above preparation method the partial aluminate to provide substance NaAlO 2, KAlO 2 or HAlO 2.
  • the above preparation method comprises the following steps:
  • Step 1 At normal temperature, according to the ratio of the aluminate supply material and the aluminum salt in the water, the mixture is stirred and mixed uniformly. Under stirring, the p-tert-butylbenzoic acid is added according to the ratio, then the reaction is stirred and the circulating pump is started for 3 to 5 hours. ;
  • Step 2 removing the anion from the cation and aluminum salt brought by the material provided by the metaaluminate by pressure filtration or suction filtration and rinsing, and drying to prepare a final product.
  • the reaction time in the first step is 4 hours.
  • the preparation method of the invention proves that the following reaction principle is feasible through a large number of experiments, that is, solves the solubility problem because p-tert-butylbenzoic acid has low solubility in water, but has certain solubility and reacts with alkali metal hydroxide.
  • the bis-[4-tert-butylbenzoic acid] hydroxyaluminum prepared by the preparation method of the invention has a unique crystal of a crystal form nucleating agent, which can significantly improve the rigidity of the polyolefin, and is an alpha crystal nucleating agent.
  • the method of the invention does not use an organic solvent such as acetone, avoids the process of recovering the organic solvent, is simple in operation, and reduces disadvantages such as manufacturing cost and environmental pollution.
  • Figure 1 Infrared spectrum of bis(2,4-di-tert-butylbenzoate) hydroxyaluminum prepared by the process of the invention.
  • the reaction tank 1m 3 in water was added 0.15M 3, and tert-butylbenzoic acid into 148.2Kg 50KgNaOH, then added with stirring to a solution of aluminum salt at a concentration of 200Kg (AlCl 3 ⁇ 6H 2 O ) / M 3 of 0.475M 3, and to start the circulation pump was stirred for 4 hours.
  • a concentration of 200Kg (AlCl 3 ⁇ 6H 2 O ) solution of the aluminum salt / M 3 of about 0.027M 3 the solution was adjusted to a pH of 4.5 to 5.0, The mixture was filtered, rinsed to remove NaCl, and dried to obtain a white solid product.
  • the product was determined to be bis(2,4-di-tert-butylbenzoic acid) hydroxyaluminum by mass spectrometry and infrared analysis. The yield was 98.5%, and the Al content was 6.50. %.
  • the salt-forming solvent consisted of acetone and water, wherein the water content was 35% by weight of the salt-forming solvent, 2,4-di-tert-butylbenzoic acid. And the mass ratio of the salt-forming solvent is 1:30, stirring, firstly adding 18.6 ml of 10% by weight sodium hydroxide, heating to 80 ° C, adding a 30% by weight aqueous solution of aluminum chloride to 2,4-two The salt formation reaction is carried out in a solution of tert-butylbenzoic acid.
  • the molar ratio of 2,4-di-tert-butylbenzoic acid to the salt forming agent is 2:1, and the reaction is carried out for 4 hours. After the reaction is completed, the concentration is 10% by weight of hydrogen. 8.2 ml of sodium oxide was adjusted to adjust the pH of the solution to neutrality, filtered, washed, and dried to obtain a white solid product. The product was identified as bis(2,4-di-tert-butylbenzoic acid) hydroxyaluminum by mass spectrometry and infrared analysis. The rate was 97.2% and the Al content was 6.38%.
  • Example 1-3 is a molar ratio of p-tert-butylbenzoic acid to the water-soluble salt added of 8:1, and the corresponding ratio in the comparative example is 2:1, which greatly reduces the addition of the water-soluble salt, and reduces The difficulty of rinsing reduces the amount of rinsing water.
  • the nucleating agents 1-5 prepared in Examples 1-5 and the comparative nucleating agents prepared in Comparative Example 1 were respectively added to the homopoly PP and the copolymerized PP according to the 0.10% addition amount of the PP mass, and the twin-screw extrusion at 210 ° C was carried out. Extrusion granulation was carried out and injection molded into a standard spline at 230 °C.
  • nucleating agent reinforced rigid modified polypropylene is stipulated in GB 2918-1998 (standard environment for plastic sample state adjustment and test), at (23 ⁇ 2) °C, relative humidity (RH) is (50 ⁇ 5)%. The conditions were adjusted under the conditions of 48 h. Physical performance tests were carried out according to national standards: flexural modulus implementation standard GB/T9341-2000, heat distortion temperature implementation standard GB/T 1634-2004, crystallization temperature implementation standard GB/T19466.3-2004. The test results are listed in Table 1 below.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明涉及一种二-[4-叔丁基苯甲酸]羟基铝的制备方法，由4-叔丁基苯甲酸、偏铝酸盐根提供物质、铝盐在水中化学反应制备得到二-[4-叔丁基苯甲酸]羟基铝。相比现有的方法而言，采用本发明方法，不仅产率提高，反应过程中，不使用有机溶剂作反应介质，在常温下反应，不需要加热，节能环保；同时避免了有机溶剂回收和造成环境污染，生产成本大幅度降低。

Description

成核剂的制备方法 技术领域
本发明涉及聚丙烯添加剂的制备技术领域，特别是涉及一种成核剂的制备方法。
技术背景
成核剂是适用于聚合物，特别是不完全结晶的聚合物，例如聚乙烯和聚丙烯等，并且用于改变其结晶行为的添加剂。成核剂可以通过加快结晶速率、增加结晶密度和促使晶粒尺寸微细化等，达到缩短成型周期和提高制品透明性、表面光泽、抗拉强度、刚性、热变形温度、抗冲击性以及抗蠕变性等性能。
关于二-[4-叔丁基苯甲酸]羟基铝的制备，CN102850578B公开了该类化合物的制备，具体为首先将2,4-二叔丁基苯甲酸溶于成盐溶剂(由丙酮和水组成)中，随后滴加金属氢氧化物，最后加入成盐剂氯化铝，进行成盐反应，制得最终产物二-[4-叔丁基苯甲酸]羟基铝。
上述现有的制备方法的特点是反应在高温如80℃下进行，先进行皂化反应后再加铝盐进行成盐反应，其加温步骤和合成步骤分步完成。该制备方法不仅操作复杂，而且还必须使用大量的有机溶剂和水溶性盐氯化铝，这给后续的漂洗带来困扰，存在着造成环境污染、增加制造费用等缺点。
为了解决现有的作为聚丙烯成核剂的二-[4-叔丁基苯甲酸]羟基铝制备技术中存在的缺点，本发明采用一种全新的制备工艺，在实现了工艺简单，流程短，克服了存在着造成环境污染、增加制造费用等缺点的同时，还实现了产品的产率和生产成本更优的优点。
发明内容
本发明提供一种聚丙烯成核剂的制备方法，用以解决现有技术中不仅工艺操作复杂，而且还必须使用大量的有机溶剂和水溶性盐氯化铝，存在着造成环境污染、增加制造费用等问题。
为达上述目的，本发明提供了一种二-[4-叔丁基苯甲酸]羟基铝的制备方法，其特征在于由4-叔丁基苯甲酸、偏铝酸根提供物质、铝盐在水中化学反应制备得到二-[4-叔丁 基苯甲酸]羟基铝。
优选地，上述方法中，化学反应的反应式如下：
Figure PCTCN2016101724-appb-000001
该反应的反应体系的溶剂为水。
优选地，上述制备方法中，铝盐为硝酸铝、硫酸铝或氯化铝中的一种或多种；
优选地，上述制备方法中，偏铝酸根提供物质为NaAlO2、KAlO2或HAlO2。
优选地，上述制备方法包括如下步骤：
步骤一、于常温下，按配比将偏铝酸根提供物质、铝盐在水中搅拌混合均匀后，在搅拌下，按配比加入对叔丁基苯甲酸，然后搅拌并开动循环泵反应3～5小时；
步骤二、通过压滤或抽滤、漂洗除去由偏铝酸根提供物质带来的阳离子和铝盐带来的阴离子，干燥制备得到最终产物。
优选地，上述制备方法中，步骤一中反应时间为4小时。
本发明的制备方法通过大量试验证明了如下的反应原理是可行的，也就是解决溶解度问题，因为对叔丁基苯甲酸在水中溶解度小，但是还有一定的溶解度，与碱金属氢氧化物反应可生成可溶于水的对叔丁基苯甲酸盐，再与铝化合物反应生成二-[4-叔丁基苯甲酸]羟基铝，由于二-[4-叔丁基苯甲酸]羟基铝在水中的溶解度比对叔丁基苯甲酸要小，故能使化学反应不断向正反应方向进行，最终全部生成二-[4-叔丁基苯甲酸]羟基铝。
本发明的有益效果如下：
1、本发明的制备方法制备得到的二-[4-叔丁基苯甲酸]羟基铝具有特有的α晶型成核剂结晶，可以显著提高聚烯烃的刚性，是α晶型成核剂中综合机械性能、性价比较好的成核剂。
2、由于本发明的二-[4-叔丁基苯甲酸]羟基铝是在室温下进行的，相比现有方法必须加温至80℃简化了工艺，同时节能环保；
3、本发明的方法不使用有机溶剂如丙酮，避免了有机溶剂回收的工序，操作简单，降低了制造费用和环境污染等缺点。
附图说明
图1：采用本发明方法制备二(2，4-二叔丁基苯甲酸)羟基铝的红外光谱图。
具体实施方式
以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不限定本发明。
实施例1
于常温下，在1m3反应罐中，投入25.6Kg的NaAlO2，加水0.4m3，搅拌溶解，投入148.2Kg对叔丁基苯甲酸，开动循环泵循环搅拌反应2小时，再加入浓度为200Kg(AlCl3·6H2O)/M3的铝盐溶液0.115M3，开动循环泵搅拌反应1小时，反应结束后，加入浓度为200Kg(AlCl3·6H2O)/M3的铝盐溶液约0.0105M3，调节溶液pH值至4.5～5.0，压滤、漂洗除去NaCl，干燥，制备得到白色固体产物，经质谱和红外分析确定该产物为二(2，4-二叔丁基苯甲酸)羟基铝，产率为97.3％，Al含量为6.41％。(产物的红外光谱图参见附图1)
实施例2
于常温下，在1m3反应罐中，投入25.6Kg的NaAlO2，加水0.4m3，搅拌溶解，投入148.2Kg对叔丁基苯甲酸，开动循环泵循环搅拌反应2小时，再加入浓度为200Kg(AlCl3·6H2O)/M3的铝盐溶液0.115M3，搅拌并开动循环泵反应3小时，反应结束后，加入浓度为200Kg(AlCl3·6H2O)/M3的铝盐溶液约0.0105M3，调节溶液pH值至4.5～5.0，压滤、漂洗除去NaCl，干燥，制备得到白色固体产物，经质谱和红外分析确定该产物为二(2，4-二叔丁基苯甲酸)羟基铝，产率为97.5％，Al含量为6.48％。
实施例3
于常温下，在2m3反应罐中，投入25.6Kg的NaAlO2，加水0.4m3，搅拌溶解，投入148.2Kg对叔丁基苯甲酸，开动循环泵循环搅拌反应2小时，再加入浓度为200Kg(AlCl3·6H2O)/M3的铝盐溶液0.115M3，搅拌并开动循环泵反应2小时，反应结束后，加入浓度为200Kg(AlCl3·6H2O)/M3的铝盐溶液约0.0105M3，调节溶液pH值至 4.5～5.0，压滤，漂洗除去NaCl，干燥，制备得到白色固体产物，经质谱和红外分析确定该产物为二(2，4-二叔丁基苯甲酸)羟基铝，产率为97.5％，Al含量为6.48％。
实施例4
于常温下，在1m3反应罐中，加水0.15m3，投入148.2Kg对叔丁基苯甲酸和50KgNaOH，搅拌后再加入浓度为200Kg(AlCl3·6H2O)/M3的铝盐溶液0.475M3，搅拌并开动循环泵反应4小时，反应结束后，加入浓度为200Kg(AlCl3·6H2O)/M3的铝盐溶液约0.027M3，调节溶液pH值至4.5～5.0，压滤，漂洗除去NaCl，干燥，制备得到白色固体产物，经质谱和红外分析确定该产物为二(2，4-二叔丁基苯甲酸)羟基铝，产率为98.5％，Al含量为6.50％。
实施例5
于常温下，在1m3反应罐中，加水0.2m3，投入16.7KgNaOH和17Kg NaAlO2，搅拌溶解，投入148.2Kg对叔丁基苯甲酸，搅拌，再加入浓度为200Kg(AlCl3·6H2O)/M3的铝盐溶液0.24M3，搅拌并开动循环泵反应4小时，反应结束后，加入浓度为200Kg(AlCl3·6H2O)/M3的铝盐溶液约0.011M3，调节溶液pH值至4.5～5.0，压滤，漂洗除去NaCl，干燥，制备得到白色固体产物，经质谱和红外分析确定该产物为二(2，4-二叔丁基苯甲酸)羟基铝，产率为97.8％，Al含量为6.49％。
对比实施例1
按照目前常用的制备方法制备，具体如下：
将2,4-二叔丁基苯甲酸32g加入成盐溶剂中，成盐溶剂由丙酮和水组成，其中水的含量为成盐溶剂的35重量％，2,4-二叔丁基苯甲酸和成盐溶剂的质量比为1∶30，搅拌，先滴加浓度为10重量％氢氧化钠18.6ml，加热至80℃，将浓度为30重量％氯化铝水溶液加入到2,4-二叔丁基苯甲酸溶液中进行成盐反应，2,4-二叔丁基苯甲酸和成盐剂的摩尔比为2∶1，反应4小时，反应结束后，滴加浓度为10重量％氢氧化钠8.2ml调节溶液pH值至中性，过滤，洗涤，加热干燥后得到白色固体产物，经质谱和红外分析确定该产物为二(2，4-二叔丁基苯甲酸)羟基铝，产率为97.2％，Al含量为6.38％。
结果表明：采用本发明方法制备的成核剂除产率有所提高之外，反应过程中不用加温，节能环保；同时避免了有机溶剂回收的工序；同时在水溶性盐使用方面，本发明实施例1-3是对叔丁基苯甲酸与所加入的水溶性盐的摩尔比为8:1，而对比实施例中相应比例为2:1，大大减少了水溶性盐的加入，降低了漂洗难度，减少了漂洗水量。
应用实施例
将实施例1-5制备的成核剂1-5和对比实施例1制备的对比成核剂，按照PP质量的0.10％添加量分别添加到均聚PP和共聚PP中，210℃双螺杆挤出机挤出造粒，230℃注塑成标准样条。
成核剂增刚改性聚丙烯的测试按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：弯曲模量执行标准GB/T9341-2000，热变形温度执行标准GB/T 1634-2004，结晶温度执行标准GB/T19466.3-2004。测试结果列于下表1
表1本发明成核剂改性PP的多种性能
Figure PCTCN2016101724-appb-000002
结果表明：采用本发明实施例1-5所制得的成核剂1-5与现有技术所公开的制备方法所制得的对比成核剂应用于均聚PP和共聚PP时，在弯曲模量、热变形温度以及结晶温度方面无差异。
本发明的一种成核剂的制备方法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。

Claims (6)

  1. 一种二-[4-叔丁基苯甲酸]羟基铝的制备方法，其特征在于，由4-叔丁基苯甲酸、偏铝酸盐根提供物质、铝盐在水中化学反应制备得到二-[4-叔丁基苯甲酸]羟基铝。
  2. 根据权利要求1所述的制备方法，其特征在于，该方法中化学反应的反应式如下：
    Figure PCTCN2016101724-appb-100001
    该反应的反应体系的溶剂为水。
  3. 根据权利要求1或2所述的制备方法，其特征在于，铝盐为硝酸铝、硫酸铝或氯化铝中的一种或多种；
  4. 根据权利要求1或2所述的制备方法，其特征在于，偏铝酸盐根提供物质为NaAlO2、KAlO2或HAlO2。
  5. 根据权利要求1-4任一项所述的制备方法，其特征在于，该方法包括如下步骤：
    步骤一、于常温下，按配比将偏铝酸根提供物质、铝盐在水中搅拌混合均匀后，在搅拌下，按配比加入对叔丁基苯甲酸，然后搅拌并开动循环泵反应3～5小时；
    步骤二、通过压滤或抽滤、漂洗除去由偏铝酸根提供物质带来的阳离子和铝盐带来的阴离子，干燥制备得到最终产物。
  6. 根据权利要求5所述的制备方法，其特征在于，步骤一中反应时间为4小时。
PCT/CN2016/101724 2015-12-04 2016-10-11 成核剂的制备方法 WO2017092506A1 (zh)

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