WO2021003760A1 - Composite material of octadecyldimethyl-tertiary-amine-modified zeolite and natural rubber and preparation method therefor - Google Patents

Composite material of octadecyldimethyl-tertiary-amine-modified zeolite and natural rubber and preparation method therefor Download PDF

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WO2021003760A1
WO2021003760A1 PCT/CN2019/096252 CN2019096252W WO2021003760A1 WO 2021003760 A1 WO2021003760 A1 WO 2021003760A1 CN 2019096252 W CN2019096252 W CN 2019096252W WO 2021003760 A1 WO2021003760 A1 WO 2021003760A1
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tertiary amine
zeolite
dimethyl tertiary
modified zeolite
octadecyl dimethyl
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French (fr)
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于福家
陈晓龙
胡杰
楚文城
张淘忠
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东北大学
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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
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3009—Physical treatment, e.g. grinding; treatment with ultrasonic vibrations
    • C09C1/3018—Grinding
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3009—Physical treatment, e.g. grinding; treatment with ultrasonic vibrations
    • C09C1/3027—Drying, calcination
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3063—Treatment with low-molecular organic compounds

Definitions

  • the invention belongs to the field of non-metal mineral materials, and relates to a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber and a preparation method thereof.
  • Natural zeolite is a kind of silicate with silicate tetrahedron and aluminum oxide tetrahedron as the framework, which has a large distribution of resource reserves in my country. From the analysis of the composition and crystal structure of natural zeolite, zeolite can be used as a filler, and can reduce the amount of composite material high polymer to a certain extent, to achieve the purpose of reducing costs and environmentally friendly production. In addition, because the density of zeolite is relatively small, using zeolite as a filler can also reduce the density of the composite material to a certain extent and achieve the purpose of lightweight.
  • zeolite When natural zeolite is used as a filler, it needs to undergo surface organic modification treatment to enhance its surface hydrophobicity and improve its compatibility with rubber.
  • surface modifiers include silicone oils, titanates, organic amines, fatty acids and coupling agents. Different modifiers are adsorbed on the surface of the zeolite and have different mechanisms of action during the mixing and vulcanization of natural rubber. The tensile strength, tear strength, elongation at break and Shore hardness of the rubber composite material obtained The performance is also different.
  • the invention provides a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber and a preparation method thereof.
  • the method involves organic modification of the surface of natural zeolite and the use of modified zeolite and natural rubber. Refining preparation process.
  • the natural zeolite is organically modified by a wet process, and the modified zeolite is mixed with natural rubber. This method can significantly improve the mechanical properties of natural rubber.
  • the preparation method of octadecyl dimethyl tertiary amine modified zeolite of the present invention includes the following steps:
  • the natural zeolite is subjected to wet ultrafine grinding to obtain zeolite slurry; wherein the particle size distribution of the zeolite in the zeolite slurry is D 90 of 5 ⁇ m to 30 ⁇ m;
  • Adjust the pH of the zeolite slurry to 6-10, preferably pH 7, add a completely dissolved salt solution of octadecyl dimethyl tertiary amine, and then configure the zeolite slurry with a mass percentage of 20-30%; wherein, According to the mass ratio, zeolite powder in zeolite slurry: octadecyl dimethyl tertiary amine 100: (0.5 ⁇ 1.5);
  • the ore pulp is subjected to wet modification for 5-60 minutes at a modification temperature of 40-100°C and a high-speed mixer rotating speed of 800-1000r/min to obtain a modified product;
  • the modified product is dried to a constant weight, pulverized and crushed to obtain dry octadecyl dimethyl tertiary amine modified zeolite; among them, the D of stearyl dimethyl tertiary amine modified zeolite 90 is 5 ⁇ m to 30 ⁇ m.
  • the grinding concentration of the wet ultrafine grinding is 45-60%, and the medium filling rate is 70%.
  • the speed of the high-speed mixer is preferably 900 r/min.
  • the drying is carried out in an oven at 100-120°C for 24 hours.
  • the octadecyl dimethyl tertiary amine modified zeolite has a contact angle of 100°-120° and an activation index of 90%-100%.
  • the octadecyl dimethyl tertiary amine modified zeolite of the present invention is prepared by the above preparation method.
  • the composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber of the present invention includes the above-mentioned octadecyl dimethyl tertiary amine modified zeolite and natural rubber.
  • Dimethyl tertiary amine modified zeolite: natural rubber (10 ⁇ 70):100.
  • the method for preparing a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber of the present invention includes the following steps:
  • the prepared octadecyl dimethyl tertiary amine modified zeolite is added to the rubber formula, mixed and vulcanized to obtain a composite material of the stearyl dimethyl tertiary amine modified zeolite and rubber.
  • the composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber prepared with the above formula was placed at a constant temperature of 25°C for 24 hours and then its mechanical properties were tested.
  • the obtained stearyl dimethyl tertiary amine modified zeolite The material composited with natural rubber has a tensile strength of 20 MPa to 30 MPa, a tear strength of 25 MPa to 35 MPa, an elongation at break of 600% to 1000%, and a Shore hardness of 35 to 45.
  • the vulcanization time and vulcanization temperature are determined according to the vulcanization curve obtained by the inspection of the mixed materials.
  • Natural zeolite has more silicic hydroxyl groups on the surface, strong water absorption, and easy to agglomerate when the surface is negatively charged.
  • Octadecyl dimethyl tertiary amine is a cationic surfactant that is positively charged. Compared with other agents, it is easier to electrostatically adsorb the negative charge on the surface of the zeolite to make the zeolite hydrophobic, so that the modified zeolite has more Good hydrophobicity and dispersibility.
  • the present invention uses octadecyl dimethyl tertiary amine to modify the zeolite.
  • the octadecyl dimethyl tertiary amine is a kind of long-chain alkyl dimethyl tertiary amine, and its carbon chain length is the hydrophobic chain length.
  • Good hydrophobicity, polar groups are easy to be embedded, which greatly improves the hydrophobicity of modified zeolite, and its long-chain alkyl group has good flexibility, which can improve the mechanical properties of subsequent composite natural rubber.
  • the method of the present invention is suitable for natural rubber, because in natural rubber, the rubber structure is cis 1,4-polyisoprene, which has the characteristics of low melting point and high solubility.
  • a network structure is formed inside the rubber, which will also enhance the mechanical properties of natural rubber.
  • the present invention adopts a wet ultrafine grinding process for zeolite, which has better ore dispersibility and a uniform particle size than dry grinding, and combined with the subsequent wet modification process, the process flow is simple, no drying is required, and the cost is lower.
  • the natural zeolite and natural rubber raw materials used are easily available, large in reserve, and low in cost.
  • the framework structure of the zeolite can improve the mechanical properties of the composite material.
  • concentration refers to mass concentration
  • a method for preparing a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber including the following steps:
  • step 1
  • the natural zeolite is subjected to wet ultrafine grinding to obtain zeolite slurry; among them, the particle size distribution of zeolite powder in the zeolite slurry is D 90 of 20 ⁇ m; the grinding concentration in the wet ultrafine grinding is the zeolite slurry concentration of 50 %, the medium filling rate is 70%;
  • the ore slurry was subjected to wet modification for 20 minutes at a modification temperature of 80° C. and a high-speed mixer rotating speed of 900 r/min to obtain a modified product.
  • a method for preparing a composite material of zeolite and natural rubber is the same as in Example 1, except that:
  • step 4 an unmodified zeolite is used to replace the stearyl dimethyl tertiary amine modified zeolite, and the others are the same to obtain a composite material of unmodified zeolite and natural rubber.
  • a preparation method of a composite material of titanate JN-114 modified zeolite and natural rubber is the same as that in Example 1, except that:
  • step 4 use titanate JN-114 modified zeolite instead of octadecyl dimethyl tertiary amine modified zeolite, and the others are the same to obtain a composite of titanate JN-114 modified zeolite and natural rubber material.
  • a preparation method of a composite material of Si69 coupling agent modified zeolite and natural rubber is the same as in Example 1, except that:
  • step 4 the Si69 coupling agent modified zeolite is used to replace the stearyl dimethyl tertiary amine modified zeolite, and the others are the same, to obtain a Si69 coupling agent modified zeolite and natural rubber composite material.
  • a method for preparing a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber including the following steps:
  • step 1
  • Natural zeolite is subjected to wet ultrafine grinding to obtain zeolite slurry; among them, the particle size distribution of zeolite powder in the zeolite slurry is D 90 of 20 ⁇ m; in wet ultrafine grinding, the grinding concentration is 50%, and the medium filling rate 70%;
  • the ore slurry was subjected to wet modification for 20 minutes at a modification temperature of 80° C. and a high-speed mixer rotating speed of 900 r/min to obtain a modified product.
  • the modified product is dried in an oven at 110°C for 24 hours to a constant weight, and is ground and crushed to obtain the stearyl dimethyl tertiary amine modified zeolite.
  • the contact angle of the stearyl dimethyl tertiary amine modified zeolite is 113°, and the activation index is 98.32%.
  • a method for preparing a composite material of zeolite and natural rubber is the same as in Example 2, except that:
  • step 4 an unmodified zeolite is used to replace the stearyl dimethyl tertiary amine modified zeolite, and the others are the same to obtain a composite material of unmodified zeolite and natural rubber.
  • a preparation method of a composite material of titanate JN-114 modified zeolite and natural rubber is the same as in Example 2, except that:
  • step 4 use titanate JN-114 modified zeolite instead of octadecyl dimethyl tertiary amine modified zeolite, and the others are the same to obtain a composite of titanate JN-114 modified zeolite and natural rubber material.
  • a preparation method of a composite material of Si69 coupling agent modified zeolite and natural rubber is the same as in Example 2, except that:
  • step 4 the Si69 coupling agent modified zeolite is used to replace the stearyl dimethyl tertiary amine modified zeolite, and the others are the same, to obtain a Si69 coupling agent modified zeolite and natural rubber composite material.
  • Example 2 Comparative Example 4, Comparative Example 5, and Comparative Example 6 were tested for mechanical properties, and the obtained test results are shown in Table 2.

Abstract

Disclosed are a composite material of an octadecyldimethyl-tertiary-amine-modified zeolite and a natural rubber and a preparation method therefor, and the present invention belongs to the field of non-metal mineral materials. The method involves first subjecting a natural zeolite to wet ultra-fine grinding, adjusting the pH value of a zeolite mineral paste to 6-10, mixing same with a salt solution in which octadecyldimethyl tertiary amine is completely dissolved, subjecting same to wet modification at 40-100°C for 5-60 min, and drying and grinding the modified product to obtain an octadecyldimethyl-tertiary-amine-modified zeolite; and adding the octadecyldimethyl-tertiary-amine-modified zeolite to a rubber formulation, and mixing and vulcanizing same to obtain a composite material of the octadecyldimethyl-tertiary-amine-modified zeolite and a rubber. The method involves subjecting the surface of a natural zeolite to organic modification and mixing the modified zeolite with a natural rubber, and can significantly increase the mechanical properties of the natural rubber.

Description

十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料及其制法Composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber and its preparation method 技术领域Technical field
本发明属于非金属矿物材料领域，涉及十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料及其制法。The invention belongs to the field of non-metal mineral materials, and relates to a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber and a preparation method thereof.
背景技术Background technique
天然沸石是一种以硅氧四面体和铝氧四面体为骨架的硅酸盐，在我国资源储量大分布广。从天然沸石的组成成分和晶体结构来分析，沸石可以用作填充剂，并可以在一定程度上减少复合材料高聚物的用量，达到降低成本、环保生产的目的。此外，因为沸石的密度较小，将沸石用作填充材料也能在一定程度降低复合材料的密度，实现轻量化的目的。Natural zeolite is a kind of silicate with silicate tetrahedron and aluminum oxide tetrahedron as the framework, which has a large distribution of resource reserves in my country. From the analysis of the composition and crystal structure of natural zeolite, zeolite can be used as a filler, and can reduce the amount of composite material high polymer to a certain extent, to achieve the purpose of reducing costs and environmentally friendly production. In addition, because the density of zeolite is relatively small, using zeolite as a filler can also reduce the density of the composite material to a certain extent and achieve the purpose of lightweight.
天然沸石用作填料时需要对其进行表面有机改性处理，以增强其表面疏水性来提高与橡胶的相容性。常用的表面改性剂有硅油类、钛酸脂类、有机胺类、脂肪酸类和偶联剂类等。不同的改性药剂吸附在沸石表面后与天然橡胶混炼和硫化的过程中会有不同的作用机制，制得的橡胶复合材料的拉伸强度，撕裂强度，断裂伸长率和邵氏硬度等性能也不同。When natural zeolite is used as a filler, it needs to undergo surface organic modification treatment to enhance its surface hydrophobicity and improve its compatibility with rubber. Commonly used surface modifiers include silicone oils, titanates, organic amines, fatty acids and coupling agents. Different modifiers are adsorbed on the surface of the zeolite and have different mechanisms of action during the mixing and vulcanization of natural rubber. The tensile strength, tear strength, elongation at break and Shore hardness of the rubber composite material obtained The performance is also different.
发明概述Summary of the invention
技术问题technical problem
问题的解决方案The solution to the problem
技术解决方案Technical solutions
本发明提供了一种十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料及其制法，该方法涉及天然沸石表面有机改性、以及采用改性后的沸石和天然橡胶混炼的制备工艺。采用湿法工艺对天然沸石进行表面有机改性，将制得的改性沸石与天然橡胶混炼。该方法能够显著提高天然橡胶的力学性能。The invention provides a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber and a preparation method thereof. The method involves organic modification of the surface of natural zeolite and the use of modified zeolite and natural rubber. Refining preparation process. The natural zeolite is organically modified by a wet process, and the modified zeolite is mixed with natural rubber. This method can significantly improve the mechanical properties of natural rubber.
本发明的一种十八烷基二甲基叔胺改性沸石的制备方法，包括以下步骤：The preparation method of octadecyl dimethyl tertiary amine modified zeolite of the present invention includes the following steps:
步骤1：超细粉磨Step 1: Superfine grinding
将天然沸石进行湿法超细粉磨，得到沸石矿浆；其中，沸石矿浆中沸石的粒度分布为D 90为5μm～30μm； The natural zeolite is subjected to wet ultrafine grinding to obtain zeolite slurry; wherein the particle size distribution of the zeolite in the zeolite slurry is D 90 of 5 μm to 30 μm;
步骤2：湿法改性Step 2: Wet modification
将盐酸和十八烷基二甲基叔胺按比例在去离子水中混溶，得到溶解完全的十八烷基二甲基叔胺的盐溶液；其中比例按摩尔比，盐酸∶十八烷基二甲基叔胺＝1∶1；The hydrochloric acid and octadecyl dimethyl tertiary amine are mixed in deionized water in proportion to obtain a completely dissolved salt solution of octadecyl dimethyl tertiary amine; the ratio is molar ratio, hydrochloric acid: octadecyl Dimethyl tertiary amine=1:1;
调节沸石矿浆pH值为6～10，优选为pH值为7，加入溶解完全的十八烷基二甲基叔胺的盐溶液，然后配置成沸石质量百分比为20～30％的矿浆；其中，按质量比，沸石矿浆中沸石粉∶十八烷基二甲基叔胺＝100∶(0.5～1.5)；Adjust the pH of the zeolite slurry to 6-10, preferably pH 7, add a completely dissolved salt solution of octadecyl dimethyl tertiary amine, and then configure the zeolite slurry with a mass percentage of 20-30%; wherein, According to the mass ratio, zeolite powder in zeolite slurry: octadecyl dimethyl tertiary amine = 100: (0.5 ~ 1.5);
将矿浆，在改性温度40～100℃，高速混合机转速为800～1000r/min的条件下进行湿法改性5～60min，得到改性后的产物；The ore pulp is subjected to wet modification for 5-60 minutes at a modification temperature of 40-100°C and a high-speed mixer rotating speed of 800-1000r/min to obtain a modified product;
步骤3：干燥处理Step 3: Drying
将改性后的产物进行烘干至恒重，粉磨打碎，得到干燥的十八烷基二甲基叔胺改性沸石；其中，十八烷基二甲基叔胺改性沸石的D 90为5μm～30μm。 The modified product is dried to a constant weight, pulverized and crushed to obtain dry octadecyl dimethyl tertiary amine modified zeolite; among them, the D of stearyl dimethyl tertiary amine modified zeolite 90 is 5 μm to 30 μm.
所述的步骤1中，湿法超细粉磨的磨矿浓度为45～60％，介质填充率为70％。In the step 1, the grinding concentration of the wet ultrafine grinding is 45-60%, and the medium filling rate is 70%.
所述的步骤2中，高速混合机转速优选为900r/min。In the step 2, the speed of the high-speed mixer is preferably 900 r/min.
所述的步骤3中，所述的烘干，采用置于烘箱中在100～120℃烘干24h。In the step 3, the drying is carried out in an oven at 100-120°C for 24 hours.
本发明得到的十八烷基二甲基叔胺改性沸石的接触角100°～120°，活化指数为90％～100％。The octadecyl dimethyl tertiary amine modified zeolite has a contact angle of 100°-120° and an activation index of 90%-100%.
本发明的一种十八烷基二甲基叔胺改性沸石，采用上述制备方法制得。The octadecyl dimethyl tertiary amine modified zeolite of the present invention is prepared by the above preparation method.
本发明的一种十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料，包括上述十八烷基二甲基叔胺改性沸石和天然橡胶，按质量比，十八烷基二甲基叔胺改性沸石∶天然橡胶＝(10～70)∶100。The composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber of the present invention includes the above-mentioned octadecyl dimethyl tertiary amine modified zeolite and natural rubber. Dimethyl tertiary amine modified zeolite: natural rubber=(10～70):100.
本发明的一种十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料的制备方法，包括以下步骤：The method for preparing a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber of the present invention includes the following steps:
将制备的十八烷基二甲基叔胺改性沸石加入橡胶配方中，进行混炼，硫化，得到十八烷基二甲基叔胺改性沸石和橡胶复合的材料。The prepared octadecyl dimethyl tertiary amine modified zeolite is added to the rubber formula, mixed and vulcanized to obtain a composite material of the stearyl dimethyl tertiary amine modified zeolite and rubber.
所述的橡胶配方，根据天然橡胶的用途可选用以下配方：According to the rubber formula, the following formulas can be selected according to the use of natural rubber:
天然橡胶100phr，硬脂酸3phr，石蜡1phr，促进剂0.7phr，氧化锌5phr，防老剂1phr，硫3phr，改性沸石10phr～70phr。Natural rubber 100phr, stearic acid 3phr, paraffin wax 1phr, accelerator 0.7phr, zinc oxide 5phr, antioxidant 1phr, sulfur 3phr, modified zeolite 10phr～70phr.
将采用上述配方制得的十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料恒温25℃放置24h后测试其力学性能，得到的十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料的拉伸强度20MPa～30MPa，撕裂强度25MPa～35MPa，扯断伸长率600％～1000％，邵氏硬度35～45。The composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber prepared with the above formula was placed at a constant temperature of 25°C for 24 hours and then its mechanical properties were tested. The obtained stearyl dimethyl tertiary amine modified zeolite The material composited with natural rubber has a tensile strength of 20 MPa to 30 MPa, a tear strength of 25 MPa to 35 MPa, an elongation at break of 600% to 1000%, and a Shore hardness of 35 to 45.
所述的硫化，其硫化时间和硫化温度，根据混炼后的物料检测得到的硫化曲线确定。For the vulcanization, the vulcanization time and vulcanization temperature are determined according to the vulcanization curve obtained by the inspection of the mixed materials.
发明的有益效果The beneficial effects of the invention
有益效果Beneficial effect
本发明的十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料及其制法，其优点是：The composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber and its preparation method of the present invention have the following advantages:
1、天然沸石表面硅羟基较多，吸水性强，表面带负电容易团聚。十八烷基二甲基叔胺是一种阳离子表面活性剂荷正电，相比于其他药剂更容易与沸石表面的负电荷发生静电吸附作用使沸石疏水，从而使改性后的沸石有更好的疏水性和分散性。1. Natural zeolite has more silicic hydroxyl groups on the surface, strong water absorption, and easy to agglomerate when the surface is negatively charged. Octadecyl dimethyl tertiary amine is a cationic surfactant that is positively charged. Compared with other agents, it is easier to electrostatically adsorb the negative charge on the surface of the zeolite to make the zeolite hydrophobic, so that the modified zeolite has more Good hydrophobicity and dispersibility.
2、本发明采用十八烷基二甲基叔胺改性沸石，十八烷基二甲基叔胺是长链烷基二甲基叔胺的一种，其碳链长，即疏水链长，憎水性好，极性基团容易被包埋，对提高改性沸石的疏水性提高很大，并且其长链烷基，柔顺性好，能够提高后续复合的天然橡胶的机械性能。2. The present invention uses octadecyl dimethyl tertiary amine to modify the zeolite. The octadecyl dimethyl tertiary amine is a kind of long-chain alkyl dimethyl tertiary amine, and its carbon chain length is the hydrophobic chain length. , Good hydrophobicity, polar groups are easy to be embedded, which greatly improves the hydrophobicity of modified zeolite, and its long-chain alkyl group has good flexibility, which can improve the mechanical properties of subsequent composite natural rubber.
3、本发明的方法适用于天然橡胶，是因为天然橡胶中，橡胶结构是顺式1，4-聚异戊二烯，其具有较低的熔点，溶解度大的特点，十八烷基二甲基叔胺是碱性物质，其中的胺基可以和天然橡胶中的C＝O键在碱性条件下发生酰化反应，促进硫化作用，增强硫化胶的交联密度，从而提高橡胶复合材料的机械性能。另外，十八烷基二甲基叔胺改性沸石与天然橡胶复合之后，在橡胶内部形成网状结构，也会增强了天然橡胶力学性能。3. The method of the present invention is suitable for natural rubber, because in natural rubber, the rubber structure is cis 1,4-polyisoprene, which has the characteristics of low melting point and high solubility. The tertiary amine is an alkaline substance. The amine group can react with the C=O bond in natural rubber under alkaline conditions to promote vulcanization and enhance the crosslinking density of the vulcanizate, thereby improving the rubber composite material. Mechanical behavior. In addition, after the octadecyl dimethyl tertiary amine modified zeolite is compounded with natural rubber, a network structure is formed inside the rubber, which will also enhance the mechanical properties of natural rubber.
4、本发明对沸石采用湿法超细粉磨工艺，磨矿分散性较好，粒度较干磨均匀 ，并且结合后续湿法改性工艺，工艺流程简单，不用烘干，成本较低。4. The present invention adopts a wet ultrafine grinding process for zeolite, which has better ore dispersibility and a uniform particle size than dry grinding, and combined with the subsequent wet modification process, the process flow is simple, no drying is required, and the cost is lower.
5、本发明的方法中，采用的天然沸石、天然橡胶原料易得，储量大，成本低，沸石的骨架结构可以提高复合材料的力学性能。5. In the method of the present invention, the natural zeolite and natural rubber raw materials used are easily available, large in reserve, and low in cost. The framework structure of the zeolite can improve the mechanical properties of the composite material.
发明实施例Invention embodiment
本发明的实施方式Embodiments of the invention
下面结合实施例对本发明作进一步的详细说明。The present invention will be further described in detail below in conjunction with the embodiments.
以下实施例中，除非特殊说明，浓度指质量浓度。In the following examples, unless otherwise specified, concentration refers to mass concentration.
实施例1Example 1
一种十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料的制备方法，包括以下步骤：A method for preparing a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber, including the following steps:
步骤1：step 1:
将天然沸石进行湿法超细粉磨，得到沸石矿浆；其中，沸石矿浆中沸石粉的粒度分布为D 90为20μm；在湿法超细粉磨的磨矿浓度，即为沸石矿浆浓度为50％，介质充填率70％； The natural zeolite is subjected to wet ultrafine grinding to obtain zeolite slurry; among them, the particle size distribution of zeolite powder in the zeolite slurry is D 90 of 20 μm; the grinding concentration in the wet ultrafine grinding is the zeolite slurry concentration of 50 %, the medium filling rate is 70%;
步骤2：Step 2:
将十八烷基二甲基叔胺和盐酸，按摩尔比为十八烷基二甲基叔胺∶盐酸＝1∶1在去离子水中溶解后，得到溶解完全的十八烷基二甲基叔胺的盐溶液；Dissolve octadecyl dimethyl tertiary amine and hydrochloric acid at a molar ratio of octadecyl dimethyl tertiary amine: hydrochloric acid = 1:1 in deionized water to obtain completely dissolved octadecyl dimethyl amine Salt solution of tertiary amine;
加入无机酸或碱调节沸石矿浆至pH＝7，将十八烷基二甲基叔胺的盐溶液加入沸石矿浆中，然后配置成沸石质量百分比为25％的矿浆；其中，十八烷基二甲基叔胺的药剂用量为沸石质量的1％。Add inorganic acid or alkali to adjust the zeolite slurry to pH=7, add the salt solution of octadecyl dimethyl tertiary amine to the zeolite slurry, and then configure it into a slurry with a mass percentage of 25% zeolite; The dosage of methyl tertiary amine is 1% of the mass of zeolite.
将矿浆在改性温度80℃，高速混合机转速为900r/min的条件下进行湿法改性20min，得到改性后的产物。The ore slurry was subjected to wet modification for 20 minutes at a modification temperature of 80° C. and a high-speed mixer rotating speed of 900 r/min to obtain a modified product.
步骤3：Step 3:
将改性后的产物放在烘箱中110℃烘干24h至恒重，粉磨打碎，得到十八烷基二甲基叔胺改性沸石，十八烷基二甲基叔胺改性沸石的接触角为113°，活化指数为98.32％。Place the modified product in an oven at 110°C for 24h to constant weight, pulverize and crush to obtain octadecyl dimethyl tertiary amine modified zeolite, stearyl dimethyl tertiary amine modified zeolite The contact angle is 113°, and the activation index is 98.32%.
步骤4：Step 4:
按照天然橡胶100phr，硬脂酸3phr，石蜡1phr，促进剂0.7phr，氧化锌5phr，防 老剂1phr，硫3phr和十八烷基二甲基叔胺改性沸石30phr的配方，进行混炼、硫化，制得十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料。According to the formula of 100 phr of natural rubber, 3 phr of stearic acid, 1 phr of paraffin, 0.7 phr of accelerator, 5 phr of zinc oxide, 1 phr of antioxidant, 3 phr of sulfur and 30 phr of stearyl dimethyl tertiary amine modified zeolite for mixing and vulcanization , The composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber is prepared.
对比例1Comparative example 1
一种沸石和天然橡胶复合的材料的制备方法，同实施例1，不同之处在于：A method for preparing a composite material of zeolite and natural rubber is the same as in Example 1, except that:
(1)无步骤1、步骤2、步骤3；(1) No step 1, step 2, step 3;
(2)在步骤4中，采用未改性的沸石替代十八烷基二甲基叔胺改性沸石，其他相同，得到未改性沸石和天然橡胶复合的材料。(2) In step 4, an unmodified zeolite is used to replace the stearyl dimethyl tertiary amine modified zeolite, and the others are the same to obtain a composite material of unmodified zeolite and natural rubber.
对比例2Comparative example 2
一种钛酸脂JN-114改性沸石和天然橡胶复合的材料的制备方法，同实施例1，不同之处在于：A preparation method of a composite material of titanate JN-114 modified zeolite and natural rubber is the same as that in Example 1, except that:
(1)无步骤1、步骤2、步骤3；(1) No step 1, step 2, step 3;
(2)在步骤4中，采用钛酸脂JN-114改性沸石替代十八烷基二甲基叔胺改性沸石，其他相同，得到钛酸脂JN-114改性沸石和天然橡胶复合的材料。(2) In step 4, use titanate JN-114 modified zeolite instead of octadecyl dimethyl tertiary amine modified zeolite, and the others are the same to obtain a composite of titanate JN-114 modified zeolite and natural rubber material.
对比例3Comparative example 3
一种Si69偶联剂改性沸石和天然橡胶复合的材料的制备方法，同实施例1，不同之处在于：A preparation method of a composite material of Si69 coupling agent modified zeolite and natural rubber is the same as in Example 1, except that:
(1)无步骤1、步骤2、步骤3；(1) No step 1, step 2, step 3;
(2)在步骤4中，采用Si69偶联剂改性沸石替代十八烷基二甲基叔胺改性沸石，其他相同，得到Si69偶联剂改性沸石和天然橡胶复合的材料。(2) In step 4, the Si69 coupling agent modified zeolite is used to replace the stearyl dimethyl tertiary amine modified zeolite, and the others are the same, to obtain a Si69 coupling agent modified zeolite and natural rubber composite material.
对实施例1、对比例1、对比例2、对比例3得到的复合的材料进行力学性能测试，得到的测试结果见表1。The mechanical properties of the composite materials obtained in Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 were tested, and the obtained test results are shown in Table 1.
表1填充未改性沸石和不同药剂改性沸石的力学性能测试结果如下：Table 1 The test results of the mechanical properties of filled unmodified zeolite and modified zeolite with different agents are as follows:
[Table 1][Table 1]
Figure PCTCN2019096252-appb-000001
Figure PCTCN2019096252-appb-000001
实施例2Example 2
一种十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料的制备方法，包括以下步骤：A method for preparing a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber, including the following steps:
步骤1：step 1:
将天然沸石进行湿法超细粉磨，得到沸石矿浆；其中，沸石矿浆中沸石粉的粒度分布为D 90为20μm；在湿法超细粉磨中，磨矿浓度为50％，介质充填率70％； Natural zeolite is subjected to wet ultrafine grinding to obtain zeolite slurry; among them, the particle size distribution of zeolite powder in the zeolite slurry is D 90 of 20μm; in wet ultrafine grinding, the grinding concentration is 50%, and the medium filling rate 70%;
步骤2：Step 2:
将十八烷基二甲基叔胺和盐酸，按摩尔比为十八烷基二甲基叔胺∶盐酸＝1∶1在去离子水中溶解后，得到溶解完全的十八烷基二甲基叔胺的盐溶液；Dissolve octadecyl dimethyl tertiary amine and hydrochloric acid at a molar ratio of octadecyl dimethyl tertiary amine: hydrochloric acid = 1:1 in deionized water to obtain completely dissolved octadecyl dimethyl amine Salt solution of tertiary amine;
加入无机酸或碱调节沸石矿浆至pH＝7，将十八烷基二甲基叔胺的盐溶液加入沸石矿浆中，然后配置成沸石质量百分比为25％的矿浆；其中，十八烷基二甲基叔胺的药剂用量为沸石质量的1％。Add inorganic acid or alkali to adjust the zeolite slurry to pH=7, add the salt solution of octadecyl dimethyl tertiary amine to the zeolite slurry, and then configure it into a slurry with a mass percentage of 25% zeolite; The dosage of methyl tertiary amine is 1% of the mass of zeolite.
将矿浆在改性温度80℃，高速混合机转速为900r/min的条件下进行湿法改性20min，得到改性后的产物。The ore slurry was subjected to wet modification for 20 minutes at a modification temperature of 80° C. and a high-speed mixer rotating speed of 900 r/min to obtain a modified product.
步骤3：Step 3:
将改性后的产物放在烘箱中110℃烘干24h至恒重，粉磨打碎，得到十八烷基二甲基叔胺改性沸石。十八烷基二甲基叔胺改性沸石的接触角为113°，活化指数为98.32％。The modified product is dried in an oven at 110°C for 24 hours to a constant weight, and is ground and crushed to obtain the stearyl dimethyl tertiary amine modified zeolite. The contact angle of the stearyl dimethyl tertiary amine modified zeolite is 113°, and the activation index is 98.32%.
步骤4：Step 4:
按照天然橡胶100phr，硬脂酸3phr，石蜡1phr，促进剂0.7phr，氧化锌5phr，防老剂1phr，硫3phr和十八烷基二甲基叔胺改性沸石10phr的配方，进行混炼、硫化，制得十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料。According to the formula of 100phr of natural rubber, 3phr of stearic acid, 1phr of paraffin, 0.7phr of accelerator, 5phr of zinc oxide, 1phr of antioxidant, 3phr of sulfur and 10phr of stearyl dimethyl tertiary amine modified zeolite for mixing and vulcanization , The composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber is prepared.
对比例4Comparative example 4
一种沸石和天然橡胶复合的材料的制备方法，同实施例2，不同之处在于：A method for preparing a composite material of zeolite and natural rubber is the same as in Example 2, except that:
(1)无步骤1、步骤2、步骤3；(1) No step 1, step 2, step 3;
(2)在步骤4中，采用未改性的沸石替代十八烷基二甲基叔胺改性沸石，其他相同，得到未改性沸石和天然橡胶复合的材料。(2) In step 4, an unmodified zeolite is used to replace the stearyl dimethyl tertiary amine modified zeolite, and the others are the same to obtain a composite material of unmodified zeolite and natural rubber.
对比例5Comparative example 5
一种钛酸脂JN-114改性沸石和天然橡胶复合的材料的制备方法，同实施例2，不同之处在于：A preparation method of a composite material of titanate JN-114 modified zeolite and natural rubber is the same as in Example 2, except that:
(1)无步骤1、步骤2、步骤3；(1) No step 1, step 2, step 3;
(2)在步骤4中，采用钛酸脂JN-114改性沸石替代十八烷基二甲基叔胺改性沸石，其他相同，得到钛酸脂JN-114改性沸石和天然橡胶复合的材料。(2) In step 4, use titanate JN-114 modified zeolite instead of octadecyl dimethyl tertiary amine modified zeolite, and the others are the same to obtain a composite of titanate JN-114 modified zeolite and natural rubber material.
对比例6Comparative example 6
一种Si69偶联剂改性沸石和天然橡胶复合的材料的制备方法，同实施例2，不同之处在于：A preparation method of a composite material of Si69 coupling agent modified zeolite and natural rubber is the same as in Example 2, except that:
(1)无步骤1、步骤2、步骤3；(1) No step 1, step 2, step 3;
(2)在步骤4中，采用Si69偶联剂改性沸石替代十八烷基二甲基叔胺改性沸石，其他相同，得到Si69偶联剂改性沸石和天然橡胶复合的材料。(2) In step 4, the Si69 coupling agent modified zeolite is used to replace the stearyl dimethyl tertiary amine modified zeolite, and the others are the same, to obtain a Si69 coupling agent modified zeolite and natural rubber composite material.
对实施例2、对比例4、对比例5、对比例6得到的复合的材料进行力学性能测试，得到的测试结果见表2。The composite materials obtained in Example 2, Comparative Example 4, Comparative Example 5, and Comparative Example 6 were tested for mechanical properties, and the obtained test results are shown in Table 2.
表2填充未改性沸石和不同药剂改性沸石的力学性能测试结果如下：Table 2 The test results of the mechanical properties of the filled unmodified zeolite and the modified zeolite with different agents are as follows:
[Table 2][Table 2]
Figure PCTCN2019096252-appb-000002
Figure PCTCN2019096252-appb-000002
通过表1、表2数据可以说明十八烷基二甲基叔胺改性沸石能够显著提高天然橡胶的机械力学性能。The data in Table 1 and Table 2 shows that the octadecyl dimethyl tertiary amine modified zeolite can significantly improve the mechanical properties of natural rubber.

Claims (10)

  1. 一种十八烷基二甲基叔胺改性沸石的制备方法，其特征在于，包括以下步骤：A preparation method of octadecyl dimethyl tertiary amine modified zeolite is characterized in that it comprises the following steps:
    步骤1：超细粉磨Step 1: Superfine grinding
    将天然沸石进行湿法超细粉磨，得到沸石矿浆；其中，沸石矿浆中沸石的粒度分布为D 90为5μm～30μm； The natural zeolite is subjected to wet ultrafine grinding to obtain zeolite slurry; wherein the particle size distribution of the zeolite in the zeolite slurry is D 90 of 5 μm to 30 μm;
    步骤2：湿法改性Step 2: Wet modification
    将盐酸和十八烷基二甲基叔胺按比例在去离子水中混溶，得到溶解完全的十八烷基二甲基叔胺的盐溶液；其中比例按摩尔比，盐酸∶十八烷基二甲基叔胺＝1∶1；The hydrochloric acid and octadecyl dimethyl tertiary amine are mixed in deionized water in proportion to obtain a completely dissolved salt solution of octadecyl dimethyl tertiary amine; the ratio is molar ratio, hydrochloric acid: octadecyl Dimethyl tertiary amine=1:1;
    调节沸石矿浆pH值为6～10，加入溶解完全的十八烷基二甲基叔胺的盐溶液，然后配置成沸石质量百分比为20～30％的矿浆；其中，按质量比，沸石矿浆中沸石粉∶十八烷基二甲基叔胺＝100∶(0.5～1.5)；Adjust the pH value of the zeolite pulp to 6-10, add the completely dissolved salt solution of octadecyl dimethyl tertiary amine, and then configure the zeolite pulp with a mass percentage of 20-30%; among them, according to the mass ratio, the zeolite pulp Zeolite powder: octadecyl dimethyl tertiary amine = 100: (0.5～1.5);
    将矿浆，在改性温度40～100℃，高速混合机转速为800～1000r/min的条件下进行湿法改性5～60min，得到改性后的产物；The ore pulp is subjected to wet modification for 5-60 minutes at a modification temperature of 40-100°C and a high-speed mixer rotating speed of 800-1000r/min to obtain a modified product;
    步骤3：干燥处理Step 3: Drying
    将改性后的产物进行烘干至恒重，粉磨打碎，得到干燥的十八烷基二甲基叔胺改性沸石；其中，十八烷基二甲基叔胺改性沸石的D 90为5μm～30μm。 The modified product is dried to a constant weight, pulverized and crushed to obtain dry octadecyl dimethyl tertiary amine modified zeolite; among them, the D of stearyl dimethyl tertiary amine modified zeolite 90 is 5 μm to 30 μm.
  2. 根据权利要求1所述的十八烷基二甲基叔胺改性沸石的制备方法，其特征在于，所述的步骤1中，湿法超细粉磨的磨矿浓度为45～60％，介质填充率为70％。The method for preparing octadecyl dimethyl tertiary amine modified zeolite according to claim 1, characterized in that, in the step 1, the grinding concentration of the wet ultrafine grinding is 45-60%, The medium filling rate is 70%.
  3. 根据权利要求1所述的十八烷基二甲基叔胺改性沸石的制备方法，其特征在于，所述的步骤2中，高速混合机转速为900r/min。The method for preparing octadecyl dimethyl tertiary amine modified zeolite according to claim 1, wherein in the step 2, the speed of the high-speed mixer is 900 r/min.
  4. 根据权利要求1所述的十八烷基二甲基叔胺改性沸石的制备方法，其特征在于，所述的步骤3中，所述的烘干，采用置于烘箱中在100～120℃烘干24h。The method for preparing octadecyl dimethyl tertiary amine modified zeolite according to claim 1, characterized in that, in the step 3, the drying is carried out in an oven at 100-120°C Dry for 24h.
  5. 一种十八烷基二甲基叔胺改性沸石，其特征在于，该十八烷基二甲基叔胺改性沸石采用权利要求1～4任意一项所述的制备方法制得。An octadecyl dimethyl tertiary amine modified zeolite, characterized in that the octadecyl dimethyl tertiary amine modified zeolite is prepared by the preparation method of any one of claims 1 to 4.
  6. 根据权利要求5所述的十八烷基二甲基叔胺改性沸石，其特征在于，十八烷基二甲基叔胺改性沸石的接触角100°～120°，活化指数为90％～100％。The octadecyl dimethyl tertiary amine modified zeolite according to claim 5, wherein the octadecyl dimethyl tertiary amine modified zeolite has a contact angle of 100° to 120° and an activation index of 90% ~100%.
  7. 一种十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料，其特征在于，该十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料包括权利要求5-6任意一项所述的十八烷基二甲基叔胺改性沸石和天然橡胶，按质量比，十八烷基二甲基叔胺改性沸石∶天然橡胶＝(10～70)∶100。A composite material of stearyl dimethyl tertiary amine modified zeolite and natural rubber, characterized in that, the composite material of stearyl dimethyl tertiary amine modified zeolite and natural rubber comprises claims 5-6 According to the mass ratio of the octadecyl dimethyl tertiary amine modified zeolite and natural rubber, the octadecyl dimethyl tertiary amine modified zeolite: natural rubber=(10-70):100.
  8. 权利要求7所述的十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料的制备方法，其特征在于，包括以下步骤：The method for preparing a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber according to claim 7, characterized in that it comprises the following steps:
    将制备的十八烷基二甲基叔胺改性沸石加入橡胶配方中，进行混炼，硫化，得到十八烷基二甲基叔胺改性沸石和橡胶复合的材料；其中，所述的硫化，其硫化时间和硫化温度，根据混炼后的物料检测得到的硫化曲线确定。The prepared octadecyl dimethyl tertiary amine modified zeolite is added to the rubber formula, mixed and vulcanized to obtain a composite material of octadecyl dimethyl tertiary amine modified zeolite and rubber; wherein, For vulcanization, the vulcanization time and vulcanization temperature are determined according to the vulcanization curve obtained from the inspection of the mixed materials.
  9. 根据权利要求8所述的十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料的制备方法，其特征在于，所述的橡胶配方，根据天然橡胶的用途可选用以下配方：The method for preparing a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber according to claim 8, wherein the rubber formula can be selected from the following formulas according to the use of natural rubber:
    天然橡胶100phr，硬脂酸3phr，石蜡1phr，促进剂0.7phr，氧化锌5phr，防老剂1phr，硫3phr，改性沸石10phr～70phr。Natural rubber 100phr, stearic acid 3phr, paraffin wax 1phr, accelerator 0.7phr, zinc oxide 5phr, antioxidant 1phr, sulfur 3phr, modified zeolite 10phr～70phr.
  10. 根据权利要求9所述的十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料的制备方法，其特征在于，采用权利要求9所述的橡胶配方制得的十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料恒温25℃放置24h后测试其力学性能，得到的十八烷基二甲基叔胺改性沸石和天然橡胶复合的材料的拉伸强度20MPa～30MPa，撕裂强度25MPa～35MPa，扯断伸长率600％～1000％，邵氏硬度35～4 5。The method for preparing a composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber according to claim 9, characterized in that the octadecyl dimethyl tertiary amine modified zeolite and natural rubber compound material are prepared by using the rubber formula of claim 9 The composite material of methyl tertiary amine modified zeolite and natural rubber was placed at a constant temperature of 25°C for 24 hours and its mechanical properties were tested. The tensile strength of the composite material of octadecyl dimethyl tertiary amine modified zeolite and natural rubber was 20MPa～ 30MPa, tear strength 25MPa～35MPa, elongation at break 600%～1000%, Shore hardness 35～45.
PCT/CN2019/096252 2019-07-11 2019-07-17 Composite material of octadecyldimethyl-tertiary-amine-modified zeolite and natural rubber and preparation method therefor WO2021003760A1 (en)

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