WO2017088503A1 - 一种半开式过热蒸汽喷雾干燥法制备高填充复合母胶的方法 - Google Patents

一种半开式过热蒸汽喷雾干燥法制备高填充复合母胶的方法 Download PDF

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WO2017088503A1
WO2017088503A1 PCT/CN2016/090640 CN2016090640W WO2017088503A1 WO 2017088503 A1 WO2017088503 A1 WO 2017088503A1 CN 2016090640 W CN2016090640 W CN 2016090640W WO 2017088503 A1 WO2017088503 A1 WO 2017088503A1
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rubber
inorganic filler
carbon black
suspension
spray drying
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PCT/CN2016/090640
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French (fr)
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张立群
王益庆
吴晓辉
沈家锋
张志辉
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北京化工大学
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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
    • C08L7/02—Latex
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • C08L11/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C08L9/04—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C08L9/08—Latex

Definitions

  • the invention relates to a method for preparing a high-filled composite masterbatch by a semi-open superheated steam spray drying method.
  • the rubber high-filled nano-composite masterbatch obtained by the method is mainly applied to the fields of car tread rubber, engineering tread rubber and the like.
  • the conventional method for preparing rubber is a rubber prepared by using a rubber emulsion as a raw material, solidified by adding acid, and then being tableted or granulated, dried and dehydrated.
  • the traditional process not only has a long preparation time period, but also is basically manual operation, and there is a large error. A large amount of acid is required as a desiccant in the production process, and the wastewater generated during the treatment cannot be treated and pollutes the environment. At the same time, the quality of traditionally prepared rubber processes is not easy to control, resulting in poor product consistency.
  • nanocomposite technology has been introduced into the field of spray drying.
  • the inorganic filler is often added in a rubber matrix by dry mixing. Whether it is the addition of an open mill or the addition of an internal mixer, there is a high energy consumption, and it is difficult to achieve the effect of nano-scale dispersion, which is also a key technology for obtaining a significant improvement in the comprehensive performance of the composite material.
  • the masterbatch technology has become a hot spot in the field of rubber research.
  • the nano-scale dispersion of inorganic fillers such as carbon black, white carbon black and clay in rubber emulsion has become the focus of research in masterbatch technology.
  • the structure of the inorganic filler and the rubber particles which are well dispersed is formed after interpenetrating and separating with the rubber emulsion.
  • the latex particles and the latex particles are also present due to the inorganic filler, forming a mutual isolation effect, so that the latex particles do not stick together to block the feed tube, thereby solving the difficulty in blocking the tube during the spray drying process.
  • superheated steam is an advanced technology in the field of drying in spray drying technology.
  • the drying mechanism is to form fine atomized droplets under the action of high-speed centrifugation or high pressure by liquid materials such as suspensions and solutions, which greatly increases the drying of liquid raw materials.
  • the specific surface area of the heat in the medium greatly shortens the drying speed.
  • the superheated steam spray drying equipment is steamed by the drying medium, thereby ensuring that the material does not generate local high temperature during the drying process, and also reduces the heat of the material. Degree of oxidation and aging.
  • a semi-open superheated steam dryer is used because the water vapor is continuously increasing during the drying process. If the superheated steam is closed, the pressure in the spray tower increases as the reaction time increases. When the pressure reaches 1.5 MPa, the pressure valve will automatically open, and excess water vapor will be discharged into the tower to achieve pressure balance in the tower.
  • the high-filled nano-composite masterbatch is prepared by spray-drying by modifying the inorganic filler, mixing and grinding to form a mixed liquid, and the process adopts a relatively simple and quick one-step drying method, which reduces the processes of flocculation, washing and the like in the conventional process, and shortens the process time. At the same time, it saves costs. And condensed water, ethanol, etc. produced during the production process will also be used for recycling. It is in response to national environmental protection policies that reduce water waste and environmental pollution.
  • the object of the present invention is to provide a novel high-filled nano-composite masterbatch production technology with simple operation, low cost and easy industrialization, and a method for preparing a high-filled nano-composite masterbatch by a semi-open superheated steam spray drying method.
  • the process steps are mainly to prepare the inorganic filler into a suspension slurry, and after the modification treatment, the mixture is blended with the rubber paste, and the mixture is uniformly stirred to ensure that the mixed liquid is not demulsified, and superheated steam spray drying is performed to obtain a high-filled nano-composite masterbatch.
  • the fraction of the inorganic filler is 25 to 120 parts, and in the general dry mixing, it is a high part filling process.
  • the inorganic filler treated by the modifier changes the surface structure of the particles during the grinding process, and acts with the rubber emulsion to form a mixed emulsion which is not demulsified, and is formed by a high-speed centrifugation of the atomizer of the spray drying device to form 30-100 ⁇ m.
  • Fine droplets large specific surface area in the steam medium of 100 ⁇ 350 ° C, rapid dehydration and drying, because a large amount of filler is present, forming a better isolation layer, so that the formation of powder or granular rubber will not be due to itself Viscosity and adhesion, wall hanging and other phenomena. Finally, it is brought into the transport zone by the air-inducing action to obtain a powder-filled nano-composite masterbatch.
  • the preparation process of the masterbatch solves the problems of acid treatment, flocculation wastewater treatment, flocculation of the gel, and long drying time of the drying chamber in the conventional process.
  • the inorganic filler is modified, the inorganic fillers such as silica, carbon black and clay can be better compatible with the rubber compound, and the inorganic filler in the conventional dry mixing is difficult to disperse in the rubber matrix and consume energy. Big, dusty and other issues.
  • the superheated steam spray drying process is caused by superheated steam, which is different from the direct contact of hot air with the rubber compound, which makes the rubber compound dry quickly, avoids the characteristics of long drying time, easy oxidation and aging of the rubber in the traditional drying process, and the obtained nanometer.
  • the composite masterbatch has the advantages of low heat history, less oxidative aging and low energy consumption.
  • the process of solving the present invention employs the following steps:
  • a method for preparing a high-filled composite masterbatch by a semi-open superheated steam spray drying method characterized in that: adding an inorganic filler suspension having a content of 2% to 30% by adding water, grinding the mixture for 15 minutes after adding a modifier, The treated inorganic filler suspension is added to the rubber emulsion, and the quality of the inorganic filler is 25-120% of the mass of the rubber emulsion dry glue. After stirring, a mixed suspension of the inorganic filler/rubber emulsion is obtained, and the particle diameter of the mixed suspension is 5-20 ⁇ m. , spray drying treatment, atomized droplet size of 30 ⁇ 100 ⁇ m, spray drying equipment inlet temperature of 150 ⁇ 350 ° C, outlet temperature of 100 ⁇ 120 ° C, to obtain a powdery rubber composite masterbatch.
  • the inorganic filler is carbon black, white carbon or clay.
  • the concentration of the suspension is 3 to 30%, and the amount of carbon black is 30 to 60% of the mass of the rubber emulsion.
  • the modifier is selected from ethanol as an sizing agent, and the amount of ethanol is 50 to 100% of the mass of the carbon black.
  • the concentration of the suspension is 10 to 30%, and the amount of white carbon black is 30 to 120% of the mass of the rubber emulsion.
  • the modifier is selected from the group consisting of polyethylene glycol, silicon-oxygen coupling agent and polyol, and the amount is 1% to 5% of the mass of the white carbon black.
  • the white carbon black suspension needs to be heated at 70-90 ° C before being mixed with the latex. The next treatment is 1 to 3 hours.
  • the concentration of the suspension is 2-20%, and the amount of the clay is 25-120% of the mass of the rubber emulsion dry glue.
  • the modifier is a quaternary ammonium salt, and the quaternary ammonium salt used is preferably a quaternary ammonium salt having a main chain having a carbon number of 12 to 18, and a mass ratio to the clay of 0.1% to 5%.
  • the rubber emulsion is a mixture of a skim latex, a natural rubber emulsion, a styrene-butadiene rubber emulsion, a neoprene emulsion, a nitrile rubber emulsion, a styrene-butadiene rubber emulsion, a buty-butadiene rubber emulsion, and the above rubber emulsion.
  • the inorganic filler is selected from a solid powder and water to prepare a suspension, which is treated by a treating agent to obtain a uniform suspension.
  • a treating agent For example, carbon black and water are difficult to infiltrate to form a relatively uniform suspension, so it is necessary to add an sizing agent, and then grind repeatedly. It can be prepared as a homogeneous aqueous solution.
  • white carbon black is added into water to form a suspension, sedimentation and agglomeration tend to occur, and some organic modifiers need to be added to prevent sinking to form a uniform aqueous solution.
  • the inorganic clay is modified and organicized by the quaternary ammonium salt, the lamellar structure changes, and the interlamellar spacing increases, so that the effect is better and better when it is combined with the colloidal particles.
  • the clay is added to the water to form a clay liquid, and a suitable modifier can be added to increase the interlayer spacing of the clay, so that the latex particles in the rubber emulsion can better enter the layer of the clay-modified clay.
  • a suitable modifier can be added to increase the interlayer spacing of the clay, so that the latex particles in the rubber emulsion can better enter the layer of the clay-modified clay.
  • the invention discloses a method for preparing a high-filled composite masterbatch by a semi-open superheated steam spray drying method.
  • the process step is mainly to prepare an inorganic filler into a well-dispersed suspension slurry, and after being modified and ground, blended with the rubber emulsion, and uniformly stirred to ensure no Under the condition of demulsification, spray drying is carried out to obtain a nano-composite masterbatch.
  • the invention uses a modifier to modify the inorganic filler to improve the dispersibility of the inorganic filler in the rubber matrix.
  • the process is simple, the equipment requirements are low, and the production efficiency is high.
  • the nano-composite masterbatch prepared by the method of the invention solves the problem of dust flying and environmental pollution caused by the dry mixing process, reduces environmental pollution and saves cost.
  • the preparation process of the invention saves the flocculation time, shortens the product production cycle, saves manpower and energy consumption, has small influence factors on the process, and is easy to obtain a product with stable quality, and is suitable for continuous industrial production.
  • the implementation equipment of the present invention is a conventional device, and all performance test standards are performed in accordance with corresponding national standards.
  • Example 1 the spray drying inlet temperature was 220 ° C, and the outlet temperature was 110 ° C to obtain a powdery nanocomposite masterbatch. 180 phr of the above masterbatch was taken, and the remaining steps were the same as in Example 1.
  • Example 1 the spray drying inlet temperature was 180 ° C, and the outlet temperature was 100 ° C to obtain a granular nanocomposite masterbatch.
  • the spray drying inlet temperature was 180 ° C
  • the outlet temperature was 100 ° C to obtain a granular nanocomposite masterbatch.
  • the uniformly mixed mixture was subjected to a semi-open superheated steam spray drying treatment, and the atomized droplets were controlled at 70 ⁇ m.
  • the spray drying inlet temperature was 280 ° C, and the outlet temperature was 90 ° C to obtain a powdery nanocomposite masterbatch.
  • the above-mentioned masterbatch was 125 phr, and the remaining steps were the same as in Example 1.
  • the liquid mixture was subjected to a semi-open superheated steam spray drying treatment, the atomized droplets were controlled at 30 ⁇ m, the spray drying inlet temperature was 350 ° C, and the outlet temperature was 110 ° C to obtain a powdery nanocomposite masterbatch.
  • the above-mentioned masterbatch was 150 phr, and the remaining steps were the same as in Example 1.
  • the superheated steam spray drying treatment, the atomized droplets are controlled at 40 ⁇ m, the spray drying inlet temperature is 350 ° C, and the outlet temperature is 110 ° C to obtain a powdery nanocomposite masterbatch.
  • the above-mentioned masterbatch was 150 phr, and the remaining steps were the same as in Example 1.
  • Example 1 Formulated on a two-roll mill: 100 phr of nitrile rubber, 50 phr of carbon black (N330), the remaining compounding agent is as in Example 1, and the remaining steps are as in Example 1.
  • Example 1 Formulated on a two-roll mill: 100 phr of neoprene, 60 phr of white carbon, the remaining compounding agent is as in Example 1, and the remaining steps are as in Example 1.
  • Example 1 Formulated on a two-roll mill: 100 phr of natural rubber and styrene-butadiene rubber, 50 phr of carbon black, the other compounding agent is as in Example 1, and the remaining steps are as in Example 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Dispersion Chemistry (AREA)

Abstract

一种半开式过热蒸汽喷雾干燥法制备高填充复合母胶的方法，其特点是：加水配制无机填料悬浮液，加入改性剂处理，充分研磨后的无机填料悬浮液加入到橡胶乳液中，搅拌均匀，在无破乳条件下进行喷雾干燥，获得粉末或微珠状复合母胶产品。该方法工艺简单，橡胶成分保留完全，解决高填充母胶的问题，无絮凝剂无污染，干燥时间短，人为因素少，能够连续性生产，产品质量稳定，易于工业化。制备的纳米复合母胶能够使无机填料在橡胶基体中以纳米级的形式均匀分散，可用于轿车轮胎、工程胎面胶等领域。

Description

一种半开式过热蒸汽喷雾干燥法制备高填充复合母胶的方法 技术领域
本发明涉及一种半开式过热蒸汽喷雾干燥法制备高填充复合母胶的方法。该方法所得橡胶高填充纳米复合母胶主要应用于轿车胎面胶，工程胎面胶等领域。
背景技术
传统制备橡胶的方法以橡胶乳液为原料，经加酸凝固，再经压片或造粒、干燥脱水而制成的橡胶。传统工艺不仅制备时间周期长，且基本为人工操作，存在较大误差。生产过程中需要大量的酸为干燥剂，处理过程中产生的废水无法处理，污染环境。同时，传统制备橡胶工艺质量不易控制，导致了产品一致性较差。
在橡胶工业领域内，喷雾干燥工艺有少量应用。但是橡胶乳液由于其粘度较大，使得在喷雾干燥过程中容易粘壁，堵塞进料管，甚至堵塞雾化器等问题，制约了喷雾干燥在橡胶干燥领域的应用。
为了解决上述问题，人们将纳米复合技术引入到喷雾干燥领域。传统工艺中，无机填料在橡胶基体中的添加方式往往为干法混炼。无论是开炼机添加，还是密炼机中添加，都存在着高耗能，不易实现纳米级分散的效果，这也是获得复合材料综合性能显著提升的关键技术。
当下，母胶技术成为橡胶领域研究的热点，炭黑、白炭黑、粘土等无机填料在橡胶乳液中的纳米级分散成为母胶技术中研究的重点。
无机填料经过处理剂处理后，在与橡胶乳液的混合过程中相互穿插隔离作用后形成了分散较好的无机填料与橡胶颗粒复合的结构。而胶乳粒子与胶乳粒子间也因无机填料存在，形成一种相互隔离的作用使得胶乳粒子间不粘连成块堵塞进料管，从而解决了喷雾干燥工艺制备橡胶过程中堵管的难点。
中国石油化工集团公司北京化工研究院的乔金粱教授等人发明了一种全硫化粉末橡胶的制备方法(专利号：00816450.9)。他们是利用辐照实 现橡胶胶乳的乳胶粒交联硫化，后进行喷雾干燥得到全硫化的粉末橡胶。它极易分散在塑料基体中，可以用来制备各种增韧塑料和热塑性弹性体。清华大学的朱跃峰教授等人发明了一种碳纳米管改性的粉末天然橡胶(专利号：200510058999.6)；他们是将碳纳米管表面处理后在水中分散，与天然胶乳混合，然后采用喷雾干燥法制备含有碳纳米管改性的粉末天然橡胶。
但喷雾干燥在橡胶领域中应用存在着许多问题，从而限制了喷雾干燥在橡胶干燥领域的发展。主要限制在于干燥过程中，由于局部温度过高会导致橡胶热氧老化较为严重，甚至会发生燃烧等现象。最重要的是橡胶干燥，会因为橡胶粘性，使得胶乳堵塞管道，挂壁等现象发生。
目前过热蒸汽在喷雾干燥技术在干燥领域中属于先进工艺，其干燥机理为将悬浮液、溶液等液体原料在高速离心或高压的作用下，形成细小雾化液滴，大大增加了液体原料在干燥介质中的受热比表面积，极大程度地缩短了干燥速度，同时，过热蒸汽喷雾干燥设备由于其干燥介质为蒸汽，从而保证了物料在干燥过程中不会产生局部高温，也减少了物料的热氧化及老化程度。
采用半开式过热蒸汽干燥机，这是因为水蒸气在干燥过程中，不断增加，若是闭合过热蒸汽，喷雾塔内压力会随着反应时间延长而增大。当压力达到1.5MPa时，压力阀会自动打开，将多余的水蒸气排出塔内，从而实现塔内压力平衡。
通过对无机填料改性，混合研磨形成混合液后采用喷雾干燥制备高填充纳米复合母胶，该工艺采用了较为简单快捷的一步干燥方式，减少了传统工艺中絮凝，水洗等过程，缩短工艺时间同时节约了成本。并且在生产过程中产生的冷凝水、乙醇等也将作为回收使用。正是响应了国家环境保护的政策，减少了水资源的浪费及环境污染，
发明内容
本发明的目的是提出一种操作简单、成本低、易于工业化的新型高填充纳米复合母胶生产技术，提供了一种半开式过热蒸汽喷雾干燥法制备高填充纳米复合母胶的方法。工艺步骤主要为将无机填料配制成悬浮浆液，改性处理研磨后与胶清进行共混，搅拌均匀保证混合液无破乳的条件下，进行过热蒸汽喷雾干燥得到高填充纳米复合母胶。
本工艺中，无机填料份数为25～120份，在一般的干法混炼中，尚属高份数填充工艺。经过改性剂处理的无机填料，在研磨处理过程中粒子表面结构发生了变化，与橡胶乳液作用，形成不破乳的混合乳液，经过喷雾干燥设备的雾化器高速离心作用后形成30～100μm的细小液滴，较大的比表面积在100～350℃的蒸汽介质中快速脱水干燥，因为含有大量的填料存在，形成了较好的隔离层，使得形成粉末状或颗粒状胶料不会因为本身黏度而发生粘连，挂壁等现象。最后再经引风作用而带入输送区，得到粉末高填充纳米复合母胶。这样的母胶制备工艺，解决了传统工艺中加酸处理、絮凝废水处理不易、絮凝胶块不易清洗、烘房干燥时间长等问题。另外，因为无机填料经过改性之后，白炭黑、炭黑、粘土等无机填料能与胶料更好相容，也解决了传统干法混炼中无机填料不易在橡胶基体中分散、能耗大、粉尘大等问题。过热蒸汽喷雾干燥工艺因过热蒸汽存在，不同于热空气直接与胶料的接触，使得胶料干燥效率快，避免了传统干燥工艺中干燥时间长、胶料易氧化、老化等特点，得到的纳米复合母胶热历史低、氧化老化少、能耗低等优点。
解决本发明的工艺采用如下步骤：
1.一种半开式过热蒸汽喷雾干燥法制备高填充复合母胶的方法，其特征为：加水配制含量为2％～30％的无机填料悬浮液，加入改性剂处理后研磨15min，将处理后的无机填料悬浮液加入橡胶乳液，无机填料质量为橡胶乳液干胶质量的25～120％，搅拌均匀后得到无机填料/橡胶乳液的混合悬浮液，混合悬浮液中颗粒物直径为5～20μm，喷雾干燥处理，雾化液滴粒径为30～100μm，喷雾干燥设备进口温度150～350℃，出口温度100～120℃，得到粉末状橡胶复合母胶。
进一步，无机填料为炭黑、白炭黑或粘土。
当无机填料为炭黑粉末，悬浮液浓度为3～30％，炭黑用量为橡胶乳液干胶质量的30～60％。改性剂选乙醇作为浸润剂，乙醇用量为炭黑质量的50～100％。
当无机填料为白炭黑粉末，悬浮液浓度为10～30％，白炭黑用量为橡胶乳液干胶质量的30～120％。改性剂选聚乙二醇、硅氧偶联剂、多元醇，用量为白炭黑质量的1％～5％，白炭黑悬浮液在与胶乳混合前，需在70～90℃加热条件下处理1～3h。
当无机填料为粘土，悬浮液浓度为2～20％，粘土用量为橡胶乳液干胶质量的25～120％。改性剂为季铵盐，所使用的季铵盐优选主链含碳数为12至18的季铵盐，其与粘土的质量比为0.1％～5％。
进一步，橡胶乳液为胶清乳液、天然橡胶乳液、丁苯橡胶乳液、氯丁橡胶乳液、丁腈橡胶乳液、丁苯吡橡胶乳液、丁吡橡胶乳液，以及上述橡胶乳液的混合。
无机填料选用固体粉末加水配制成悬浮液，经处理剂处理得到均一的悬浮液，比如炭黑与水较难浸润形成较为均一的悬浮液，因此需要加入浸润剂处理，再加上研磨机反复研磨下可制备成均匀水溶液。而白炭黑加水配制成悬浮液后容易发生沉降团聚现象，需要加入一些有机改性剂防降沉从而形成均匀的水溶液。无机粘土经过季铵盐改性有机化后，其片层结构发生变化，片层间距增大，使得在与胶粒作用时，效果更佳良好。
均匀的炭黑、白炭黑悬浮液加入橡胶乳液中搅拌后，因改性剂的作用，可使得大量的无机粒子与橡胶粒子作用在一起，在迅速干燥后可得到分散较好的母胶产品。
而粘土加入水中水化作用形成粘土液，加入适当的改性剂，能够将粘土的片层间距增大，从而使得橡胶乳液中的胶乳颗粒更好进入粘土改性粘土的片层间，在喷雾干燥瞬间干燥工艺中，胶乳粒子嵌入粘土片层的结构得以完好保留，形成性能较好的粘土填充橡胶产品。
本发明的有益效果
一种半开式过热蒸汽喷雾干燥法制备高填充复合母胶的方法，工艺步骤主要为将无机填料配制成分散良好的悬浮浆液，改性处理研磨后与橡胶乳液进行共混，搅拌均匀保证无破乳的条件下，进行喷雾干燥得到纳米复合母胶，此法的优点在于：
1.避免使用强酸作为凝固剂，无污水处理，环境友好。
2.降低生产成本，减少水资源的浪费。
3.本发明采用改性剂对无机填料进行改性，提高无机填料在橡胶基体中分散性。
4.非胶成分保留完整，提升橡胶的品质。
5.工艺简单，设备要求低，生产效率高。
6.过热蒸汽干燥，产品热历史低、氧化老化少。
7.本发明方法制备的纳米复合母胶，解决了干法混炼过程中造成的粉尘飞扬，污染环境的问题，减少了环境污染，节省了成本。
8.本发明的制备工艺，节省了絮凝时间，缩短了产品生产周期，节约人力与能耗，工艺人为影响因素小，易于得到质量稳定的产品，适用于连续性的工业化生产。
本发明的实施设备均为常规设备，所有性能测试标准均按照相应的国家标准进行。
具体实施方式
实施例1
将市售的炭黑N234粉末30g加入970g水中，搅拌均匀后，加入15g乙醇，搅拌后研磨15min，得到炭黑悬浮液。在搅拌下，混入333.3g固含量为30％的天然乳液，得到粒径为5μm胶粒的混合液，将搅拌均匀的混合液进行半开式过热蒸汽喷雾干燥处理，雾化液滴控制在30μm，喷雾干燥进口温度为150℃，出口温度为80℃，得到粉末状纳米复合母胶，干燥过程中冷凝回收乙醇。取上述母胶130phr、ZnO 5phr、硬脂酸2phr、防老剂1010NA 1phr、促进剂CZ 1.2phr、硫磺2phr，炼胶，停放8h后测硫化曲线和橡胶加工性能，143℃下硫化，测机械性能。
实施例2
将市售的炭黑N330粉末60g加入140g水中，搅拌均匀后，加入60g乙醇，搅拌后研磨15min，得到炭黑悬浮液。在搅拌下，混入333.3g固含量为30％的天然胶乳，得到粒径为20μm胶粒的混合液，将搅拌均匀的混合液进行半开式过热蒸汽喷雾干燥处理，雾化液滴控制在100μm，喷雾干燥进口温度为350℃，出口温度为120℃，得到粉末状纳米复合母胶，干燥过程中冷凝回收乙醇。取上述母胶160phr，其余步骤同实施例1。
实施例3
将市售的炭黑N110粉末50g加入450g水中，搅拌均匀后，加入30g乙醇，搅拌后研磨15min，得到炭黑悬浮液。在搅拌下，混入250g固含量为40％的丁苯胶乳，得到粒径为10μm胶粒的混合液，将搅拌均匀的混合液进行半开式过热蒸汽喷雾干燥处理，雾化液滴控制在50μm，喷雾干燥进口温度为250℃，出口温度为100℃，得到粉末状纳米复合母胶，干燥过程中冷凝回收乙醇。取上述母胶150phr，其余步骤同实施例1。
实施例4
将市售的炭黑N234粉末50g加入450g水中，搅拌均匀后，加入30g乙醇，搅拌后研磨15min，得到炭黑悬浮液。在搅拌下，混入200g固含量为25％的田间天然胶乳和125g固含量为40％的丁苯橡胶乳液，得到粒径为5μm胶粒的混合液，将搅拌均匀的混合液进行半开式过热蒸汽喷雾干燥处理，雾化液滴控制在70μm，喷雾干燥进口温度为300℃，出口温度为120℃，得到粉末状纳米复合母胶，干燥过程中冷凝回收乙醇。取上述母胶150phr，其余步骤同实施例1。
实施例5
将市售的白炭黑粉末30g加入270g水中，搅拌均匀后，加入0.3g聚乙二醇8000，在70℃加热下处理3h，处理后研磨15min，得到白炭黑悬浮液。在搅拌下，混入200g固含量为40％的丁苯乳液，得到含有粒径为1μm胶粒的混合液，将搅拌均匀的混合液进行半开式过热蒸汽喷雾干燥处理，雾化液滴控制在30μm，喷雾干燥进口温度为350℃，出口温度为120℃，得到粉末状纳米复合母胶。取上述母胶130phr，其余步骤同实施例1。
实施例6
将市售的白炭黑粉末120g加入280g水中，搅拌均匀后，加入4g异丁基三乙氧基硅烷，在90℃加热下处理1h，处理后研磨15min，得到白炭黑悬浮液。在搅拌下，混入166.7g固含量为60％的浓缩天然胶乳，得到粒径为6μm胶粒的混合液，将搅拌均匀的混合液进行半开式过热蒸汽喷雾干燥处理，雾化液滴控制在60μm，喷雾干燥进口温度为220℃，出口温度为110℃，得到粉末状纳米复合母胶。取上述母胶180phr，其余步骤同实施例1。
实施例7
将市售的白炭黑粉末60g加入140g水中，搅拌均匀后，加入2.4g正丁醇，在90℃加热下处理2h，处理后倒入胶体磨中研磨15min，得到白炭黑悬浮液。在搅拌下，混入250g固含量为40％的氯丁橡胶乳液，得到粒径为8μm胶粒的混合液，将搅拌均匀的混合液进行半开式过热蒸汽喷雾干燥处理，雾化液滴控制在80μm，喷雾干燥进口温度为180℃，出口温度为100℃，得到颗粒状纳米复合母胶。取上述母胶160phr，其余步骤 同实施例1。
实施例8
将市售的白炭黑粉末60g加入140g水中，搅拌均匀后，加入2.4g硅氧偶联剂KH590，在90℃加热下处理2h，处理后倒入胶体磨中研磨15min，得到白炭黑悬浮液。在搅拌下，混入125g固含量为40％的丁苯橡胶乳液和125g固含量为40％的丁吡橡胶乳液，得到粒径为10μm胶粒的混合液，将搅拌均匀的混合液进行半开式过热蒸汽喷雾干燥处理，雾化液滴控制在70μm，喷雾干燥进口温度为280℃，出口温度为110℃，得到颗粒状纳米复合母胶。上述母胶160phr，其余步骤同实施例1。
实施例9
将市售的天然钠基膨润土500g加入10L去离子水中，在800r/min的转速下搅拌5小时，静置24小时后，得到固含量为2.0％的粘土/水悬浮液；取1250g粘土/水悬浮液，加入1g十六烷基溴化铵，处理后倒入胶体磨中研磨15min，得到白炭黑悬浮液。在搅拌下，混入1250g固含量为8％的胶清乳液，得到粒径为13μm胶粒的混合液，将搅拌均匀的混合液进行半开式过热蒸汽喷雾干燥处理，雾化液滴控制在70μm，喷雾干燥进口温度为280℃，出口温度为90℃，得到粉末状纳米复合母胶。上述母胶125phr，其余步骤同实施例1。
实施例10
将市售的天然钠基膨润土100g加入400g去离子水中，得到固含量为20％的粘土/水悬浮液，加入1g十八烷基溴化铵，处理后倒入胶体磨中研磨15min，得到均匀的粘土悬浮液。在搅拌下，混入333.3g固含量为30％的天然乳液，得到粒径为15μm胶粒的混合液，将搅拌均匀的混合液进行半开式过热蒸汽喷雾干燥处理，雾化液滴控制在90μm，喷雾干燥进口温度为260℃，出口温度为110℃，得到粉末状纳米复合母胶。取上述母胶200phr，其余步骤同实施例1。
实施例11
将市售的天然钠基膨润土50g加入450g去离子水中，得到固含量为10％的粘土/水悬浮液，加入1g十四烷基氯化铵，处理后倒入胶体磨中研磨15min，得到均匀的粘土悬浮液。在搅拌下，混入250g固含量为40％的丁苯吡橡胶乳液，得到粒径为10μm胶粒的混合液，将搅拌均匀的混 合液进行半开式过热蒸汽喷雾干燥处理，雾化液滴控制在30μm，喷雾干燥进口温度为350℃，出口温度为110℃，得到粉末状纳米复合母胶。取上述母胶150phr，其余步骤同实施例1。
实施例12
将市售的天然钠基膨润土60g加入340g去离子水中，得到固含量为15％的粘土/水悬浮液，加入1.2g十二烷基氯化铵，处理后倒入胶体磨中研磨15min，得到均匀的粘土悬浮液。在搅拌下，混入125g固含量为40％的丁苯吡橡胶乳液和125g固含量为40％的丁腈橡胶乳液，得到粒径为20μm胶粒的混合液，将搅拌均匀的混合液进行半开式过热蒸汽喷雾干燥处理，雾化液滴控制在40μm，喷雾干燥进口温度为350℃，出口温度为110℃，得到粉末状纳米复合母胶。取上述母胶150phr，其余步骤同实施例1。
对比实施例1
在双辊开练机上按配方：天然胶(云标1号)100phr、炭黑30phr、其余配合剂如实施例1，其余步骤如实施例1。
对比实施例2
在双辊开练机上按配方:天然胶(云标1号)100phr、白炭黑30phr，其余配合剂如实施例1，其余步骤如实施例1。
对比实施例3
在双辊开练机上按配方:天然胶(云标1号)100phr、粘土20phr，其余配合剂如实施例1，其余步骤如实施例1。
对比实施例4
在双辊开练机上按配方：丁腈胶100phr、炭黑(N330)50phr，其余配合剂如实施例1，其余步骤如实施例1
对比实施例5
在双辊开练机上按配方:氯丁胶100phr、白炭黑60phr，其余配合剂如实施例1，其余步骤如实施例1
对比实施例6
在双辊开练机上按配方:天然胶和丁苯胶混合胶100phr、炭黑50phr，其余配合剂如实施例1，其余步骤如实施例1。
对比实施例7
将市售的炭黑N234粉末30g加入970g水中，搅拌均匀后，加入15g乙醇，搅拌后倒入胶体磨中研磨15min，得到炭黑悬浮液。与400g质量百分比为25％的田间天然乳胶进行搅拌混合，加入硫酸溶液进行絮凝，清洗至中性，烘干得到30g炭黑/100g天然橡胶的纳米复合材料，在双辊开练机上按配方:取上述材料130phr，其余配合剂如实施例1，其余步骤如实施例1。
对比实施例8
将市售的白炭黑粉末30g加入970g水中，搅拌均匀后，加入0.3g聚乙二醇8000，在90℃加热下处理2h，处理后倒入胶体磨中研磨15min，得到白炭黑悬浮液。与400g质量百分比为25％的田间天然乳胶进行搅拌混合，加入硫酸溶液进行絮凝，清洗至中性，烘干得到30g白炭黑/100g天然橡胶的纳米复合材料，在双辊开练机上按配方:取上述材料130phr，其余配合剂如实施例1，其余步骤如实施例1。
对比实施例9
将市售的天然钠基膨润土500g加入10L去离子水中，在800r/min的转速下搅拌5小时，静置24小时后，得到固含量为2.0％的黏土/水悬浮液；取1000g粘土/水悬浮液，与400g质量百分比为25％的田间天然乳胶进行搅拌混合，加入硫酸溶液进行絮凝，清洗至中性，烘干得到20g粘土/100g天然橡胶的纳米复合材料，在双辊开练机上按配方:取上述材料120phr，其余配合剂如实施例1，其余步骤如实施例1。
表一实施例和对比例机械性能对比
Figure PCTCN2016090640-appb-000001
Figure PCTCN2016090640-appb-000002

Claims (7)

  1. 一种半开式过热蒸汽喷雾干燥法制备高填充复合母胶的方法，其特征在于：加水配制质量百分比浓度为2％～30％的无机填料悬浮液，加入改性剂处理后研磨15min，将处理后无机填料悬浮液加入橡胶乳液，无机填料质量为橡胶乳液干胶质量的25～120％，搅拌均匀后得到无机填料/橡胶乳液的混合悬浮液，混合悬浮液中颗粒物直径为5～20μm，半开式过热蒸汽喷雾干燥处理，雾化液滴粒径为30～100μm，喷雾干燥设备进口温度150～350℃，出口温度100～120℃，得到粉末状或微珠状橡胶复合母胶。
  2. 根据权利要求1所述的制备方法，其特征在于：无机填料为炭黑、白炭黑或粘土。
  3. 根据权利要求1所述的制备方法，其特征在于：无机填料为炭黑粉末，悬浮液质量百分比浓度为3～30％，炭黑用量为橡胶乳液干胶质量的30～60％；改性剂选乙醇作为浸润剂，乙醇用量为炭黑质量的50～100％。
  4. 根据权利要求1所述的制备方法，其特征在于：无机填料为白炭黑粉末，悬浮液浓度为10～30％，白炭黑用量为橡胶乳液干胶质量的30～120％；改性剂选聚乙二醇、硅氧偶联剂、多元醇，用量为白炭黑质量的1％～5％，白炭黑悬浮液在与胶乳混合前，需在70～90℃加热条件下处理1～3h。
  5. 根据权利要求1所述的制备方法，其特征在于：无机填料为粘土，悬浮液浓度为2～20％，粘土用量为橡胶乳液干胶质量的25～100％；改性剂为季铵盐，其与粘土的质量比为0.1％～5％。
  6. 根据权利要求1所述的制备方法，其特征在于：所使用的季铵盐为主链含碳数为12至18的季铵盐。
  7. 根据权利要求1所述的制备方法，其特征在于：橡胶乳液为胶清乳液、天然橡胶乳液、丁苯橡胶乳液、氯丁橡胶乳液、丁腈橡胶乳液、丁苯吡橡胶乳液、丁吡橡胶乳液，或者上述橡胶乳液的混合。
PCT/CN2016/090640 2015-11-29 2016-07-20 一种半开式过热蒸汽喷雾干燥法制备高填充复合母胶的方法 WO2017088503A1 (zh)

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