WO2017084036A1 - 一种高纯度低粘度二甲基硅油的连续化制备工艺 - Google Patents

一种高纯度低粘度二甲基硅油的连续化制备工艺 Download PDF

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WO2017084036A1
WO2017084036A1 PCT/CN2015/094861 CN2015094861W WO2017084036A1 WO 2017084036 A1 WO2017084036 A1 WO 2017084036A1 CN 2015094861 W CN2015094861 W CN 2015094861W WO 2017084036 A1 WO2017084036 A1 WO 2017084036A1
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preparation process
continuous preparation
process according
low
nitrogen
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PCT/CN2015/094861
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French (fr)
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王跃林
冯钦邦
吴利民
段先健
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广州道林合成材料有限公司
宜昌科林硅材料有限公司
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Priority to PCT/CN2015/094861 priority Critical patent/WO2017084036A1/zh
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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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

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  • the invention relates to a continuous preparation process of high-purity low-viscosity dimethicone.
  • the moisture of raw materials and end-capping agents sold on the market is usually about 100 ppm.
  • the main function of the mixing drying kettle in the device for producing dimethyl silicone oil is to remove the nitrogen gas at a low dew point (about -65 ° C) under vacuum.
  • an air duct is connected from the top of the mixing dryer to the bottom of the kettle.
  • the air duct is connected to an annular duct.
  • the duct has an air outlet and a low dew point. Nitrogen is discharged from the vent hole and the water in the mixing drying kettle is dehydrated.
  • a nitrogen inlet is left at the bottom of the mixing drying kettle, and a nitrogen conduit is connected to the annular conduit.
  • the conduit is provided with an air outlet, and the nitrogen gas is imported from the nitrogen gas.
  • the material is dehydrated after entering the mixing and drying vessel.
  • the nitrogen outlets of the above two devices are fixed, the contact position of nitrogen with the material is relatively fixed, the nitrogen gas cannot be in full contact with the material, and the water removal time is long and The effect is poor, and the annular duct is difficult to fix, which increases the processing difficulty of the equipment.
  • the moisture of the raw material and the blocking agent can only be controlled at 30-50 ppm, and in the ion exchange resin catalytic equilibrium method, the residual moisture will make A small amount of hydroxy silicone oil is formed during the reaction, which affects the quality of the product.
  • the selected catalysts are generally macroporous cation (hydrogen ion) exchange resins, polar substances such as water have a great influence on their catalytic activity, such as D72H catalytic resin, dry resin hydrogen ion concentration ⁇ 4.8 mmol / gram, and wet The resin hydrogen ion concentration is ⁇ 1.5 mmol/g. That is to say, the dry resin catalytic activity is more than three times that of the wet resin. It can be seen that the conventional method for preparing dimethicone not only causes the catalytic activity of the ion exchange resin to be gradually reduced, but also reduces the catalytic efficiency, and also causes a small amount of hydroxy silicone oil to be formed, and the blocking ratio of trimethylsiloxy is not obtained. improve.
  • the reaction product may carry more and more solid impurities such as broken resin into the de-lowing process, affecting the de-lowing effect and product quality.
  • the object of the present invention is to provide a continuous preparation process of high-purity and low-viscosity dimethicone.
  • the invention discloses a continuous preparation process of high-purity and low-viscosity dimethicone oil, comprising the steps of: methylcyclosiloxane and a blocking agent are frozen and removed by liquid nitrogen, and then heated to 40 to 70 ° C under vacuum while stirring. Deep nitrogen removal is carried out to dry the nitrogen to make the water content of the mixture below 300 ppb.
  • the mixture is filtered through an adsorption filter, filtered through an ultrafiltration membrane, preheated, and then introduced into a fluidized bed containing a catalyst to catalyze the reaction.
  • the liquid is filtered by adsorption filtration, ultrafiltration membrane, and then removed into a de-lowing process to remove low-boiling substances to obtain dimethicone.
  • the top of the mixing and drying kettle is provided with a rotating shaft of a hollow structure, and one end of the rotating shaft is connected to a nitrogen gas device disposed outside the mixing and drying vessel through a gas supply pipe, and the other end of the rotating shaft is installed with a hollow hole therethrough.
  • a plurality of stirring blades of the structure are placed in the mixing drying kettle, and a venting hole is evenly arranged on the stirring blade at the bottom of the rotating shaft;
  • the heating drying device is provided in the mixing drying kettle;
  • the upper end surface of the mixing drying kettle is A vacuum port is provided, and the vacuum port is connected to the vacuum pump through a pipeline.
  • the nitrogen-passing device is a liquid nitrogen vaporization pressurization system.
  • the dry nitrogen gas introduced by the deep water removal is nitrogen gas vaporized by liquid nitrogen.
  • the adsorption filtration uses at least one of activated carbon fiber and ion exchange resin as an adsorbent.
  • the freezing and dewatering temperature is -15 to -5 ° C, and the freezing and water removing time is 1 to 3 h.
  • the deep water removal time is 1 to 3 hours.
  • the methylcyclosiloxane is octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetradecamethylcyclohexasiloxane or dimethyl
  • the siloxane blends the ring.
  • the catalyst is a macroporous cation exchange resin.
  • the catalytic reaction temperature is 30 to 90 ° C, and the catalytic reaction time is 20 to 60 min.
  • the ultrafiltration membrane filtration is carried out using a tubular membrane module having a tubular ultrafiltration membrane element.
  • the product dimethicone and low-boiling substances are obtained, and the low-boiling substance is recycled as a raw material after detecting the content of the methylcyclosiloxane and the blocking agent.
  • the degassing temperature is controlled at 170 to 220 ° C, and the depressurization vacuum is controlled at -0.098 to -0.101 Mpa.
  • the invention adopts the method of freezing water removal and deep water removal to control the water content in the raw material methylcyclosiloxane and the terminal blocking agent to be below 300 ppb, and controls the residual hydroxyl content in the silicone oil product, thereby making the trimethylsiloxy group.
  • the capping rate is maximized while also ensuring the catalytic activity of the catalyst ion exchange resin.
  • the mixing drying kettle in the invention is improved: the rotating shaft is a hollow structure, one end of which is connected to the nitrogen-passing device through a gas supply pipe, and the other end is provided with a plurality of stirring blades which are connected with a hollow structure, and the stirring at the bottom of the rotating shaft A vent hole is evenly arranged on the paddle.
  • the mixed drying kettle is filled with nitrogen gas from the upper end of the rotating shaft, and the gas is discharged from the vent hole of the stirring paddle.
  • the nitrogen gas is in full contact with the material, the water removal time is short and the effect is good, the water removal efficiency is greatly improved, and the equipment processing is reduced.
  • the difficulty is also achieved by making the water content of the mixture below 300 ppb.
  • the ions and impurities which may be carried in the raw materials and the blocking agent are removed by adsorption filtration and ultrafiltration membrane to ensure the catalytic activity and product quality of the ion exchange resin.
  • the solid impurities such as ions and broken resin are removed by filtration through adsorption filtration and ultrafiltration membrane, and then the degassing step is carried out to improve the de-lowing effect and product quality.
  • the low boiler obtained by the invention passes through the detection of the content of the methylcyclosiloxane and the terminal blocking agent, and then returns to the raw material process for recycling to form a closed circulation system, so that the utilization rate of the raw material reaches 100% and reaches zero emission.
  • the preparation process of the invention can not only produce high-purity silicone oil which can meet the requirements of use in the high-end field, but also ensure the catalytic activity of the ion exchange resin, and the prepared dimethyl silicone oil has high purity, low ion content, hydroxyl content and solid content, and It can make the utilization rate of raw materials reach 100% and achieve zero emission. It is an environmentally friendly and efficient green preparation process for preparing high-purity and low-viscosity silicone oil, which is suitable for the production of low-viscosity dimethicone.
  • the filter element of the stainless steel filter described in the examples is a mixture of activated carbon fibers and ion exchange resins having a mass ratio of 2:1; and the ultrafiltration membrane filter is a tubular membrane module having a tubular ultrafiltration membrane element.
  • the structure of the mixing and drying kettle in the embodiment is shown in FIG. 1.
  • the top of the mixing and drying kettle 10 is provided with a rotating shaft 1 of a hollow structure, and one end of the rotating shaft 1 passes through a gas supply pipe and a nitrogen gas disposed outside the mixing drying vessel 10.
  • the device 2 is connected, and the other end of the rotating shaft is mounted with a plurality of stirring blades 3 having a hollow structure penetrating therethrough and placed in the mixing drying kettle 10, and a venting hole 4 is uniformly disposed on the stirring blade at the bottom of the rotating shaft;
  • the mixing and drying kettle 10 is provided with a heating and heat preservation device 5; the upper end surface of the mixing and drying kettle 10 is provided with a vacuuming port 6, and the vacuuming port is connected to the vacuum pump 7 through a pipeline; at least one of the mixing and drying kettles 10 is provided
  • the feed port 8 is also provided with at least one discharge port 9.
  • the mixing and drying kettle of the invention is uniformly provided with a venting hole only on the stirring blade at the bottom of the rotating shaft, and since the nitrogen gas is discharged from the venting hole, since the vacuuming port is opened on the upper end surface of the mixing drying kettle, the discharged air is discharged. The gas flows from bottom to top. If the nitrogen gas consumed by the other agitating blades is obviously increased, the efficiency of deep water removal is not obvious. Therefore, only the venting holes are provided on the stirring blade at the bottom of the rotating shaft. While ensuring deep water removal efficiency, it can achieve significant cost and resource savings.
  • the dimethylsiloxane mixed ring (DMC) and the blocking agent (MD 2 M) are transported to the pretreatment kettle at a mass ratio of 100:4.92, and the water is first frozen by liquid nitrogen to control the freezing temperature to be - 10 ° C, freezing and water removal time is 2h, frozen and water is transported to the mixing drying kettle, after heating to 50 ° C, the vacuum is controlled at -0.085 ⁇ -0.095Mpa, and dry nitrogen is introduced while stirring (liquid nitrogen vaporization Nitrogen) is subjected to deep water removal for 2 h, and the mixture after deep dewatering is sequentially sent to a stainless steel filter and an ultrafiltration membrane filter through a vortex pump to remove ions and solid impurities, and then sent to a preheater for preheating to At 80 ° C, and then transferred to a fluidized bed containing LDX-604 macroporous cation exchange resin, the reaction temperature was controlled at 60 ° C, the reaction residence time was 40 min, and the reaction mixture was sequentially transported
  • the ultrafiltration membrane filter is filtered to further remove ions and remove solid impurities such as broken resin, and then enter the high-efficiency deduction process to remove low-boiling substances, control the de-lowing temperature at 190 ° C, and control the de-lowing process vacuum degree at -0.0995 - -0.101Mpa, get two Methyl silicone oil, while the low boilers are tested for the content of methylcyclosiloxane and blocking agent, and then returned to the raw material process for recycling.
  • the dimethylsiloxane mixed ring (DMC) and the blocking agent (MDM) were transported to the pretreatment kettle at a mass ratio of 100:2.16, and the water was first frozen by liquid nitrogen to control the freezing temperature to -5 °C.
  • the freezing and dewatering time is 3h. After freezing and removing water, it is transported to the mixing drying kettle.
  • the vacuum degree is controlled at -0.090 ⁇ -0.095Mpa, and dry nitrogen is introduced while stirring (nitrogen vaporized by liquid nitrogen)
  • the deep dewatered mixture is sequentially sent to a stainless steel filter and an ultrafiltration membrane filter through a vortex pump to remove ions and solid impurities, and then sent to the preheater for preheating to 40.
  • the dimethylsiloxane mixed ring (DMC) and the blocking agent (MD 3 M) are transported to the pretreatment kettle at a mass ratio of 100:1.48, and the water is first frozen by liquid nitrogen to control the freezing temperature to be - 15 ° C, freezing and water removal time is 1h, frozen water and then transported to the mixing drying kettle, the vacuum is controlled at -0.085 ⁇ -0.095Mpa, after heating to 70 ° C, while stirring, dry nitrogen is introduced (liquid nitrogen vaporization Nitrogen) After deep dewatering for 1 h, the deep dewatered mixture is sequentially transferred to a stainless steel filter and an ultrafiltration membrane filter by a vortex pump to remove ions and solid impurities, and then sent to the preheater for preheating.
  • DMC dimethylsiloxane mixed ring
  • MD 3 M blocking agent
  • the reaction temperature is controlled at 90 ° C, the reaction residence time is 20 min, and the mixture formed by the reaction is sequentially sent to a stainless steel filter through a gear pump for filtration.
  • the ultrafiltration membrane filter is filtered to further remove ions and remove solid impurities such as broken resin, and then enter the high-efficiency deduction process to remove low-boiling substances, control the de-lowing temperature at 220 ° C, and control the de-lowing process vacuum degree at -0.099 - -0.101Mpa Dimethyl silicone oil is obtained, and the low boiler is subjected to the detection of the content of the methylcyclosiloxane and the terminal blocking agent, and then returned to the raw material process for recycling.
  • the dimethylsiloxane mixed ring (DMC) and the blocking agent (MD 2 M) were transported to the mixing kettle at a mass ratio of 100:4.92, and after heating to 50 ° C, the degree of vacuum was controlled at -0.085 ⁇ 0.095Mpa, with stirring, pass the dry nitrogen with dew point of -65 °C for 2h, transfer to preheater to preheat to 80 °C, then transport to the fluidized bed containing LDX-604 catalyst to control the reaction temperature.
  • the reaction residence time is 40 min
  • the mixture formed by the reaction is transported to the high-efficiency de-lowing process by the gear pump to remove the low-boiling substance
  • the de-lowing temperature is controlled at 190 ° C
  • the vacuum degree of the de-lowing process is controlled to be -0.0995 to -0.101 Mpa. , to obtain dimethyl silicone oil.
  • the mixture of the methylcyclosiloxane and the blocking agent used in each of the examples and the comparative examples was sent to the preheater before the preheating, and the water content of the mixture and the physical properties of the product dimethyl silicone oil are shown in Table 1. It can be seen from Table 1 that the water content of the methylcyclosiloxane and the terminal blocking agent can be reduced to below 300 ppb, and the obtained dimethyl silicone oil has high purity, close to 100%, low ion content, hydroxyl content and solid content. low. The resulting high purity dimethicone can be used in the cosmetics, pharmaceutical, food and electronics industries.
  • the present invention can effectively improve the purity of the product dimethyl silicone oil, and significantly reduce the low content of the product dimethyl silicone oil ion, the hydroxyl content and the solid content.

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Abstract

本发明公开了一种高纯度低粘度二甲基硅油的连续化制备工艺，包括以下步骤：甲基环硅氧烷和封端剂依次经液氮冷冻除水、深度除水使混合物的含水量至300ppb以下，然后经吸附过滤、超滤膜过滤、预热，进入到装有催化剂的流化床中催化反应，所得反应物经吸附过滤、超滤膜过滤、脱低工序脱去低沸物，得二甲基硅油。本发明制备得到的二甲基硅油纯度高，且离子含量、羟基含量、固含量低，又可使原料利用率达到100％，达到零排放，是一种与环境友好的高效制备高纯低粘度硅油的绿色环保工艺，适用于低粘度二甲基硅油的生产。

Description

一种高纯度低粘度二甲基硅油的连续化制备工艺 技术领域
本发明涉及一种高纯度低粘度二甲基硅油的连续化制备工艺。
背景技术
近年来在整个有机硅市场发展良好的情况下，二甲基硅油作为有机硅家族的一份子，发展前景被普遍看好。中国近5年二甲基硅油的表观消费量年均增长率在15％左右，成为全球增长最快的市场。国内二甲基硅油的生产厂家众多，技术水平参差不齐，并且大多数企业目前还采用间歇法生产低粘度硅油，造成生产效率低，产品批次质量波动大，产品性能差，副产物利用率低等问题。目前国产硅油在羟基含量、离子含量及固含物含量等方面控制存在不足导致其含量过高，造成硅油难以进入高端市场。而国外有机硅企业凭借技术垄断，占据了硅油市场的高端领域，如电子级硅油等。
市场上出售的原料及封端剂的水分通常在100ppm左右，目前生产二甲基硅油的装置中的混合干燥釜主要作用是在真空条件下,加热通低露点(约-65℃)的氮气除水，其通低露点氮气除水的方式有两种：第一种方式，从混合干燥釜顶部引一根导气管到釜底,导气管连接一个环形导管,导管上开有出气孔，低露点氮气从出气孔排出并对混合干燥釜内的物料进行除水；第二种方式，在混合干燥釜底部留有氮气进口,氮气进口连接一个环形导管,导管上开有出气孔，氮气从氮气进口进入混合干燥釜内后对物料进行除水。而上述两种装置的氮气出口固定,氮气与物料接触位置相对固定,氮气不能和物料充分接触,除水时间长且 效果差,并且环形导管较难固定,增加设备加工难度，现有技术均只能将原料及封端剂的水份控制在30～50ppm，而离子交换树脂催化平衡法中，残余的水分会使得反应过程中生成微量的羟基硅油，影响产品质量。并且所选用的催化剂一般都为大孔阳离子(氢离子)交换树脂，极性物质如水对其催化活性影响非常大，如D72H催化树脂，干树脂的氢离子浓度≥4.8毫摩尔/克，而湿树脂氢离子浓度≥1.5毫摩尔/克。也就是说干树脂催化活性是湿树脂的3倍多。由此可见，传统制备二甲基硅油的方法不但会造成离子交换树脂的催化活性逐渐减低，降低催化效率，还使得反应生成微量的羟基硅油，三甲基硅氧基的封端率得不到提高。
另一方面，由于原料及封端剂中可能携带的离子及杂质，会降低离子交换树脂的催化活性及影响产品质量。因此，物料进入流化床反应前必须除去离子及杂质。由于连续法采用流化床的形式，必须控制原料混合物在流化床的停留时间并且反应生成物料具有一定粘度，因此流化床常带有一定压力，同时由于大孔阳离子交换树脂与原料混合物接触后导致其体积膨胀，在压力作用下，离子交换树脂容易破损。因此，随着生产的进行，反应产物可能会携带越来越多破碎的树脂等固体杂质进入脱低工序，影响脱低效果及产品质量。
因此，迫切需要开发高效高纯低粘度二甲基硅油的连续化制备工艺，所述低粘度二甲基硅油是指粘度低于1000±80mm2/s的二甲基硅油，打破国外有机硅企业技术垄断，使得国产硅油能得以进入高端领域，进而促进我国相关新材料的发展。
发明内容
本发明的目的在于提供一种高纯度低粘度二甲基硅油的连续化制备工艺。
本发明所采用的技术方案为：
一种高纯度低粘度二甲基硅油的连续化制备工艺，包括以下步骤：甲基环硅氧烷和封端剂经液氮冷冻除水后，在真空下升温至40～70℃边搅拌边通入干燥氮气进行深度除水，使混合物的含水量至300ppb以下，混合液依次经过吸附过滤、超滤膜过滤、预热，然后进入到装有催化剂的流化床中催化反应，所得反应混合液经吸附过滤、超滤膜过滤，再进入脱低工序脱去低沸物，得二甲基硅油。
优选的，所述混合干燥釜顶部设有空心结构的转动轴，转动轴的一端通过供气管道与设置在混合干燥釜外的通氮气装置连接，转动轴的另一端安装有与其贯通的呈空心结构的多个搅拌叶片并置于混合干燥釜内，转动轴最下方的搅拌叶片上均匀设有排气孔；所述混合干燥釜内设有加热保温装置；所述混合干燥釜的上端面上设有抽真空口，抽真空口通过管路与真空泵连接。优选的，通氮气装置为液氮汽化增压系统。
优选的，所述深度除水通入的干燥氮气为液氮汽化后的氮气。
优选的，所述吸附过滤采用活性炭纤维、离子交换树脂中的至少一种作为吸附剂。
优选的，冷冻除水温度为-15～-5℃，冷冻除水时间为1～3h。
优选的，深度除水时间为1～3h。
优选的，甲基环硅氧烷为八甲基环四硅氧烷、十甲基环五硅氧烷、十二甲基环六硅氧烷、十四甲基环七硅氧烷或二甲基硅氧烷混合环体。
优选的，催化剂为大孔阳离子交换树脂。
优选的，催化反应温度30～90℃，催化反应时间20～60min。
优选的，采用内设管式超滤膜元件的管式膜组件进行超滤膜过滤。
优选的，脱低工序脱低后，得到产物二甲基硅油和低沸物，低沸物经过检测甲基环硅氧烷及封端剂的含量后，作为原料循环利用。
优选的，脱低温度控制在170～220℃，脱低的真空度控制在-0.098～-0.101Mpa。
本发明采用冷冻除水及深度除水的方法将原料甲基环硅氧烷和封端剂中的含水量控制在300ppb以下，控制硅油产品中的残余羟基含量，从而使得三甲基硅氧基的封端率得到最大限度的提高，同时还保证了催化剂离子交换树脂的催化活性。
本发明中的混合干燥釜经过改进:转动轴为空心结构，其一端通过供气管道与通氮气装置连接，另一端安装有与其贯通的呈空心结构的多个搅拌桨，转动轴最下方的搅拌桨上均匀设有排气孔。经过改进有混合干燥釜从转动轴上端通入氮气，从搅拌桨的排气孔出气，搅拌过程中氮气与物料充分接触，除水时间短且效果好,大大提高除水效率,并降低设备加工难度，也使混合物的含水量至300ppb以下得以实现。
本发明的原料和封端剂除水后，通过吸附过滤及超滤膜过滤除去原料和封端剂中可能携带的离子及杂质，保证了离子交换树脂的催化活性及产品质量。
本发明的原料经过催化剂催化反应后，通过吸附过滤及超滤膜过滤除去离子及破碎的树脂等固体杂质后，再进入脱低工序，提高了脱低效果及产品质量。
本发明将得到的低沸物经过检测甲基环硅氧烷及封端剂的含量后，返回原料工序循环利用，形成一个闭式循环系统，使得原料利用率达到100％，达到零排放，是一种与环境友好的高效制备高纯低粘度硅油的绿色环保工艺。
本发明的有益效果是：
本发明的制备工艺既可生产能满足高端领域的使用要求的高纯硅油，保证离子交换树脂的催化活性，制备得到的二甲基硅油纯度高，且离子含量、羟基含量、固含量低，又可使原料利用率达到100％，达到零排放，是一种与环境友好的高效制备高纯低粘度硅油的绿色环保工艺，适用于低粘度二甲基硅油的生产。
具体实施方式
下面结合具体的实施例对本发明作进一步的说明，但并不局限如此。
实施例中所述的不锈钢过滤器的滤芯为质量比为2：1的活性炭纤维、离子交换树脂的混合物；所述超滤膜过滤器为内设管式超滤膜元件的管式膜组件。
实施例中所述混合干燥釜的结构见图1，所述混合干燥釜10顶部设有空心结构的转动轴1，转动轴1的一端通过供气管道与设置在混合干燥釜10外的通氮气装置2连接，转动轴的另一端安装有与其贯通的呈空心结构的多个搅拌叶片3并置于混合干燥釜10内，转动轴最下方的搅拌叶片上均匀设有排气孔4；所述混合干燥釜10内设有加热保温装置5；所述混合干燥釜10的上端面设有抽真空口6，抽真空口通过管路与真空泵7连接；所述混合干燥釜10上设有至少一个进料口8，还设有至少一个出料口9。本发明混合干燥釜仅在转动轴最下方的搅拌叶片上均匀设有排气孔，由于通入的氮气从排气孔排出后，由于抽真空口开在混合干燥釜的上端面，故排出的气体是由下往上流动的，若其它的搅拌叶片开孔所耗费的氮气明显提高，而深度除水的效率增加不明显，因此仅在转动轴最下方的搅拌叶片上设排气孔，可以在保证深度除水效率的同时，达到大大节约成本及资源的作用。
实施例1
将二甲基硅氧烷混合环体(DMC)与封端剂(MD2M)按100:4.92的质量比，输送至预处理釜中，先用液氮冷冻除水，控制冷冻温度为-10℃，冷冻除水时间为2h，冷冻除水后输送至混合干燥釜内，升温到50℃后，真空度控制在-0.085～-0.095Mpa，边搅拌边通入干燥氮气(液氮汽化后的氮气)进行深度除水2h，通过涡流泵将深度除水后的混合物依次输送至不锈钢过滤器、超滤膜过滤器过滤，以除去离子及固体杂质，然后再输送至预热器预热到80℃，然后输送至装有LDX-604大孔阳离子交换树脂的流化床中反应，控制反应温度为60℃，反应停留时间为40min，反应生成的混合物通过齿轮泵依次输送至不锈钢过滤器、超滤膜过滤器过滤，以进一步除去离子及除去破碎的树脂等固体杂质后，进入高效脱低工序脱去低沸物，控制脱低温度在190℃，控制脱低工序真空度在-0.0995～-0.101Mpa，得二甲基硅油，而低沸物经过检测甲基环硅氧烷及封端剂的含量后，返回原料工序循环利用。
实施例2
将二甲基硅氧烷混合环体(DMC)与封端剂(MDM)按100:2.16的质量比，输送至预处理釜中，先用液氮冷冻除水，控制冷冻温度为-5℃，冷冻除水时间为3h，冷冻除水后输送至混合干燥釜内，升温到40℃后，真空度控制在-0.090～-0.095Mpa，边搅拌边通入干燥氮气(液氮汽化后的氮气)进行深度除水3h后，通过涡流泵将深度除水后的混合物依次输送至不锈钢过滤器、超滤膜过滤器过滤，以除去离子及固体杂质，然后再输送至预热器预热至40℃，然后输送至装有D72H大孔阳离子交换树脂的流化床中反应，控制反应温度为30℃，反应停留时间为60min，反应生成的混合物通过齿轮泵依次输送至不锈钢过滤器、超滤 膜过滤器过滤，以进一步除去离子及除去破碎的树脂等固体杂质后，进入高效脱低工序脱去低沸物，控制脱低温度在170℃，控制脱低工序真空度在-0.098～-0.10Mpa，得二甲基硅油，而低沸物经过检测甲基环硅氧烷及封端剂的含量后，返回原料工序循环利用。
实施例3
将二甲基硅氧烷混合环体(DMC)与封端剂(MD3M)按100:1.48的质量比，输送至预处理釜中，先用液氮冷冻除水，控制冷冻温度为-15℃，冷冻除水时间为1h，冷冻除水然后输送至混合干燥釜内，真空度控制在-0.085～-0.095Mpa，升温到70℃后，边搅拌边通入干燥氮气(液氮汽化后的氮气)进行深度除水1h后，通过涡流泵将深度除水后的混合物依次输送至不锈钢过滤器、超滤膜过滤器过滤，以除去离子及固体杂质，然后再输送至预热器预热至100℃，然后输送至装有D72H大孔阳离子交换树脂的流化床中反应，控制反应温度为90℃，反应停留时间为20min，反应生成的混合物通过齿轮泵依次输送至不锈钢过滤器过滤、超滤膜过滤器过滤，以进一步除去离子及除去破碎的树脂等固体杂质后，进入高效脱低工序脱去低沸物，控制脱低温度在220℃，控制脱低工序真空度在-0.099～-0.101Mpa，得二甲基硅油，而低沸物经过检测甲基环硅氧烷及封端剂的含量后，返回原料工序循环利用。
对比例
将二甲基硅氧烷混合环体(DMC)与封端剂(MD2M)按100:4.92的质量比输送至混合釜内，升温到50℃后，把真空度控制在-0.085～-0.095Mpa，边搅拌边通入露点为-65℃的干燥氮气除水2h，输送至预热器预热至80℃，然后输送至装有LDX-604催化剂的流化床中反应，控制反应温度为60℃，反应停留时间 为40min，反应生成的混合物通过齿轮泵输送至高效脱低工序脱去低沸物，控制脱低温度在190℃，控制脱低工序真空度在-0.0995～-0.101Mpa，得到二甲基硅油。
各实施例和对比例所用的甲基环硅氧烷及封端剂的混合物输送至预热器预热前，混合物的含水量及产物二甲基硅油的物理性能见表1。由表1可知，本发明能将甲基环硅氧烷及封端剂的含水量降至300ppb以下，且所得二甲基硅油纯度高，接近100％，离子含量低、羟基含量、固含量均低。所得的高纯二甲基硅油能应用于化妆品、医药、食品及电子行业。
由实施例1与对比例对比可知，本发明能有效提高产物二甲基硅油纯度，显著降低产物二甲基硅油离子含量低、羟基含量、固含量。
表1各实施例及对比例的原料及产物性能对比
Figure PCTCN2015094861-appb-000001
Figure PCTCN2015094861-appb-000002

Claims (10)

  1. 一种高纯度低粘度二甲基硅油的连续化制备工艺，包括以下步骤：甲基环硅氧烷和封端剂经液氮冷冻除水后，进入混合干燥釜，在真空下升温至40～70℃边搅拌边通入干燥氮气进行深度除水，使混合物的含水量至300ppb以下，混合液依次经过吸附过滤、超滤膜过滤、预热，然后进入到装有催化剂的流化床中催化反应，所得反应混合液经吸附过滤、超滤膜过滤，再进入脱低工序脱去低沸物，得二甲基硅油。
  2. 根据权利要求1所述的连续化制备工艺，其特征在于：所述混合干燥釜顶部设有空心结构的转动轴，转动轴的一端通过供气管道与设置在混合干燥釜外的通氮气装置连接，转动轴的另一端安装有与其贯通的呈空心结构的多个搅拌叶片并置于混合干燥釜内，转动轴最下方的搅拌叶片上均匀设有排气孔；所述混合干燥釜内设有加热保温装置；所述混合干燥釜的上端面上设有抽真空口，抽真空口通过管路与真空泵连接。
  3. 根据权利要求1或2所述的连续化制备工艺，其特征在于：所述深度除水通入的干燥氮气为液氮汽化后的氮气。
  4. 根据权利要求1或2所述的连续化制备工艺，其特征在于：所述吸附过滤采用活性炭纤维、离子交换树脂中的至少一种作为吸附剂。
  5. 根据权利要求1或2所述的连续化制备工艺，其特征在于：冷冻除水温度为-15～-5℃，冷冻除水时间为1～3h。
  6. 根据权利要求2所述的连续化制备工艺，其特征在于：通氮气装置为液氮汽化增压系统。
  7. 根据权利要求1或2所述的连续化制备工艺，其特征在于：甲基环硅氧烷为 八甲基环四硅氧烷、十甲基环五硅氧烷、十二甲基环六硅氧烷、十四甲基环七硅氧烷或二甲基硅氧烷混合环体。
  8. 根据权利要求1或2所述的连续化制备工艺，其特征在于：催化反应温度30～90℃，催化反应时间20～60min。
  9. 根据权利要求1或2所述的连续化制备工艺，其特征在于：采用内设管式超滤膜元件的管式膜组件进行超滤膜过滤。
  10. 根据权利要求1或2所述的连续化制备工艺，其特征在于：脱低工序脱低后，得到产物二甲基硅油和低沸物，低沸物经过检测甲基环硅氧烷及封端剂的含量后，作为原料循环利用。
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