WO2022262156A1 - 一种改善氟橡胶乳液凝聚效果的方法 - Google Patents

一种改善氟橡胶乳液凝聚效果的方法 Download PDF

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WO2022262156A1
WO2022262156A1 PCT/CN2021/124486 CN2021124486W WO2022262156A1 WO 2022262156 A1 WO2022262156 A1 WO 2022262156A1 CN 2021124486 W CN2021124486 W CN 2021124486W WO 2022262156 A1 WO2022262156 A1 WO 2022262156A1
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emulsion
fluororubber
coagulation
solubilizer
solution
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PCT/CN2021/124486
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English (en)
French (fr)
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孟庆文
余考明
程宇
黄军
路迪
陈佳
王鑫
胡帅捷
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浙江巨圣氟化学有限公司
浙江巨化股份有限公司氟聚厂
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Priority to EP21945736.3A priority Critical patent/EP4357373A1/en
Publication of WO2022262156A1 publication Critical patent/WO2022262156A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/14—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/16—Powdering or granulating by coagulating dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms

Definitions

  • the invention relates to the technical field of synthetic rubber, in particular to a method for improving the coagulation effect of fluororubber emulsion.
  • fluorine rubber Compared with other rubbers, fluorine rubber has excellent comprehensive properties such as high temperature resistance, chemical corrosion resistance, oil resistance, and weather aging resistance, so it has become an important sealing material and chemical transportation material in the fields of automobile, aerospace, and chemical industry. Its outstanding feature is high temperature resistance, and it can work under the temperature condition of -50 ⁇ 300 °C for a long time.
  • Emulsion polymerized fluororubber is synthesized by free radical initiated copolymerization of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene or vinylidene fluoride, hexafluoropropylene or vinylidene fluoride and chlorotrifluoroethylene lotion.
  • Fluorine rubber emulsion can be further processed after coagulation.
  • the coagulation process is essentially a demulsification process.
  • the demulsification methods mainly include physical demulsification and chemical demulsification. Physical demulsification is like freezing, and chemical demulsification is like salting out.
  • the coagulation method of fluororubber emulsion is currently using the traditional coagulation method, that is, after the emulsion polymerization is completed, the unreacted raw material monomers are removed by nitrogen replacement, and then transported to the coagulation unit, and a coagulant is added to the coagulation kettle for coagulation. Fluorine rubber products are obtained after washing with water, dehydration and vacuum drying.
  • Patent CN101323657A discloses the preparation method of valeronitrile rubber emulsion and valeronitrile rubber, including the preparation of valeronitrile rubber emulsion and the steps of agglomeration into a rubber block.
  • the coagulant described in the present invention is an inorganic acid salt, and the inorganic acid salt is easy to remain in the rubber block Impurity ions, difficult to wash and dry.
  • Patent CN102875711A discloses a polyvinylidene fluoride emulsion coagulation washing method, the method is mainly after the polyvinylidene fluoride emulsion is mechanically coagulated, left to stand, and washed; because the method mechanically coagulates the polyvinylidene fluoride emulsion into a paste It is time-consuming to stand and separate, and the average particle size of the pasty glue is 5-10 ⁇ m, which is not suitable for conventional centrifugal dehydration, and the dehydration time is long, which is not conducive to industrial production.
  • the colloidal particles obtained after coagulation are dense and difficult to clean and dry; the powdery or pasty colloids are easy to lose when cleaning, and the filtration and dehydration are time-consuming, which increases the production cost.
  • Impurities in the residual colloidal particles will affect the appearance and performance of the product, resulting in a decline in product quality; impurity ions such as SO4 2- , Cl - , NO 3- in the colloidal particles will seriously corrode post-processing metal equipment.
  • the purpose of the present invention is to provide a method for improving the coagulation effect of fluororubber emulsion. After the coagulation is completed, the colloidal particles are loose, the electrical conductivity and water content are low, easy to clean and dehydrate, the drying time is short, the production cost is reduced, and the product quality and quality are improved.
  • the production efficiency can solve the problems in the background technology.
  • the technical scheme of the method for improving the coagulation effect of the fluororubber emulsion provided by the present invention is specifically as follows:
  • the embodiment of the invention discloses a method for improving the coagulation effect of the fluororubber emulsion, which uses the fluororubber emulsion as the raw material, and is characterized in that a solubilizing agent is added to the system; the step is to first add high-purity water to the emulsion, and then add a coagulant , and then add a solubilizer to it for coagulation.
  • the solubilizing agent includes methyl cellulose, polyethylene glycol monomethyl ether, polyoxyethylene fatty acid ester, polysorbate, PEG (polyethylene glycol) At least one or more combinations.
  • the coagulant includes one selected from CaCl 2 , MgCl 2 , K 2 SO 4 , NaCl, KCl, and NH 4 Cl.
  • the mass ratio of the solubilizer to the raw material is 0.08-0.5:100, and the raw material is based on the weight of the dry glue of the fluororubber emulsion.
  • the mass ratio of the coagulant, solubilizer, and raw materials is 0.3-1.0:0.08-0.5:100, and the raw materials are based on the weight of the dry glue of the fluororubber emulsion.
  • the method for improving the coagulation effect of the fluororubber emulsion comprises the following steps:
  • coagulant solution 0.3-1.0 parts by weight of coagulant is dissolved in high-purity water to make a 15-25% solution for later use;
  • solubilizer solution 0.08-0.5 parts by weight of solubilizer are dissolved in high-purity water to prepare a 10-15% solution for later use;
  • the present invention can recycle the removed unpolymerized monomers.
  • the present invention has the following effects:
  • the solubilizing agent used in the invention has good water solubility and is harmless to the environment.
  • the use of compatibilizers to solubilize the micelles of inorganic salts achieves the effect of loosening, dispersing and lubricating the colloidal particles during the coagulation process, which helps to form pore gaps inside the colloidal particles, and reduces the density and agglomeration of the colloidal particles.
  • the colloidal particles are sponge-like, with an average particle size of 0.5-2cm, which is easy to wash and dry, reduces waste water discharge and saves energy consumption, and at the same time reduces residual impurities in the product, improves product quality and reduces inorganic acid ion Corrosion of metal equipment in the post-processing process.
  • solubilizer solution Accurately weigh 8g of PEG400 solubilizer, dissolve it in high-purity water, and prepare a 10% solution for later use;
  • solubilizer solution Accurately weigh 20g of PEG300 solubilizer, dissolve it in high-purity water, and prepare a 10% solution for later use;
  • solubilizer solution Accurately weigh 50g of PEG400 solubilizer, dissolve it in high-purity water, and prepare a 10% solution for later use;
  • solubilizer solution Accurately weigh 5g of PEG600 solubilizer, dissolve it in high-purity water, and prepare a 10% solution for later use;
  • 4Coagulation of emulsion Add the raw materials prepared in step 3 into the coagulation kettle, stir at a rate of 500rpm, add the coagulant solution prepared in step 1, and stir for 4min at 2000rpm; then add the solubilizer solution prepared in step 2 Add the coagulation kettle, continue to stir for 5 minutes, and condense until the colloidal particles are uniform and the slurry is clear. After stopping the stirring, the fluorine rubber particles separated by demulsification are obtained. The precipitated colloidal particles are washed 10 times, passed through a vibrating sieve, and vacuum-dried for 3 hours to obtain Viton products.
  • solubilizer solution Accurately weigh 5g of PEG400 solubilizer, dissolve it in high-purity water, and prepare a 10% solution for later use;
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • solubilizer solution Accurately weigh 5g of polysorbate solubilizer, dissolve it in high-purity water, and prepare a 10% solution for later use;
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • solubilizer solution Accurately weigh 100g of polysorbate solubilizer, dissolve in high-purity water, make a 10% solution, and set aside;
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • solubilizer solution Accurately weigh 100g of polysorbate solubilizer, dissolve in high-purity water, make a 10% solution, and set aside;
  • Example 2 Other conditions are the same as those in Example 1, except that no solubilizing agent is added during the coagulation process for coagulation.
  • Example 4 Other conditions are the same as in Example 4, except that no solubilizing agent is added during the coagulation process for coagulation.
  • the FE30 conductivity meter is selected, and the electrode with a built-in temperature probe (such as the LE701 conductivity electrode);
  • the sieve plate of the vibrating sieve is set with four layers of different sieve diameters from top to bottom: 2.0cm, 1.5cm, 1.0cm cm, 0.5cm, after being screened, it is sent to the tray for collection through the belt;
  • Example 1 100 margin 0.3 0.08 A+ 0.118 0.8cm 1.3
  • Example 2 100 margin 1 0.2 A+ 0.100 1.9cm 1.4
  • Example 3 100 margin 0.3 0.5 A 0.075 1.6cm 1.6
  • Example 4 100 margin 1 0.5 A 0.078 1.2cm 2.4
  • Example 5 100 margin 0.1 0.05 B 0.109 0.3cm 2.6
  • Example 6 100 margin 3 0.05 B 0.142 0.4cm 2.8
  • Example 7 100 margin 0.1 1 B 0.112 0.2cm 2.5
  • Example 8 100 margin 1.5 1 B 0.117 0.4cm 2.6
  • Comparative example 1 100 margin 0.3 none C 0.229 0.1cm 16
  • Comparative example 2 100 margin 1 none C 0.311 0.3cm 20

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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)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本发明涉及一种改善氟橡胶乳液凝聚效果的方法，是以氟橡胶乳液为原料，其特征在于在体系中加入增溶剂；其步骤是向乳液中，先加入高纯水，再加入凝聚剂，然后向其中加入增溶剂进行凝聚。凝聚完成后胶体颗粒疏松，电导率及含水率低，易于清洗和脱水，干燥时间短，降低了生产成本，提高了产品质量和生产效率。

Description

一种改善氟橡胶乳液凝聚效果的方法 技术领域
本发明涉及合成橡胶技术领域，尤其涉及一种改善氟橡胶乳液凝聚效果的方法。
背景技术
氟橡胶同其他橡胶相比具有耐高温、耐化学腐蚀、耐油、耐气候老化等优异的综合性能，因而成为汽车、航空航天、化学工业等领域中重要的密封材料和化学品输送材料。其突出特点是耐高温，可长期在-50～300℃温度条件下工作。
乳液聚合的氟橡胶是偏二氟乙烯、四氟乙烯、六氟丙烯三种或偏二氟乙烯、六氟丙烯或偏二氟乙烯、三氟氯乙烯两种单体经自由基引发共聚合成的乳液。氟橡胶乳液需经过凝聚之后才可以进一步加工。凝聚过程实质是一个破乳的过程，破乳方法主要有物理破乳和化学破乳两种，物理破乳如冷冻，化学破乳如盐析等。
氟橡胶乳液的凝聚方法目前使用的是传统凝聚方法，即乳液聚合反应完成后，经氮气置换脱除未反应的原料单体，再输送至凝聚单元，在凝聚釜中加入凝聚剂进行凝聚，经水洗、脱水、真空烘干后得到氟橡胶产品。
专利CN101323657A公开了戊腈橡胶乳液及戊腈橡胶的制备方法，包括戊腈橡胶乳液的制备和凝聚成胶块步骤，本发明所述的凝聚剂为无机酸盐，胶块中容易残留无机酸盐杂质离子，难以清洗和干燥。
专利CN102875711A公开了一种聚偏氟乙烯乳液的凝聚洗涤方法，该方 法主要是将聚偏氟乙烯乳液经机械凝聚后，静置，洗涤；由于该方法机械凝聚后的聚偏氟乙烯乳液为糊状胶粒，静置分离耗时，并且其糊状胶的平均粒径较小5～10μm，不适用于常规的离心脱水，脱水时间较长，不利于工业化生产。
总的来说，现有技术中的氟橡胶乳液凝聚方法，存在如下不足：
凝聚后制得的胶粒密实，不易清洗和烘干；粉末状或糊状胶体清洗时容易流失，并且过滤脱水很耗时，生产成本提高。
残留胶粒中的杂质会影响到产品的外观和性能，导致产品质量下降；胶粒中的SO4 2-、Cl -、NO 3-等杂质离子对后处理金属设备腐蚀严重。
发明内容
本发明的目的在于提供一种改善氟橡胶乳液凝聚效果的方法，凝聚完成后胶体颗粒疏松，电导率及含水率低，易于清洗和脱水，干燥时间短，降低了生产成本，提高了产品质量和生产效率，可以解决背景技术中的问题。
为了解决上述技术问题，本发明提供的改善氟橡胶乳液凝聚效果的方法的技术方案具体如下：
本发明实施例公开了一种改善氟橡胶乳液凝聚效果的方法，是以氟橡胶乳液为原料，其特征在于在体系中加入增溶剂；其步骤是向乳液中，先加入高纯水，再加入凝聚剂，然后向其中加入增溶剂进行凝聚。
在上述任一方案中优选的是，所述增溶剂包括选自甲基纤维素、聚乙二醇单甲醚、聚氧乙烯脂肪酸酯、聚山梨酯、PEG(聚乙二醇)中的至少一种或多种组合。
在上述任一方案中优选的是，所述凝聚剂包括选自CaCl 2、MgCl 2、K 2SO 4、NaCl、KCl、NH 4Cl中的一种。
在上述任一方案中优选的是，所述的增溶剂、原料的质量比为0.08～0.5:100，原料以氟橡胶乳液的干胶的重量计。
在上述任一方案中优选的是，所述的凝聚剂、增溶剂、原料的质量比为0.3～1.0:0.08～0.5:100，原料以氟橡胶乳液的干胶的重量计。
在上述任一方案中优选的是，所述的一种改善氟橡胶乳液凝聚效果的方法，包括以下步骤：
①凝聚剂溶液的配制：将0.3～1.0重量份凝聚剂，溶解于高纯水中，配成15～25％的溶液，备用；
②增溶剂溶液的配制：将0.08～0.5重量份增溶剂，溶解于高纯水中，配成10～15％的溶液，备用；
③原料的配制：将相当于100重量份干胶的氟橡胶乳液预热至20-60℃，去除未聚合的单体，备用；
④乳液的凝聚：将步骤③配制的原料加入凝聚釜中，再向凝聚釜内加入高纯水稀释至固含量为10～20％，在小于500rpm的速率下搅拌，加入步骤①配制的含有0.3～1.0重量份凝聚剂的凝聚剂溶液，并以大于1000rpm的条件下搅拌2～5min；然后将步骤②配制的含有0.08～0.5重量份增溶剂溶液加入凝聚釜，继续搅拌3～8min，凝聚至胶粒颗粒均匀、浆液清澈为止，停止搅拌后得到破乳析出的氟橡胶颗粒，将析出的胶粒进行洗涤、过振动筛、干燥，得到氟橡胶产品。
在上述任一方案中优选的是，本发明可以对脱除的未聚合的单体进行 回收利用。
本发明相比现有技术，具有如下效果：
本发明使用的增溶剂，水溶性较好，对环境无害。利用增容剂对无机盐的胶束增溶在凝聚过程中达到疏松、分散和润滑胶粒作用，有助于胶粒内部形成孔道间隙，降低胶粒密实程度和结块现象。凝聚完成后，胶粒呈海绵状，平均粒径0.5～2cm，易于洗涤和干燥，减少了废水排放和节约能耗，同时降低了产品内部残留的杂质，提升了产品质量和减轻了无机酸根离子对后处理过程金属设备的腐蚀。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
为了更好地理解上述技术方案，下面将结合具体实施方式对本发明技术方案进行详细说明。
实施例1：
按照如下方法步骤对氟橡胶乳液进行凝聚处理：
①凝聚剂溶液的配制：准确称取30g MgCl 2凝聚剂，溶解于高纯水中，配成15％的溶液，备用；
②增溶剂溶液的配制：准确称取8g PEG400增溶剂，溶解于高纯水中，配成10％的溶液，备用；
③原料的配制：把相当于1kg干胶，固含量20％的氟橡胶乳液5kg预热至30℃，备用；
④乳液的凝聚：将步骤③配制的原料加入凝聚釜中，在250rpm的速率下搅拌，加入步骤①配制的凝聚剂溶液，并以1500rpm的条件下搅拌2～5min；然后将步骤②配制的增溶剂溶液加入凝聚釜，继续搅拌3～8min，凝聚至胶粒颗粒均匀、浆液清澈为止，停止搅拌后得到破乳析出的氟橡胶颗粒，将析出的胶粒进行洗涤10次、过振动筛、真空干燥3h，得到氟橡胶产品；
实施例2：
按照如下方法步骤对氟橡胶乳液进行凝聚处理：
①凝聚剂溶液的配制：准确称取100g K 2SO 4凝聚剂，溶解于高纯水中，配成15％的溶液，备用；
②增溶剂溶液的配制：准确称取20g PEG300增溶剂，溶解于高纯水中，配成10％的溶液，备用；
③原料的配制：把相当于1kg干胶，固含量20％的氟橡胶乳液5kg预热至30℃，备用；
④乳液的凝聚：将步骤③配制的原料加入凝聚釜中，在300rpm的速率下搅拌，加入步骤①配制的凝聚剂溶液，并以1200rpm的条件下搅拌2min；然后将步骤②配制的增溶剂溶液加入凝聚釜，继续搅拌3min，凝聚至胶粒颗粒均匀、浆液清澈为止，停止搅拌后得到破乳析出的氟橡胶颗粒，将析出的胶粒进行洗涤10次、过振动筛、真空干燥3h，得到氟橡胶产品。
实施例3：
按照如下方法步骤对氟橡胶乳液进行凝聚处理：
①凝聚剂溶液的配制：准确称取30g MgCl 2凝聚剂，溶解于高纯水中， 配成15％的溶液，备用；
②增溶剂溶液的配制：准确称取50g PEG400增溶剂，溶解于高纯水中，配成10％的溶液，备用；
③原料的配制：把相当于1kg干胶，固含量15％的氟橡胶乳液5kg预热至30℃，备用；
④乳液的凝聚：将步骤③配制的原料加入凝聚釜中，在400rpm的速率下搅拌，加入步骤①配制的凝聚剂溶液，并以2000rpm的条件下搅拌3min；然后将步骤②配制的增溶剂溶液加入凝聚釜，继续搅拌4min，凝聚至胶粒颗粒均匀、浆液清澈为止，停止搅拌后得到破乳析出的氟橡胶颗粒，将析出的胶粒进行洗涤10次、过振动筛、真空干燥3h，得到氟橡胶产品。
实施例4：
按照如下方法步骤对氟橡胶乳液进行凝聚处理：
①凝聚剂溶液的配制：准确称取100g MgCl 2凝聚剂，溶解于高纯水中，配成15％的溶液，备用；
②增溶剂溶液的配制：准确称取5g PEG600增溶剂，溶解于高纯水中，配成10％的溶液，备用；
③原料的配制：把相当于1kg干胶，固含量15％的氟橡胶乳液5kg预热至30℃，备用；
④乳液的凝聚：将步骤③配制的原料加入凝聚釜中，在500rpm的速率下搅拌，加入步骤①配制的凝聚剂溶液，并以2000rpm的条件下搅拌4min；然后将步骤②配制的增溶剂溶液加入凝聚釜，继续搅拌5min，凝聚至胶粒颗粒均匀、浆液清澈为止，停止搅拌后得到破乳析出的氟橡胶颗粒， 将析出的胶粒进行洗涤10次、过振动筛、真空干燥3h，得到氟橡胶产品。
实施例5：
按照如下方法步骤对氟橡胶乳液进行凝聚处理：
①凝聚剂溶液的配制：准确称取10g MgCl 2凝聚剂，溶解于高纯水中，配成15％的溶液，备用；
②增溶剂溶液的配制：准确称取5g PEG400增溶剂，溶解于高纯水中，配成10％的溶液，备用；
③原料的配制：把相当于1kg干胶，固含量10％的氟橡胶乳液5kg预热至30℃，备用；
④乳液的凝聚：将步骤③配制的原料加入凝聚釜中，在300rpm的速率下搅拌，加入步骤①配制的凝聚剂溶液，并以1800rpm的条件下搅拌5min；然后将步骤②配制的增溶剂溶液加入凝聚釜，继续搅拌6min，凝聚至胶粒颗粒均匀、浆液清澈为止，停止搅拌后得到破乳析出的氟橡胶颗粒，将析出的胶粒进行洗涤10次、过振动筛、真空干燥3h，得到氟橡胶产品。
实施例6：
按照如下方法步骤对氟橡胶乳液进行凝聚处理：
①凝聚剂溶液的配制：准确称取300g MgCl 2凝聚剂，溶解于高纯水中，配成15％的溶液，备用；
②增溶剂溶液的配制：准确称取5g聚山梨酯增溶剂，溶解于高纯水中，配成10％的溶液，备用；
③原料的配制：把相当于1kg干胶，固含量10％的氟橡胶乳液5kg预热至30℃，备用；
④乳液的凝聚：将步骤③配制的原料加入凝聚釜中，在400rpm的速率下搅拌，加入步骤①配制的凝聚剂溶液，并以1800rpm的条件下搅拌2～5min；然后将步骤②配制的增溶剂溶液加入凝聚釜，继续搅拌3～8min，凝聚至胶粒颗粒均匀、浆液清澈为止，停止搅拌后得到破乳析出的氟橡胶颗粒，将析出的胶粒进行洗涤10次、过振动筛、真空干燥3h，得到氟橡胶产品。
实施例7：
按照如下方法步骤对氟橡胶乳液进行凝聚处理：
①凝聚剂溶液的配制：准确称取10g MgCl 2凝聚剂，溶解于高纯水中，配成15％的溶液，备用；
②增溶剂溶液的配制：准确称取100g聚山梨酯增溶剂，溶解于高纯水中，配成10％的溶液，备用；
③原料的配制：把相当于1kg干胶，固含量10％的氟橡胶乳液5kg预热至30℃，备用；
④乳液的凝聚：将步骤③配制的原料加入凝聚釜中，在500rpm的速率下搅拌，加入步骤①配制的凝聚剂溶液，并以2000rpm的条件下搅拌2～5min；然后将步骤②配制的增溶剂溶液加入凝聚釜，继续搅拌3～8min，凝聚至胶粒颗粒均匀、浆液清澈为止，停止搅拌后得到破乳析出的氟橡胶颗粒，将析出的胶粒进行洗涤10次、过振动筛、真空干燥3h，得到氟橡胶产品。
实施例8：
按照如下方法步骤对氟橡胶乳液进行凝聚处理：
①凝聚剂溶液的配制：准确称取150g MgCl 2凝聚剂，溶解于高纯水中，配成15％的溶液，备用；
②增溶剂溶液的配制：准确称取100g聚山梨酯增溶剂，溶解于高纯水中，配成10％的溶液，备用；
③原料的配制：把相当于1kg干胶，固含量10％的氟橡胶乳液5kg预热至30℃，备用；
④乳液的凝聚：将步骤③配制的原料加入凝聚釜中，在300rpm的速率下搅拌，加入步骤①配制的凝聚剂溶液，并以1800rpm的条件下搅拌2～5min；然后将步骤②配制的增溶剂溶液加入凝聚釜，继续搅拌3～8min，凝聚至胶粒颗粒均匀、浆液清澈为止，停止搅拌后得到破乳析出的氟橡胶颗粒，将析出的胶粒进行洗涤10次、过振动筛、真空干燥3h，得到氟橡胶产品。
对比例1：
其他条件同实施例1，所不同的是凝聚过程不添加增溶剂进行凝聚。
对比例2：
其他条件同实施例4，所不同的是凝聚过程不添加增溶剂进行凝聚。
实验例
将实施例1至8和对比例1至2得到的产品按照以下测试方法进行测试，结果如表1所示。
氟橡胶洗涤水电导率的测试
1、当氟橡胶产品在洗涤桶内洗涤次数达到一定次数后，从洗涤桶排水口用烧杯接一杯水(水位合适即可不需要称量)送分析室测试；
2、由于测试样品的电导率较低，选用的是FE30电导率仪，具有内置温度探头的电极(如LE701电导电极)；
3、电导率仪开机；
4、仪器自检通过后，将电极充分浸入待测样品中，然后按读数键开始测量，测量时小数点在闪动，显示屏显示样品的电导率值，屏幕上有A图标显示。当结果稳定后测量停止，小数点不再闪动，同时√A显示在屏幕上；
5、测试完毕；
氟橡胶生胶的含水率测试
1、将铝盒放入烘箱15min干燥；
2、取出铝盒放入干燥器冷却30min；
3、称空铝盒质量，记为m0；
4、称取5g以上剪成粒状的白胶，记为m1；
5、将称好的白胶放入铝盒中在105℃的烘箱中烘1.5h；
6、拿出冷却30min称取白胶和铝盒的质量，记为m2；
7、含水率X的公式为:
Figure PCTCN2021124486-appb-000001
氟橡胶粒径测试方法
1、氟橡胶经洗涤干净后，排放至振动筛内进行过滤脱除吸附的水分和粒度分析，振动筛筛板从上往下依次设置四层不同的筛孔直径：2.0cm，1.5cm，1.0cm，0.5cm，经过筛选后通过皮带送入料盘收集；
2、称重，记录不同筛孔上收集到的产品对应的重量占总产品重量的 百分数，然后根据该百分数计算其平均粒径。
表1实施例和对比例实验数据
组分和参数 氟橡胶乳液 高纯水 凝聚剂 增溶剂 效果 含水率 粒径 电导率
实施例1 100 余量 0.3 0.08 A+ 0.118 0.8cm 1.3
实施例2 100 余量 1 0.2 A+ 0.100 1.9cm 1.4
实施例3 100 余量 0.3 0.5 A 0.075 1.6cm 1.6
实施例4 100 余量 1 0.5 A 0.078 1.2cm 2.4
实施例5 100 余量 0.1 0.05 B 0.109 0.3cm 2.6
实施例6 100 余量 3 0.05 B 0.142 0.4cm 2.8
实施例7 100 余量 0.1 1 B 0.112 0.2cm 2.5
实施例8 100 余量 1.5 1 B 0.117 0.4cm 2.6
对比例1 100 余量 0.3 无 C 0.229 0.1cm 16
对比例2 100 余量 1 无 C 0.311 0.3cm 20
由实施例1至6与对比例1至2对比分析可以看出，采用同样的凝聚方法使用了增溶剂制得的平均胶粒径要大于未使用的，在同样的干燥时间和洗涤次数条件下，使用了增溶剂制得的胶粒含水率和洗涤水电导率均比未使用的低。本方法的使用可以减少用水量和缩短干燥时间，制得的产品杂质含量更低。同时，在特定含量的增溶剂作用下效果更佳。在特定比例范围内的凝聚剂和增溶剂会产生协同效果，采用该范围时效果最优。
以上仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种改善氟橡胶乳液凝聚效果的方法，以氟橡胶乳液为原料，其特征在于在体系中加入增溶剂；其步骤是向乳液中，先加入高纯水，再加入凝聚剂，然后向其中加入增溶剂进行凝聚。
  2. 根据权利要求所述的一种改善氟橡胶乳液凝聚效果的方法，所述增溶剂包括选自甲基纤维素、聚乙二醇单甲醚、聚氧乙烯脂肪酸酯、聚山梨酯、PEG(聚乙二醇)中的至少一种或多种组合。
  3. 根据权利要求所述的一种改善氟橡胶乳液凝聚效果的方法，所述凝聚剂包括选自CaCl 2、MgCl 2、K 2SO 4、NaCl、KCl、NH 4Cl中的一种。
  4. 根据权利要求1-3任一项所述的一种改善氟橡胶乳液凝聚效果的方法，所述的增溶剂、原料的质量比为0.08～0.5:100，原料以氟橡胶乳液的干胶的重量计。
  5. 根据权利要求1-4任一项所述的一种改善氟橡胶乳液凝聚效果的方法，所述的凝聚剂、增溶剂、原料的质量比为0.3～1.0:0.08～0.5:100，原料以氟橡胶乳液的干胶的重量计。
  6. 根据权利要求5所述的一种改善氟橡胶乳液凝聚效果的方法，包括以下步骤：
    ①凝聚剂溶液的配制：将0.3～1.0重量份凝聚剂，溶解于高纯水中，配成15～25％的溶液，备用；
    ②增溶剂溶液的配制：将0.08～0.5重量份增溶剂，溶解于高纯水中，配成10～15％的溶液，备用；
    ③原料的配制：将相当于100重量份干胶的氟橡胶乳液预热至20-60℃，去除未聚合的单体，备用；
    ④乳液的凝聚：将步骤③配制的原料加入凝聚釜中，再向凝聚釜内加入高纯水稀释至固含量为10～20％，在小于500rpm的速率下搅拌，加入步骤①配制的含有0.3～1.0重量份凝聚剂的凝聚剂溶液，并以大于1000rpm的条件下搅拌2～5min；然后将步骤②配制的含有0.08～0.5重量份增溶剂溶液加入凝聚釜，继续搅拌3～8min，凝聚至胶粒颗粒均匀、浆液清澈为止，停止搅拌后得到破乳析出的氟橡胶颗粒，将析出的胶粒进行洗涤、过振动筛、干燥，得到氟橡胶产品。
  7. 一种氟橡胶，其根据权利要求1-6任一项所述的改善氟橡胶乳液凝聚效果的方法制得。
  8. 根据权利要求7所述的一种氟橡胶，其胶粒粒径在0.5-2cm之间。
  9. 根据权利要求7所述的一种氟橡胶，其电导率在1-5μs/cm之间。
  10. 前述任一项权利要求所述的氟橡胶作为密封材料和化学品输送材料的应用。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101323657A (zh) 2008-03-07 2008-12-17 上海生大医保股份有限公司 戊腈橡胶乳液及戊腈橡胶的制备方法
CN101605823A (zh) * 2007-02-08 2009-12-16 杜邦特性弹性体有限责任公司 凝结含氟弹性体的方法
CN102159597A (zh) * 2008-09-18 2011-08-17 杜邦特性弹性体有限责任公司 凝结含氟弹性体的方法
WO2012067937A2 (en) * 2010-11-18 2012-05-24 3M Innovative Properties Company Method of coagulating an amorphous fluoropolymer using modified inorganic nanoparticles
CN102875711A (zh) 2012-09-20 2013-01-16 中昊晨光化工研究院有限公司 一种聚偏氟乙烯乳液的凝聚洗涤方法
CN104356276A (zh) * 2014-11-06 2015-02-18 浙江孚诺林化工新材料有限公司 一种采用氟醚磺酸盐制备26型氟橡胶的制备方法
CN110078857A (zh) * 2019-04-04 2019-08-02 浙江巨圣氟化学有限公司 一种氟橡胶生胶的制备方法
CN112279943A (zh) * 2019-07-25 2021-01-29 中昊晨光化工研究院有限公司 一种氟橡胶乳液的凝聚洗涤方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101605823A (zh) * 2007-02-08 2009-12-16 杜邦特性弹性体有限责任公司 凝结含氟弹性体的方法
CN101323657A (zh) 2008-03-07 2008-12-17 上海生大医保股份有限公司 戊腈橡胶乳液及戊腈橡胶的制备方法
CN102159597A (zh) * 2008-09-18 2011-08-17 杜邦特性弹性体有限责任公司 凝结含氟弹性体的方法
WO2012067937A2 (en) * 2010-11-18 2012-05-24 3M Innovative Properties Company Method of coagulating an amorphous fluoropolymer using modified inorganic nanoparticles
CN102875711A (zh) 2012-09-20 2013-01-16 中昊晨光化工研究院有限公司 一种聚偏氟乙烯乳液的凝聚洗涤方法
CN104356276A (zh) * 2014-11-06 2015-02-18 浙江孚诺林化工新材料有限公司 一种采用氟醚磺酸盐制备26型氟橡胶的制备方法
CN110078857A (zh) * 2019-04-04 2019-08-02 浙江巨圣氟化学有限公司 一种氟橡胶生胶的制备方法
CN112279943A (zh) * 2019-07-25 2021-01-29 中昊晨光化工研究院有限公司 一种氟橡胶乳液的凝聚洗涤方法

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