WO2022000725A1 - 一种控制过氧化物硫化氟橡胶门尼粘度的方法 - Google Patents

一种控制过氧化物硫化氟橡胶门尼粘度的方法 Download PDF

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WO2022000725A1
WO2022000725A1 PCT/CN2020/109529 CN2020109529W WO2022000725A1 WO 2022000725 A1 WO2022000725 A1 WO 2022000725A1 CN 2020109529 W CN2020109529 W CN 2020109529W WO 2022000725 A1 WO2022000725 A1 WO 2022000725A1
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initiator
amount
polymerization
initiator solution
added
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PCT/CN2020/109529
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French (fr)
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余金龙
刘波
钟子强
张廷健
肖忠良
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中昊晨光化工研究院有限公司
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Priority to US17/638,105 priority Critical patent/US20220298278A1/en
Priority to EP20941523.1A priority patent/EP3985036A4/en
Priority to JP2021567972A priority patent/JP7375045B2/ja
Publication of WO2022000725A1 publication Critical patent/WO2022000725A1/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
    • 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
    • C08F2/00—Processes of polymerisation
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • 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
    • C08F214/24—Trifluorochloroethene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/30—Inorganic compounds
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/34—Per-compounds with one peroxy-radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08F14/00—Homopolymers and 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
    • C08F14/18—Monomers containing fluorine
    • C08F14/22—Vinylidene fluoride

Definitions

  • the present invention relates to the field of fluorine chemical industry, and more particularly, to a method for controlling the Mooney viscosity of peroxide vulcanized fluororubber.
  • Fluorine rubber refers to a synthetic polymer elastomer containing fluorine atoms on the carbon atoms of the main chain or side chain.
  • the fluororubber vulcanized with organic peroxide (or free radical) is called peroxide vulcanized fluororubber.
  • peroxide vulcanized fluororubber vulcanized with organic peroxide (or free radical)
  • the Mooney viscosity is between 20 and 20. 70 or so, and the Mooney viscosity requirements vary according to the application field.
  • the polymerization method of peroxide vulcanized fluororubber is mainly emulsion polymerization.
  • the general operation is as follows: add emulsifiers and pH buffers and other auxiliary agents in water, add polymerization monomers to form emulsion, add initiator and pH buffer under certain temperature and pressure.
  • the chain transfer agent is reacted to obtain an elastomer emulsion, and then a coagulation agent is added for coagulation, washing and drying.
  • the common initiator is an inorganic initiator.
  • the polymerization monomer will be added to keep the pressure constant. When the initiation rate is slow, the initiator will be added once or twice appropriately.
  • the Mooney viscosity of the peroxide vulcanized fluororubber obtained by the existing emulsion polymerization reaction is unstable, the Mooney viscosity value may fluctuate within ⁇ 25 under the same reaction conditions, and the polymerization reaction time is also long, which is not conducive to Industrial production.
  • the present invention provides a method for controlling the Mooney viscosity of peroxide vulcanized fluororubber.
  • An embodiment of the present invention provides a method for controlling the Mooney viscosity of peroxide vulcanized fluororubber, comprising:
  • the initiator solution is added by continuous addition, and the addition continues until 5 to 10 minutes before the end of the polymerization reaction;
  • the initial initiator solution addition amount is 0.1-0.5% of the total amount of the polymerized monomer dry material, and the amount of the continuously added initiator solution is 0.1-2% of the total amount of the polymerized monomer dry material.
  • the total amount of the polymerized monomer dry material refers to the total amount of all the polymerized monomers added during the entire emulsion polymerization process, and is calculated as the dry material.
  • the inventor surprisingly found that in the process of peroxide vulcanized fluororubber emulsion polymerization, by changing the addition amount and addition method of the initiator, the existing initial one-time addition was changed to a part of the initial addition. , and the rest have been supplemented until the end of the reaction, which can effectively control the Mooney viscosity of peroxide vulcanized fluororubber within the expected quality (20-70), and the fluctuation does not exceed ⁇ 5, and chain transfer can be omitted in the present invention. It reduces the dosage of auxiliary agents, saves costs, and at the same time improves the reactivity of the polymerization system, effectively shortens the polymerization time, and is beneficial to industrial production.
  • the control method proposed in the present invention is basically applicable to all situations where organic peroxides (or free radicals) are used to vulcanize fluororubber, and is not limited by the polymerization monomers.
  • the polymerized monomer may be two or more of vinylidene fluoride, chlorotrifluoroethylene, tetrafluoroethylene, and hexafluoropropylene.
  • it can be the polymerization of vinylidene fluoride and chlorotrifluoroethylene, the polymerization of vinylidene fluoride and hexafluoropropylene, the polymerization of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene, and so on.
  • the initiator solution is an aqueous solution of the initiator, and the concentration is 1-8%, preferably 1-5%. At this concentration, the reaction can be efficiently initiated, and the reaction rate will not be out of control due to the excessively high concentration and the excessively fast addition rate.
  • the temperature of deionized water is adjusted to be 25-35°C.
  • the temperature will affect the solubility of the initiator and the subsequent initiation effect. If the temperature is too high, the initiator will dissolve and disperse well in the solution, but the initiator will decompose in advance. If the temperature is too low, the solubility of the initiator in the solution will decrease. The dispersion effect is poor. , the initiator decomposes less, which will affect the control of the concentration of the added initiator. Further preferably, the temperature of the deionized water is controlled to be 25-32° C., which is more conducive to the dissolution of the initiator and the reduction of the decomposition of the initiator.
  • the initiator is ammonium persulfate and/or potassium persulfate, preferably a compound initiator composed of ammonium persulfate and potassium persulfate in a mass ratio of (2-5):1.
  • the polymerization temperature is 90 ⁇ 95° C.
  • the pressure is 2.1 ⁇ 2.5 MPa.
  • the initial initiator solution is added in an amount of 0.1 to 0.5% of the total amount of the polymerized monomer dry material, and the amount of the continuously added initiator solution is the total amount of the polymerization monomer dry material. 0.1 to 0.3% of the amount.
  • the addition amount of the initial initiator solution (in terms of initiator) is controlled to be 0.1 to 0.5% of the total amount of the polymerized monomer dry material, which can effectively control the chain initiation, combined with controlling the amount of continuous addition of the initiator solution. (calculated by initiator) is 0.1-0.3% of the total amount of dry polymerized monomers, and the Mooney viscosity of the peroxide vulcanized fluororubber can be finally realized in the range of 60-70.
  • the initial initiator solution is added in an amount of 0.1-0.5% of the total amount of the polymerized monomer dry material, and the amount of the continuously added initiator solution is the total amount of the polymerized monomer dry material. 0.3 to 0.8% of the amount.
  • This solution can control the Mooney viscosity of the obtained peroxide vulcanized fluororubber to be 50-60.
  • the initial initiator solution is added in an amount of 0.1 to 0.5% of the total amount of the polymerized monomer dry material, and the amount of the continuously added initiator solution is the total amount of the polymerization monomer dry material. 0.8 to 1.2% of the amount.
  • the scheme can control the Mooney viscosity of the obtained peroxide vulcanized fluororubber to be 40-50.
  • the initial initiator solution is added in an amount of 0.1 to 0.5% of the total amount of the polymerized monomer dry material, and the amount of the continuously added initiator solution is the total amount of the polymerization monomer dry material. 1.2 to 1.5% of the amount.
  • This solution can control the Mooney viscosity of the obtained peroxide vulcanized fluororubber to be 30-40.
  • the initial initiator solution is added in an amount of 0.1 to 0.5% of the total amount of the polymerized monomer dry material, and the amount of the continuously added initiator solution is the total amount of the polymerization monomer dry material. 1.5 to 2.0% of the amount.
  • This solution can control the Mooney viscosity of the obtained peroxide vulcanized fluororubber to be 20-30.
  • the invention effectively controls the Mooney viscosity value of the peroxide vulcanized fluororubber to be within the expected range by controlling the addition amount and adding method of the initiator, and the fluctuation is small, and the peroxide vulcanized fluororubber with stable and controllable quality is obtained.
  • a chain transfer agent which reduces the amount of auxiliary agents in the polymerization process, and at the same time improves the reactivity of the polymerization system, effectively shortens the polymerization time, and is beneficial to industrial production.
  • the concentrations involved are all mass concentrations.
  • the Mooney viscosity was measured with a disc shear viscometer for unvulcanized rubber in GB/T 1232.1-2000.
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, comprising the following steps:
  • the inorganic initiator (ammonium persulfate) was dissolved in deionized water at 30°C to prepare an initiator solution with a concentration of 2%;
  • the initiator solution was continuously added until 10min before the end;
  • the polymerization reaction time is 2.5h, the initiator solution added continuously is 1100g (that is, the amount of initiator added continuously is 22g), and the total amount of dry polymerized monomers added in the whole reaction process is 11kg;
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the inorganic initiator is potassium persulfate, which is prepared into an initiator solution with a concentration of 5%;
  • the initial initiator addition amount is 25g, the continuous addition initiator amount is 18g, and the total amount of polymerized monomer dry material added in the whole reaction process is 11.2kg;
  • the polymerization temperature was 92°C
  • the pressure was 2.4MPa
  • the polymerization reaction time was 2.5h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the inorganic initiator is ammonium persulfate and potassium persulfate with a mass ratio of 2:1, prepared into an initiator solution with a concentration of 6%;
  • the initial initiator addition amount is 26g, the continuous addition initiator amount is 14g, and the total amount of polymerized monomer dry material added in the whole reaction process is 10.8kg;
  • the polymerization temperature was 94°C
  • the pressure was 2.4MPa
  • the polymerization reaction time was 2.4h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the initial initiator addition is 35g, and the continuous addition of the initiator is 42g, and the total amount of polymerized monomer dry material added in the whole reaction process is 10.0kg;
  • the polymerization temperature was 90°C
  • the pressure was 2.3MPa
  • the polymerization reaction time was 2.2h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the inorganic initiator is potassium persulfate, which is prepared into an initiator solution with a concentration of 5%;
  • the initial initiator addition amount is 14g, the continuous addition initiator amount is 65g, and the total amount of dry polymer monomers added in the entire reaction process is 11.6kg;
  • the polymerization temperature was 92°C
  • the pressure was 2.4MPa
  • the polymerization reaction time was 2.4h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the inorganic initiator is ammonium persulfate and potassium persulfate with a mass ratio of 3:1, prepared into an initiator solution with a concentration of 6%;
  • the initial initiator addition amount is 44g, the continuous addition initiator amount is 70g, and the total amount of polymerized monomer dry material added in the whole reaction process is 10.9kg;
  • the polymerization temperature was 94°C
  • the pressure was 2.4MPa
  • the polymerization reaction time was 2.8h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the inorganic initiator is ammonium persulfate, which is prepared into an initiator solution with a concentration of 3%;
  • the initial initiator addition amount is 18g
  • the continuous addition initiator amount is 96g
  • the total amount of polymerized monomer dry material added in the whole reaction process is 11.8kg
  • the polymerization temperature was 90°C
  • the pressure was 2.3MPa
  • the polymerization reaction time was 2.6h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the inorganic initiator is potassium persulfate, which is prepared into an initiator solution with a concentration of 6%;
  • the initial initiator addition amount is 42g, the continuous addition initiator amount is 98g, and the total amount of polymerized monomer dry material added in the whole reaction process is 11.5kg;
  • the polymerization temperature was 92°C
  • the pressure was 2.4MPa
  • the polymerization reaction time was 3.0h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the inorganic initiator is ammonium persulfate and potassium persulfate with a mass ratio of 4:1, prepared into an initiator solution with a concentration of 6%;
  • the initial initiator addition amount is 25g, the continuous addition initiator amount is 110g, and the total amount of polymerized monomer dry material added in the whole reaction process is 11.7kg;
  • the polymerization temperature was 90°C
  • the pressure was 2.4MPa
  • the polymerization reaction time was 2.8h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the initial initiator addition amount is 12g
  • the continuous addition initiator amount is 140g
  • the total amount of polymerized monomer dry material added in the whole reaction process is 11.0kg
  • the polymerization temperature was 90°C
  • the pressure was 2.3MPa
  • the polymerization reaction time was 2.6h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the inorganic initiator is potassium persulfate, which is prepared into an initiator solution with a concentration of 5%;
  • the initial initiator addition amount is 39g, the continuous addition initiator amount is 138g, and the total amount of polymerized monomer dry material added in the whole reaction process is 11.2kg;
  • the polymerization temperature was 92°C
  • the pressure was 2.3MPa
  • the polymerization reaction time was 2.7h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the inorganic initiator is ammonium persulfate and potassium persulfate with a mass ratio of 4:1, prepared into an initiator solution with a concentration of 6%;
  • the initial initiator addition amount is 29g
  • the continuous addition initiator amount is 150g
  • the total amount of polymerized monomer dry material added in the whole reaction process is 11.3kg
  • the polymerization temperature was 94°C
  • the pressure was 2.4MPa
  • the polymerization reaction time was 2.5h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the inorganic initiator is ammonium persulfate, which is prepared into an initiator solution with a concentration of 3%;
  • the initial initiator addition amount is 22g, the continuous addition initiator amount is 180g, and the total amount of polymerized monomer dry material added in the whole reaction process is 11.8kg;
  • the polymerization temperature was 90°C
  • the pressure was 2.3MPa
  • the polymerization reaction time was 2.3h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the inorganic initiator is potassium persulfate, which is prepared into an initiator solution with a concentration of 6%;
  • the initial initiator addition amount is 35g, the continuous addition initiator amount is 192g, and the total amount of polymerized monomer dry material added in the whole reaction process is 11.6kg;
  • the polymerization temperature was 92°C
  • the pressure was 2.4MPa
  • the polymerization reaction time was 2.5h
  • the present embodiment provides a method for preparing peroxide-vulcanized fluororubber, which is different from Embodiment 1 in that:
  • the inorganic initiator is ammonium persulfate and potassium persulfate with a mass ratio of 2:1, prepared into an initiator solution with a concentration of 6%;
  • the initial initiator addition amount is 36g
  • the continuous addition initiator amount is 185g
  • the total amount of polymerized monomer dry material added in the whole reaction process is 11.7kg
  • the polymerization temperature was 94°C
  • the pressure was 2.2MPa
  • the polymerization reaction time was 2.8h
  • the Mooney value of the peroxide-vulcanized fluororubber can be effectively controlled within a certain range by adjusting the addition amount of the continuous supplementary initiator: the supplementary initiator and the polymerization monomer are added.
  • the proportion of body mass added is (0.1-0.3)%, and the Mooney value is controlled in the range of 60 to 70; the mass addition ratio of initiator and polymerization monomer is (0.3-0.8)%, and the Mooney value is controlled in the range of 50 to 60; The mass addition ratio of the initiator and the polymerized monomer is (0.8-1.2)%, and the Mooney value is controlled in the range of 40-50; the additional initiator and the polymerized monomer are added in the mass ratio (1.2-1.5)%, and the Mooney value is controlled in the range of 30-40 ; Add the mass ratio of initiator and polymerization monomer (1.5-2.0)%, and control the Mooney value in the range of 20-30.
  • Example 2 Compared with Example 1, the difference is that the initiator is added at one time, and the added amount is 34 g. Results The polymerization reaction time was 4.5h, and the Mooney viscosity was 89. It can be seen that the Mooney value exceeds the control range, and the polymerization time is long, which is not conducive to industrial production.
  • This comparative example provides a method for preparing peroxide-vulcanized fluororubber, which is as follows: add 30L deionized water, 35g pH buffer, and 30g emulsifier to the reaction kettle, vacuumize the reaction kettle, and set the temperature in the kettle Raised to 90°C;
  • the polymerization reaction time was 3.5h, and the total amount of dry polymerized monomers added in the entire reaction process was 10.8kg;
  • the invention provides a method for controlling the Mooney viscosity of peroxide vulcanized fluorororubber.
  • the method includes: in the process of peroxide-vulcanized fluororubber emulsion polymerization, adding an initiator solution in a continuous supplementary manner, and the supplementary addition lasts 5 to 10 minutes before the end of the polymerization reaction; wherein, in terms of the initiator, the initial The added amount of the initiator solution is 0.1-0.5% of the total amount of the polymerized monomer dry material, and the amount of the continuously added initiator solution is 0.1-2% of the total amount of the polymerized monomer dry material.
  • the invention effectively controls the Mooney viscosity value of the peroxide vulcanized fluororubber to be within the expected range by controlling the added amount and adding method of the initiator, and the fluctuation is small, and the peroxide vulcanized fluororubber with stable and controllable quality is obtained.
  • There is no need to add a chain transfer agent the dosage of the auxiliary agent in the polymerization process is reduced, the reaction activity of the polymerization system is improved, and the polymerization time is effectively shortened, which is beneficial to industrial production and has good economic value and application prospect.

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Abstract

一种控制过氧化物硫化氟橡胶门尼粘度的方法，包括：在过氧化物硫化氟橡胶乳液聚合过程中，采用连续补加的方式加入引发剂溶液，补加一直持续至聚合反应结束前5～10分钟；其中，以引发剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单体干料总量的0.1～2％，通过控制引发剂的加入量和加入方式，有效控制过氧化物硫化氟橡胶的门尼粘度值在预期范围内，波动小，得到质量稳定可控的过氧化物硫化氟橡胶且不需要加入链转移剂，减少了聚合过程助剂的用量，同时提高了聚合体系的反应活性，有效缩短了聚合时间，有利于工业化生产。

Description

一种控制过氧化物硫化氟橡胶门尼粘度的方法
交叉引用
本申请要求2020年6月30日提交的专利名称为“一种控制过氧化物硫化氟橡胶门尼粘度的方法”的第202010619099.9号中国专利申请的优先权，其全部公开内容通过引用整体并入本文。
技术领域
本发明涉及氟化工领域，更具体地，涉及一种控制过氧化物硫化氟橡胶门尼粘度的方法。
背景技术
氟橡胶(fluororubber)是指主链或侧链的碳原子上含有氟原子的合成高分子弹性体。用有机过氧化物(或自由基)硫化的氟橡胶称为过氧化物硫化氟橡胶，目前过氧化物硫化氟橡胶的加工应用可分为挤出加工和模压加工等，门尼粘度在20～70左右，并且根据应用领域的不同，门尼粘度要求也有所不同。
目前，过氧化物硫化氟橡胶的聚合方法主要是乳液聚合，一般操作如下：在水中加入乳化剂和pH缓冲剂等助剂，加入聚合单体形成乳液，在一定温度和压力下加入引发剂和链转移剂进行反应，得到弹性体乳液，之后加入凝聚剂进行凝聚，洗涤，干燥即得。其中，常见的引发剂为无机引发剂，在反应过程中为保持压力恒定会补加聚合单体，当引发速率较慢时也会适当补加一两次引发剂。
但是，现有的乳液聚合反应制得的过氧化物硫化氟橡胶的门尼粘度不稳定，同样的反应条件结果门尼粘度值可能会在±25波动，而且聚合反应时间也较长，不利于工业化生产。
发明内容
针对现有技术存在的不足，本发明提供一种控制过氧化物硫化氟橡胶门尼粘度的方法。
本发明实施例提供一种控制过氧化物硫化氟橡胶门尼粘度的方法，包括：
在过氧化物硫化氟橡胶乳液聚合过程中，采用连续补加的方式加入引发剂溶液，补加一直持续至聚合反应结束前5～10分钟；
其中，以引发剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单体干料总量的0.1～2％。
上述技术方案中，所述聚合单体干料总量指整个乳液聚合过程中，加入的所有聚合单体的总量，且以干料计。
通过大量研究及中试，发明人惊奇地发现，在过氧化物硫化氟橡胶乳液聚合过程中，通过改变引发剂的加入量和加入方式，即由现有的初始一次性加入改变为初始加入一部分，其余一直采用补加方式持续到接近反应结束，可以有效控制过氧化物硫化氟橡胶门尼粘度在预期品质内(20～70)，且波动不超过±5，而且本发明中可以省略链转移剂，减少了助剂用量，节约成本，同时提高了聚合体系的反应活性，有效缩短了聚合时间，有利于工业化生产。
本发明提出的控制方法基本适用于使用有机过氧化物(或自由基)硫化氟橡胶的所有情况，不受聚合单体的限制。优选地，聚合单体可为偏氟乙烯、三氟氯乙烯、四氟乙烯、六氟丙烯中的两种或多种。具体可为偏氟乙烯与三氟氯乙烯聚合，偏氟乙烯与六氟丙烯聚合，偏氟乙烯、四氟乙烯与六氟丙烯聚合等等。
进一步地，所述引发剂溶液为引发剂的水溶液，浓度为1～8％，优选为1～5％。在此浓度下，既可保证高效地引发反应，又不会因浓度过大加入速率过快导致反应速率失控。
进一步地，配制所述引发剂溶液时，调节去离子水温度为25～35℃。温度高低会影响引发剂的溶解性和后续引发效果，若温度过高，引发剂在溶液中溶解分散效果好，但是引发剂提前分解，若温度过低，引发剂在溶液中溶解度降低分散效果差，引发剂分解较少，会影响加入引发剂的浓度 的控制。进一步优选地，控制去离子水温度为25～32℃，更有利于引发剂的溶解和减少引发剂的分解。
进一步地，所述引发剂为过硫酸铵和/或过硫酸钾，优选为由过硫酸铵和过硫酸钾以质量比(2～5):1组成的复配引发剂。
进一步地，在所述乳液聚合过程中，聚合温度为90～95℃，压力为2.1～2.5MPa。
在本发明一个优选实施方式中，以引发剂计，初始引发剂溶液的加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单体干料总量的0.1～0.3％。
上述技术方案中，将初始引发剂溶液的加入量(以引发剂计)控制为聚合单体干料总量的0.1～0.5％，可有效控制链引发，结合控制连续补加引发剂溶液的量(以引发剂计)为聚合单体干料总量的0.1～0.3％，可最终实现过氧化物硫化氟橡胶的门尼粘度在60～70范围内。
在本发明另一个优选实施方式中，以引发剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单体干料总量的0.3～0.8％。该方案可控制所得过氧化物硫化氟橡胶的门尼粘度为50～60。
在本发明另一个优选实施方式中，以引发剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单体干料总量的0.8～1.2％。该方案可控制所得过氧化物硫化氟橡胶的门尼粘度为40～50。
在本发明另一个优选实施方式中，以引发剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单体干料总量的1.2～1.5％。该方案可控制所得过氧化物硫化氟橡胶的门尼粘度为30～40。
在本发明另一个优选实施方式中，以引发剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单 体干料总量的1.5～2.0％。该方案可控制所得过氧化物硫化氟橡胶的门尼粘度为20～30。
本发明的有益效果：
本发明通过控制引发剂的加入量和加入方式，有效控制过氧化物硫化氟橡胶的门尼粘度值在预期范围内，波动小，得到质量稳定可控的过氧化物硫化氟橡胶，而且本发明不需要加入链转移剂，减少了聚合过程助剂的用量，同时提高了聚合体系的反应活性，有效缩短了聚合时间，有利于工业化生产。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件，或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可通过正规渠道商购买得到的常规产品。
以下实施例中，所涉及的浓度均为质量浓度。
门尼粘度采用GB/T 1232.1-2000未硫化橡胶用圆盘剪切粘度计进行测定。
实施例1
本实施例提供一种制备过氧化物硫化氟橡胶的方法，包括如下步骤：
先将无机引发剂(过硫酸铵)溶于30℃的去离子水中，配制成浓度为2％的引发剂溶液；
在反应釜中加入30L去离子水，35g pH缓冲剂、30g乳化剂，将反应釜进行抽真空操作，将釜内温度升高至90℃；
向反应釜中加入聚合单体A(偏氟乙烯)和聚合单体B(三氟氯乙烯)，至釜内压力达到2.3MPa，加入600g引发剂溶液(即初始引发剂加入量为12g)引发聚合反应，反应过程中适当补加聚合单体A和聚合单体B使釜内压力维持；
反应进行过程中，一直连续补加引发剂溶液至结束前10min；
聚合反应时间为2.5h，连续补加的引发剂溶液为1100g(即连续补加引发剂量为22g)，整个反应过程中加入的聚合单体干料总量为11kg；
得到弹性体乳液，加入凝聚剂进行凝聚，洗涤，真空干燥，最后得过氧化物硫化氟橡胶9.8kg，其门尼粘度为65。
实施例2
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
无机引发剂为过硫酸钾，配制成浓度为5％的引发剂溶液；
初始引发剂加入量为25g，连续补加引发剂量为18g，整个反应过程中加入的聚合单体干料总量为11.2kg；
乳液聚合过程中，聚合温度为92℃，压力为2.4MPa；聚合反应时间为2.5h；
最后得过氧化物硫化氟橡胶9.7kg，其门尼粘度为63。
实施例3
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
无机引发剂为质量比为2:1的过硫酸铵和过硫酸钾，配制成浓度为6％的引发剂溶液；
初始引发剂加入量为26g，连续补加引发剂量为14g，整个反应过程中加入的聚合单体干料总量为10.8kg；
乳液聚合过程中，聚合温度为94℃，压力为2.4MPa；聚合反应时间为2.4h；
最后得过氧化物硫化氟橡胶9.5kg，其门尼粘度为68。
实施例4
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
初始引发剂加入量为35g，连续补加引发剂量为42g，整个反应过程 中加入的聚合单体干料总量为10.0kg；
乳液聚合过程中，聚合温度为90℃，压力为2.3MPa；聚合反应时间为2.2h；
最后得过氧化物硫化氟橡胶9.2kg，其门尼粘度为53。
实施例5
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
无机引发剂为过硫酸钾，配制成浓度为5％的引发剂溶液；
初始引发剂加入量为14g，连续补加引发剂量为65g，整个反应过程中加入的聚合单体干料总量为11.6kg；
乳液聚合过程中，聚合温度为92℃，压力为2.4MPa；聚合反应时间为2.4h；
最后得过氧化物硫化氟橡胶9.9kg，其门尼粘度为57。
实施例6
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
无机引发剂为质量比为3:1的过硫酸铵和过硫酸钾，配制成浓度为6％的引发剂溶液；
初始引发剂加入量为44g，连续补加引发剂量为70g，整个反应过程中加入的聚合单体干料总量为10.9kg；
乳液聚合过程中，聚合温度为94℃，压力为2.4MPa；聚合反应时间为2.8h；
最后得过氧化物硫化氟橡胶9.3kg，其门尼粘度为54。
实施例7
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
无机引发剂为过硫酸铵，配制成浓度为3％的引发剂溶液；
初始引发剂加入量为18g，连续补加引发剂量为96g，整个反应过程中加入的聚合单体干料总量为11.8kg；
乳液聚合过程中，聚合温度为90℃，压力为2.3MPa；聚合反应时间为2.6h；
最后得过氧化物硫化氟橡胶9.8kg，其门尼粘度为46。
实施例8
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
无机引发剂为过硫酸钾，配制成浓度为6％的引发剂溶液；
初始引发剂加入量为42g，连续补加引发剂量为98g，整个反应过程中加入的聚合单体干料总量为11.5kg；
乳液聚合过程中，聚合温度为92℃，压力为2.4MPa；聚合反应时间为3.0h；
最后得过氧化物硫化氟橡胶9.6kg，其门尼粘度为48。
实施例9
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
无机引发剂为质量比为4:1的过硫酸铵和过硫酸钾，配制成浓度为6％的引发剂溶液；
初始引发剂加入量为25g，连续补加引发剂量为110g，整个反应过程中加入的聚合单体干料总量为11.7kg；
乳液聚合过程中，聚合温度为90℃，压力为2.4MPa；聚合反应时间为2.8h；
最后得过氧化物硫化氟橡胶9.8kg，其门尼粘度为41。
实施例10
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
初始引发剂加入量为12g，连续补加引发剂量为140g，整个反应过程中加入的聚合单体干料总量为11.0kg；
乳液聚合过程中，聚合温度为90℃，压力为2.3MPa；聚合反应时间为2.6h；
最后得过氧化物硫化氟橡胶9.8kg，其门尼粘度为35。
实施例11
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
无机引发剂为过硫酸钾，配制成浓度为5％的引发剂溶液；
初始引发剂加入量为39g，连续补加引发剂量为138g，整个反应过程中加入的聚合单体干料总量为11.2kg；
乳液聚合过程中，聚合温度为92℃，压力为2.3MPa；聚合反应时间为2.7h；
最后得过氧化物硫化氟橡胶9.6kg，其门尼粘度为33。
实施例12
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
无机引发剂为质量比为4:1的过硫酸铵和过硫酸钾，配制成浓度为6％的引发剂溶液；
初始引发剂加入量为29g，连续补加引发剂量为150g，整个反应过程中加入的聚合单体干料总量为11.3kg；
乳液聚合过程中，聚合温度为94℃，压力为2.4MPa；聚合反应时间为2.5h；
最后得过氧化物硫化氟橡胶9.5kg，其门尼粘度为38。
实施例13
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
无机引发剂为过硫酸铵，配制成浓度为3％的引发剂溶液；
初始引发剂加入量为22g，连续补加引发剂量为180g，整个反应过程中加入的聚合单体干料总量为11.8kg；
乳液聚合过程中，聚合温度为90℃，压力为2.3MPa；聚合反应时间为2.3h；
最后得过氧化物硫化氟橡胶9.8kg，其门尼粘度为22。
实施例14
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
无机引发剂为过硫酸钾，配制成浓度为6％的引发剂溶液；
初始引发剂加入量为35g，连续补加引发剂量为192g，整个反应过程中加入的聚合单体干料总量为11.6kg；
乳液聚合过程中，聚合温度为92℃，压力为2.4MPa；聚合反应时间为2.5h；
最后得过氧化物硫化氟橡胶9.8kg，其门尼粘度为27。
实施例15
本实施例提供一种制备过氧化物硫化氟橡胶的方法，与实施例1不同之处在于：
无机引发剂为质量比为2:1的过硫酸铵和过硫酸钾，配制成浓度为6％的引发剂溶液；
初始引发剂加入量为36g，连续补加引发剂量为185g，整个反应过程中加入的聚合单体干料总量为11.7kg；
乳液聚合过程中，聚合温度为94℃，压力为2.2MPa；聚合反应时间为2.8h；
最后得过氧化物硫化氟橡胶9.5kg，其门尼粘度为28。
为直观比较，将各实施例的聚合时间、门尼粘度及引发剂比例列入表1。
表1 各实施例的聚合时间、门尼粘度及引发剂比例
Figure PCTCN2020109529-appb-000001
由以上结果可知，采用本发明实施例的方法，过氧化物硫化氟橡胶的门尼值通过调整连续补加引发剂的加入量，可以有效控制在一定的范围内：补加引发剂与聚合单体质量加入比例(0.1-0.3)％，控制门尼值范围60～70；补加引发剂与聚合单体质量加入比例(0.3-0.8)％，控制门尼值范围50～60；补加引发剂与聚合单体质量加入比例(0.8-1.2)％，控制门尼值范围40～50；补加引发剂与聚合单体质量加入比例(1.2-1.5)％，控制门尼值范围30～40；补加引发剂与聚合单体质量加入比例(1.5-2.0)％，控制门尼值范围20～30。
对比例1
与实施例1相比，其区别在于，引发剂一次性加入，加入量为34g。结果聚合反应时间为4.5h，门尼粘度为89。可见，门尼值超出了控制范围，且聚合时间较长，不利于工业化生产。
对比例2
本对比例提供一种制备过氧化物硫化氟橡胶的方法，具体如下：在反应釜中加入30L去离子水，35g pH缓冲剂、30g乳化剂，将反应釜进行抽真空操作，将釜内温度升高至90℃；
向反应釜中加入聚合单体A(偏氟乙烯)和聚合单体B(三氟氯乙烯)，至釜内压力达到2.3MPa，加入链转移剂丙二酸二乙酯32g引发剂加入量为48g，引发聚合反应，反应过程中适当补加聚合单体A和聚合单体B使釜内压力维持；
聚合反应时间为3.5h，整个反应过程中加入的聚合单体干料总量为10.8kg；
得到弹性体乳液，加入凝聚剂进行凝聚，洗涤，真空干燥，最后得过氧化物硫化氟橡胶10.2kg，其门尼粘度为27。
该方法需加入链转移剂，引发剂用量也较多，且重复该方法几次，结果所得产品的门尼粘度波动至15甚至44。而重复实施例1的方法几次，结果基本保持不变，波动在±5之内。
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。
工业实用性
本发明提供一种控制过氧化物硫化氟橡胶门尼粘度的方法。所述方法包括：在过氧化物硫化氟橡胶乳液聚合过程中，采用连续补加的方式加入引发剂溶液，补加一直持续至聚合反应结束前5～10分钟；其中，以引发 剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单体干料总量的0.1～2％。本发明通过控制引发剂的加入量和加入方式，有效控制过氧化物硫化氟橡胶的门尼粘度值在预期范围内，波动小，得到质量稳定可控的过氧化物硫化氟橡胶，而且本发明不需要加入链转移剂，减少了聚合过程助剂的用量，同时提高了聚合体系的反应活性，有效缩短了聚合时间，有利于工业化生产，具有较好的经济价值和应用前景。

Claims (10)

  1. 一种控制过氧化物硫化氟橡胶门尼粘度的方法，其特征在于，包括：
    在过氧化物硫化氟橡胶乳液聚合过程中，采用连续补加的方式加入引发剂溶液，补加一直持续至聚合反应结束前5～10分钟；
    其中，以引发剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单体干料总量的0.1～2％。
  2. 根据权利要求1所述的方法，其特征在于，所述引发剂溶液为引发剂的水溶液，浓度为1～8％，优选为1～5％。
  3. 根据权利要求2所述的方法，其特征在于，配制所述引发剂溶液时，调节去离子水温度为25～35℃。
  4. 根据权利要求1～3任一项所述的方法，其特征在于，所述引发剂为过硫酸铵和/或过硫酸钾，优选为由过硫酸铵和过硫酸钾以质量比(2～5):1组成的复配引发剂。
  5. 根据权利要求1～4任一项所述的方法，其特征在于，在所述乳液聚合过程中，聚合温度为90～95℃，压力为2.1～2.5MPa。
  6. 根据权利要求1～5任一项所述的方法，其特征在于，以引发剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单体干料总量的0.1～0.3％。
  7. 根据权利要求1～5任一项所述的方法，其特征在于，以引发剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单体干料总量的＞0.3～0.8％。
  8. 根据权利要求1～5任一项所述的方法，其特征在于，以引发剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单体干料总量的＞0.8～1.2％。
  9. 根据权利要求1～5任一项所述的方法，其特征在于，以引发剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发 剂溶液的量为聚合单体干料总量的＞1.2～1.5％。
  10. 根据权利要求1～5任一项所述的方法，其特征在于，以引发剂计，初始引发剂溶液加入量为聚合单体干料总量的0.1～0.5％，连续补加引发剂溶液的量为聚合单体干料总量的＞1.5～2.0％。
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