CN103694396B - A polymer fluorine rubber and its preparation method and application - Google Patents

A polymer fluorine rubber and its preparation method and application Download PDF

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CN103694396B
CN103694396B CN 201310739641 CN201310739641A CN103694396B CN 103694396 B CN103694396 B CN 103694396B CN 201310739641 CN201310739641 CN 201310739641 CN 201310739641 A CN201310739641 A CN 201310739641A CN 103694396 B CN103694396 B CN 103694396B
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fluororubber
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potassium
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张海波
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中昊晨光化工研究院有限公司
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本发明涉及一种氟橡胶的制备方法,在氧化还原引发体系和乳化剂共同作用下,两种或两种以上的主聚单体在高压低温条件下共聚,并引入改性单体,聚合得到氟橡胶。 The present invention relates to a method for preparing the fluororubber, the redox initiator system and emulsifier interaction, the main of two or more comonomers at a high pressure low temperature copolymerization, and introduction of a modifying monomer, polymerization fluororubber. 本发明通过控制聚合反应条件,优化氧化还原引发体系、乳化剂等助剂,有效提高氟橡胶分子量,重均分子量达到80万以上;所得氟橡胶,氟含量在40%以上,特性粘度大于5.0;溶解后的高粘态溶液具有高氟含量、耐老化、耐候性、耐腐蚀性,可作为涂料中防沉降和抗流挂性好的增稠剂使用。 The present invention, by controlling the polymerization conditions, optimized redox system, emulsifier and other additives, effectively improve molecular fluorine rubber, weight average molecular weight of 80 million or more; the resulting fluororubber, a fluorine content of more than 40%, intrinsic viscosity greater than 5.0; dissolving highly viscous solution state has a high fluorine content, aging resistance, weathering resistance, corrosion resistance, anti-sagging anti-settling and thickening agents as good coatings.

Description

一种高分子含氟橡胶及其制备方法和应用 A polymer fluorine rubber and its preparation method and application

技术领域 FIELD

[0001] 本发明涉及一种高分子含氟橡胶及其制备方法和应用。 [0001] The present invention relates to a fluorine rubber polymer and a preparation method and application. 属于高分子制备领域。 Belongs to the field of polymer was prepared.

背景技术 Background technique

[0002] 一般来说涂料使用的助剂用量很少(通常少于5%),但往往可以用于解决生产中出现的许多问题,对提高和改善涂料及涂膜的性能起到十分关键的作用,是涂料生产与施工中必不可少的成分,亚洲是涂料与油墨助剂消费最大的地区,中国地区呈2位数增长趋势。 [0002] Generally the amount of additives used in coatings few (typically less than 5%), but can often be used to solve many problems in production, and to enhance and improve the performance of coatings and films play a critical effect, paint production and construction is an essential ingredient, Asia is the region's largest paint and ink additives consumption in China showed double-digit growth.

[0003] 溶剂型涂料常用的增稠剂有无机增稠剂和有机增稠剂;无机增稠剂有有机膨胀土、气相二氧化硅、氢化蓖麻油、聚酰胺蜡等,纳米技术实现对无机物颗粒的纳米化,但其与溶剂型涂料的相容性、分散性、沉降性一直限制了在该领域的使用。 [0003] Solvent-based coatings commonly used thickeners are inorganic thickeners and organic thickeners; inorganic thickeners organic soil, fumed silica, hydrogenated castor oil, a polyamide wax, inorganic nano-technology of nano-particles, but the compatibility, dispersibility, sedimentation solvent-borne coatings it has been restricted to use in the field. 有机增稠剂具有良好的强度、耐热性和与涂料良好的亲和性,CN1415658A公开了一种含氟碳基团疏水缔合型增稠剂,由丙烯酸或甲基丙烯酸酯、丙烯酸酯和双官能团聚合而成,其氟含量不到1%,其具有流平性、改善抗飞溅性,但其缺点是对PH值的敏感性、对表面活性剂的敏感性等;聚酰胺蜡具有较高的黏度,防沉降和抗流挂性能好,但由于不含氟,其耐老化、耐候性、耐腐蚀性等方面存在不足。 Organic thickeners having good strength, good heat resistance and affinity with the paint, CN1415658A discloses a fluorocarbon group-containing hydrophobic associative thickeners, esters of acrylic or methacrylic acid, acrylate and bifunctional polymerizable formed, a fluorine content of less than 1%, having leveling, improved spatter resistance, but its drawback is the sensitivity of the PH value of the sensitivity to a surfactant and the like; polyamide waxes having a relatively high viscosity, anti-settling and anti-sagging performance is good, but does not contain fluorine, which anti-aging, there is insufficient weather resistance, and corrosion resistance.

[0004] 氟橡胶是一类高性能材料,利用分子结构中硫化交联点,采用离子硫化交联、自由基硫化交联、辐射交联的方式得到性能优化后的混炼胶,经过模压、注射等加工方式制作成定型圈、垫、管,广泛应用于汽车的0型密封圈、阀杆密封、轴密封、垫圈、燃油胶管及油井的密封和填堵材料。 [0004] The fluorine-containing rubber is a kind of high-performance materials, utilizing the molecular structure cure crosslinking sites, sulfide ion cross-linking, vulcanization radical crosslinking, radiation crosslinking manner mix obtained after performance optimization, after molding, injections made into other processing methods styling circle, mats, pipes, is widely used in automobile 0-ring, stem seal, shaft seal, gasket, hose and oil wells and filling and blocking materials. 研究发现,利用氟橡胶可溶解于极性溶剂(如低分子酯和酮)的特点,已逐步使用在粘结剂、涂料、涂料助剂等领域。 The study found that the use of the characteristics of the fluororubber may be dissolved in a polar solvent (e.g., low molecular weight ketones and esters), and has been gradually used in adhesives, coatings, paint additives, and other fields. 利用其高剪切强度、可交联性及流变性,可以用作增稠剂提高溶剂型含氟涂料的流平效果和涂膜厚度,改善加工性能。 Use of its high shear strength, rheology and crosslinking, can be used as a thickener and improved leveling effect of the coating thickness of the fluorine-containing coating solvent, improve the processing performance.

[0005] 然而现有的氟含量大于40%的含氟橡胶,重均分子量一般在3~30万之间,特性粘度为〇. 7~2. 5之间。 [0005] However, a conventional fluorine content greater than 40% of the fluorine-containing rubber, weight average molecular weight is generally between 3 and 300,000, an intrinsic viscosity of between square. 7 ~ 2.5. 如CN101186667A所述的高强度三元氟橡胶的分子量在30万左右, 其粘度太低,难以达到涂料用增稠剂提高涂料粘度的要求。 The molecular weight of the high strength of the fluororubber three yuan CN101186667A about 300,000, its viscosity is too low, it is difficult to achieve the required coating viscosity thickener improve the coating.

发明内容 SUMMARY

[0006] 为了克服上述的缺陷,本发明提供一种分子量大于80万,特性粘度大于5. 0氟橡胶,其溶解后的高粘态溶液具有高氟含量、耐老化、耐候性、耐腐蚀性,可用于涂料的防沉降和抗流挂的增稠剂使用。 [0006] In order to overcome the above drawbacks, the present invention provides a molecular weight greater than 800,000, intrinsic viscosity greater than 5.0 fluororubber, highly viscous solution after dissolution state having a high fluorine content, aging resistance, weatherability, corrosion resistance , it can be used for anti-settling and anti-sag coating of thickeners.

[0007] 为了实现上述目的,本发明采用如下技术方案: [0007] To achieve the above object, the present invention adopts the following technical solution:

[0008] -种氟橡胶,其分子量为80万以上,分子量分布在1. 2~3. 0之间,氟含量大于40%,特性粘度大于5.0。 [0008] - species fluororubber, having a molecular weight of 800,000 or more, a molecular weight distribution between 1.2 - 30, the fluorine content of greater than 40%, intrinsic viscosity greater than 5.0.

[0009] 本发明还提供上述氟橡胶的制备方法,在氧化还原引发体系和乳化剂共同作用下,两种或两种以上的主聚单体在高压低温条件下共聚,并引入改性单体,聚合得到氟橡胶。 [0009] The present invention further provides the above method for preparing the fluororubber, the redox initiator system and emulsifier interaction, the main of two or more comonomers at a high pressure low temperature copolymerization, introduction of a modifying monomer and , fluororubber polymerization.

[0010] 其中,本发明所述氧化还原引发体系实质为加入引发剂所构建的氧化还原体系, 所述引发剂由氧化剂和还原剂组成,其中,氧化剂为过硫酸铵、过硫酸钾、高锰酸钾、硝酸、 过氧化丁二酸、全氟聚醚过氧化物中的一种或两种以上;还原剂为亚硫酸钠、偏重亚硫酸钠、溴化钾、溴化钠、氢化铝锂、三氧化硫中的一种或两种以上。 [0010] wherein the present invention is a redox system initiator is added to the substance of the constructed redox systems, the initiator by the reducing agent and oxidizing agent, wherein the oxidizing agent is ammonium persulfate, potassium persulfate, permanganate, potassium nitrate, succinic acid peroxide, perfluoropolyether peroxide of one or more; the reducing agent is sodium sulfite, sodium metabisulfite, potassium bromide, sodium bromide, lithium aluminum hydride, sulfur trioxide one or two or more kinds.

[0011] 所述乳化剂为全氟辛酸盐、含氟磺酸盐、含氟聚醚羧酸盐等中的一种或两种以上, 优选含氟聚醚羧酸盐。 [0011] The emulsifier is a salt of perfluoro octanoic acid, a fluorine-containing sulfonate, carboxylate, etc. A fluorine-containing polyether or two or more, preferably a fluorine-containing polyether carboxylates.

[0012] 所述高压低温条件:温度为20~60 °C,优选20~40 °C,反应压力为3.0~ 6. 0Mpa〇 [0012] The high pressure low temperature conditions: temperature 20 ~ 60 ° C, preferably 20 ~ 40 ° C, a reaction pressure of 3.0 to 6. 0Mpa〇

[0013] 所述改性单体为全氟甲基乙烯基醚、全氟正丙基乙烯基醚、全氟烷氧基乙烯基醚中的一种或两种以上。 [0013] The modifying monomer is a perfluoro methyl vinyl ether, perfluoro n-propyl vinyl ether, a perfluoroalkoxy vinyl ether, or two or more kinds. 其中,以主聚单体总摩尔计,全氟甲基乙烯基醚的摩尔含量为〇~ 50%,全氟正丙基乙烯基醚的摩尔含量为0~30%,全氟烷氧基乙烯基醚的摩尔含量为0~ 50% 〇 Wherein a master total moles of polymerizable monomers, perfluoro methyl vinyl ether content is square to 50 molar% content by mole of perfluoro propyl vinyl ether, n is 0 to 30%, perfluoroalkoxyethylene ether molar content of from 0 to 50% square

[0014] 在本发明技术方案中,采用氧化还原体系,确保聚合反应在高压低温反应体系中进行,从而保证良好的聚合速率;此外,在本发明中加入表面张力更高的含氟羧酸盐类乳化剂,使胶束粒子很好地分散在溶液中且按目标保持持续稳定的链增长,避免在反应结束前提前析出,使分子量达到预期目标。 [0014] In the aspect of the present invention, a redox system, to ensure a low temperature polymerization is carried out in a high pressure reaction system, thus ensuring a good rate of polymerization; Furthermore, addition of higher surface tension in the present invention, the fluorine-containing carboxylate in emulsifier, micelle particles are well dispersed in solution and the target by maintaining a steady growth in the chain, to avoid precipitation in advance of the end of the reaction, the molecular weight to achieve the desired objectives.

[0015] 作为本发明优选的实施方式,所述制备方法具体包括如下步骤: [0015] As a preferred embodiment of the invention, the preparation method includes the following steps:

[0016] (1)向反应釜中加入去离子水,预留30~50%的空间; [0016] (1) Deionized water was added to the kettle, 30 to 50% of the reserved space;

[0017] (2)抽空反应釜,除氧; [0017] (2) the reaction vessel was evacuated, oxygen;

[0018] (3)向反应釜中加入部分主聚单体至压力为2. 0~5.OMpa,温度20~40°C时,加入乳化剂、pH值调节剂、氧化剂、还原剂,在氧化还原引发体系中开始聚合反应; [0018] (3) of the main portion of comonomer was added to a pressure reactor 2. 0 ~ 5.OMpa, temperature 20 ~ 40 ° C, was added emulsifying agents, pH adjusting agents, oxidants, reducing agents, in redox system to start the polymerization reaction;

[0019] (4)反应过程中,持续补加主聚单体维持反应釜压力3. 0~5.OMpa之间,待主聚单体投加量为预投总量的75-80%时,加入改性单体,反应结束后,将聚合液凝聚得氟橡胶。 When [0019] (4) during the reaction, continuously supplemented to maintain the main polymerizable monomer reactor pressures between 3. 0 ~ 5.OMpa, the main comonomer to be pre-dosage administered 75-80% of the total , modified monomer was added. after completion of the reaction, the polymerization solution obtained fluororubber aggregation.

[0020] 在上述制备方法中,所述主聚单体为偏氟乙烯和四氟乙烯、三氟氯乙烯、全氟丙烯、乙烯、丙烯中的一种或两种以上。 [0020] In the above production method, the primary comonomer is vinylidene fluoride and tetrafluoroethylene, chlorotrifluoroethylene, perfluoro propylene, ethylene, propylene, one or two or more kinds. 其中,以主聚单体总摩尔计,偏氟乙烯占30%~80%。 Wherein the main polymerizable monomer to total moles of vinylidene fluoride, 30% to 80%.

[0021] 所述pH值调节剂为硼砂、磷酸氢二钾、氢氧化钠或氢氧化钾。 [0021] The pH regulator is borax, potassium hydrogen phosphate, sodium or potassium hydroxide. 其中,每100重量份去离子水中加入〇. 001~2重量份乳化剂、0. 001~5重量份引发剂,在引发剂中氧化剂和还原剂重量比为1~5:1、0. 1~5重量份pH值调节剂。 Wherein, per 100 parts by weight of deionized water was added to 2 billion parts by weight of emulsifier 001, 0001 - 5 parts by weight initiator in the initiator oxidizing and reducing a weight ratio of 1 ~ 5:... 1,0 1 to 5 parts by weight of a pH adjusting agent.

[0022] 本发明还提供上述氟橡胶作为涂料增稠剂的具体应用。 [0022] The present invention further provides the above-described fluorine-containing rubber paint thickener as the particular application. 将上述方法得到的聚合物溶解于极性溶剂中,得到一种介于溶解和溶胀临界状态的溶液。 The polymer obtained as described above is dissolved in a polar solvent, to obtain a critical state between dissolution and swelling solution. 其中,所述极性溶剂为低分子的酯、酮、苯类等。 Wherein said polar solvent is an ester of a low molecular weight ketone, benzene and the like.

[0023] 本发明通过控制聚合反应条件,优化氧化还原引发体系、乳化剂等助剂,有效提高氟橡胶分子量,重均分子量达到80万以上;所得氟橡胶,氟含量在40%以上,特性粘度大于5. 0 ;溶解后的高粘态溶液具有高氟含量、耐老化、耐候性、耐腐蚀性,可作为涂料中防沉降和抗流挂性好的增稠剂使用。 [0023] The present invention, by controlling the polymerization conditions, the redox system optimization, emulsifiers and other additives, effectively improve molecular fluorine rubber, weight average molecular weight of 80 million or more; the resulting fluororubber, a fluorine content of more than 40%, an intrinsic viscosity greater than 5.0; dissolving highly viscous solution state has a high fluorine content, aging resistance, weathering resistance, corrosion resistance, it can be used as coatings and anti-sagging anti-settling good thickeners.

具体实施方式 detailed description

[0024] 以下实施例用于说明本发明,但不用来限制本发明的范围。 [0024] The following examples serve to illustrate the present invention but are not intended to limit the scope of the present invention.

[0025] 实施例1 [0025] Example 1

[0026] 50L卧式反应釜,加入30L去离子水,抽空至氧含量小于50ppm,加入摩尔比为1 :1 的三氟氯乙烯和偏氟乙烯的混合单体至反应釜压力为2. 5Mpa,并同时升温至40°C,加入3g高锰酸钾、lg溴化钾、15g氢氧化钠,50g全氟聚醚羧酸钠,开始反应。 [0026] 50L horizontal reactor, 30L of deionized water was added, evacuated to an oxygen content of less than 50 ppm, was added 1 molar ratio: vinylidene fluoride, chlorotrifluoroethylene and vinyl monomer mixture to a reactor pressure of 1 to 2. 5Mpa , and the temperature was raised to 40 ° C, 3g of potassium permanganate, lg of potassium bromide, 15g of sodium hydroxide, 50g perfluoropolyether carboxylate, the reaction was started. 期间加入上述比例的混合单体维持反应爸压力在3. 5Mpa,当混合单体投料至10kg时加入lkg的全氟甲基乙烯基醚,并继续反应至混合单体投料至13kg,停止。 Was added to the mixed monomer ratio during the reaction is maintained at a pressure Dad 3. 5Mpa, lkg added perfluoro methyl vinyl ether monomer feed when mixed to 10kg, and the reaction was continued until the monomer feed mixture to 13kg, stopped. 回收未反应完单体至单体贮槽,抽空、放出乳液,加入少量的MgClJI聚出目标产物,通过采用无离子水洗涤后进行干燥送检结果见表1。 After recovery of unreacted monomers to the monomer tank, evacuated, release emulsion, adding a small amount of the desired product polyethylene MgClJI Table 1 was dried after washed inspection results deionized water.

[0027] 实施例2 [0027] Example 2

[0028] 50L卧式反应釜,加入30L去离子水,抽空至氧含量小于50ppm,加入比例为摩尔比为2 :8的全氟丙烯和偏氟乙烯的混合单体至反应釜压力为3. 5Mpa,并同时升温至40°C,加入3g高锰酸钾、lg溴化钾、15g氢氧化钠,50g全氟聚醚羧酸钠,开始反应。 [0028] 50L horizontal reactor, 30L of deionized water was added, evacuated to an oxygen content of less than 50 ppm, was added a proportion of a molar ratio of 2: 8 perfluoropropylene and vinylidene fluoride monomer mixture to a reactor pressure of ethylene of 3. 5mpa, and while warming to 40 ° C, 3g of potassium permanganate, lg of potassium bromide, 15g of sodium hydroxide, 50g perfluoropolyether carboxylate, the reaction was started. 期间加入上述比例的混合单体维持反应爸压力在5.OMpa,当投料至10kg时加入lkg的全氟甲基乙烯基醚, 并继续反应至混合单体投料至13kg,停止。 Mixed monomer was added to the reaction ratio of the sustain period Dad pressure 5.OMpa, when feed was added to lkg of 10kg perfluoromethyl vinyl ether, and the reaction was continued until the monomer feed mixture to 13kg, stopped. 回收未反应完单体至单体贮槽,抽空、放出乳液, 加入少量的MgClJI聚出目标产物,通过采用无离子水洗涤后进行干燥送检结果见表1。 After recovery of unreacted monomers to the monomer tank, evacuated, release emulsion, adding a small amount of the desired product polyethylene MgClJI Table 1 was dried after washed inspection results deionized water.

[0029] 对比例1 [0029] Comparative Example 1

[0030] 50L立式式反应釜,加入30L去离子水,抽空至氧含量小于50ppm,加入比例为摩尔比为2 :8的全氟丙烯和偏氟乙烯的混合单体至反应釜压力为2. 5Mpa,并同时升温至80°C, 加入5g过硫酸钾、15g氢氧化钠,20g全氟聚醚羧酸钠,开始反应。 [0030] 50L vertical type reactor, 30L of deionized water was added, evacuated to an oxygen content of less than 50 ppm, was added a proportion of a molar ratio of 2: 8 perfluoropropylene and vinylidene fluoride monomer mixture to a reactor ethylene pressure of 2 . of 5Mpa, and while warming to 80 ° C, was added 5g of potassium persulfate, 15g of sodium hydroxide, 20g perfluoropolyether carboxylate, the reaction was started. 期间加入上述比例的混合单体维持反应爸压力在2. 5Mpa,当投料至13kg,停止。 The monomer mixture was added the above ratio is maintained at the reaction pressure dad 2. 5Mpa, when the feed to 13kg, stopped period. 回收未反应完单体至单体槽,抽空、放出乳液,加入少量的MgClJI聚出目标产物,通过采用无离子水洗涤后进行干燥送检结果见表1。 After recovery of unreacted monomers to the monomer tank, evacuated, release emulsion, adding a small amount of the desired product polyethylene MgClJI Table 1 was dried after washed inspection results deionized water.

[0031] 表1检测数据表 [0031] Table 1 Datasheet detection

[0032] [0032]

Figure CN103694396BD00051

[0033] 实施例3 [0033] Example 3

[0034] 本实施例意在举例说明本发明所述氟橡胶对改善涂料性能情况,但不局限于实施例3所述涂料。 [0034] The present embodiments are intended to illustrate the embodiments of the present invention to improve the coating performance fluororubber case, but not limited to Example 3 Coating.

[0035] 本实施例提供一种含有氟橡胶的涂料。 [0035] The present embodiment provides a coating containing fluororubber.

[0036] 将实施例1和2、对比例1得到的氟橡胶,溶解于乙酸乙酯中,得到30wt%的呈溶胀临界状态的溶液A、B、C,在200g某种溶剂型环氧树脂涂料中,分别加入30g上述溶液A、B、 C,并分散均匀得到涂料1、2、3 ;在200g上述同类环氧树脂中加入2. 5g气相二氧化硅,得到涂料4。 [0036] Examples 1 and 2, fluororubber obtained in Comparative Example 1, was dissolved in ethyl acetate, to give 30wt% of the critical state was swelled A, B, C, in a solvent-type epoxy resins 200g paint, 30g were added to the solution A, B, C, and uniformly dispersed to obtain a coating 1,2,3; 2. 5g of fumed silica was added in 200g of the same epoxy resin to obtain a coating 4.

[0037] 取上述涂料各2%,进行分析检测,结果见表2。 [0037] 2% of each of the coating material taken and analyzed, and the results are shown in Table 2.

[0038] 表2涂料性能检测 [0038] Table 2 Coating Performance Testing

[0039] [0039]

Figure CN103694396BD00061

[0040] 由表2可知,涂料1、2在特性粘度、触变指数方面明显优于涂料3 ;而且在粘结性能、耐候性、耐腐蚀性、透水性方面也保持了现有涂料的优点,因此,综合来说,本发明制得的氟橡胶用于涂料中取得了显著的效果。 [0040] Table 2 shows that the coating 1 intrinsic viscosity, thixotropic index significantly better than the coating 3; and in adhesion properties, weather resistance, corrosion resistance, water permeability but also maintaining the advantages of conventional coating Therefore, summary, the present invention is obtained fluorine-containing rubber used in the coating has achieved remarkable results.

[0041] 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。 [0041] While the foregoing has been a general description and specific embodiments of the present invention is described in detail, but the present invention is based on, you can make some modifications or improvements, which will be apparent to those skilled in the art . 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。 Accordingly, such modifications without departing from the spirit of the present invention is based on the improvement made or, belong to the scope of the invention as claimed.

Claims (6)

  1. 1. 一种氟橡胶的制备方法,其特征在于,包括如下步骤: (1) 向反应釜中加入去离子水,预留30~50%的空间; (2) 抽空反应釜,除氧; (3) 向反应釜中加入部分主聚单体至压力为2. 0~5.OMpa,温度20~40°C时,加入乳化剂、pH值调节剂、氧化剂、还原剂,在氧化还原引发体系中开始聚合反应; (4) 反应过程中,持续补加主聚单体维持反应釜压力3. 0~5.OMpa之间,待主聚单体投加量为预投总量的75-80%时,加入改性单体,反应结束后,将聚合液凝聚得氟橡胶; 其中,所述乳化剂为含氟聚醚羧酸盐;所述改性单体为全氟甲基乙烯基醚、全氟正丙基乙烯基醚、全氟烷氧基乙烯基醚中的一种或两种以上。 1. A process for producing fluororubber, characterized by comprising the steps of: (1) Deionized water was added to the kettle, 30 to 50% of the reserved space; (2) the reaction vessel was evacuated, oxygen; ( 3) the portion of the main polymerizable monomer added to the reaction vessel to a pressure of 2. 0 ~ 5.OMpa, temperature 20 ~ 40 ° C, was added emulsifying agents, pH adjusting agents, oxidants, reducing agents, in the redox system to start the polymerization reaction; (4) during the reaction, continuously supplemented to maintain the main polymerizable monomer between 3. 0 ~ 5.OMpa autoclave pressure, until the main comonomer the total dosage of the pre-cast 75-80 %, the modifying monomer is added, after the reaction, the polymerization solution to obtain a fluororubber aggregate; wherein said emulsifying agent is a fluorine-containing polyether carboxylates; the modifying monomer is a perfluoro vinyl ether , perfluoro n-propyl vinyl ether, a perfluoroalkoxy vinyl ethers, one or two or more kinds.
  2. 2. 根据权利要求1所述制备方法,其特征在于,在所述氧化还原引发体系中,氧化剂为过硫酸铵、过硫酸钾、高锰酸钾、硝酸、过氧化丁二酸、全氟聚醚过氧化物中的一种或两种以上;还原剂为亚硫酸钠、偏重亚硫酸钠、溴化钾、溴化钠、氢化铝锂、三氧化硫中的一种或两种以上。 The production method according to claim 1, characterized in that the redox system, the oxidizing agent is ammonium persulfate, potassium persulfate, potassium permanganate, nitric acid, succinic acid peroxide, perfluoro poly ether peroxides of one or more; the reducing agent is sodium sulfite, sodium metabisulfite, potassium bromide, sodium bromide, lithium aluminum hydride, in a three or two or more of sulfur trioxide.
  3. 3. 根据权利要求1所述制备方法,其特征在于,在上述制备方法中,所述主聚单体为偏氟乙烯和四氟乙烯、三氟氯乙烯、全氟丙烯、乙烯、丙烯中的一种或两种以上;其中,以主聚单体总摩尔计,偏氟乙稀占30 %~80%。 3. The production method according to claim 1, wherein, in the above production method, the primary comonomer is vinylidene fluoride and tetrafluoroethylene, chlorotrifluoroethylene, perfluoro propylene, ethylene, propylene in one or two or more; wherein the main polymerizable monomer to total moles of vinylidene fluoride, ethylene accounts for 30% to 80%.
  4. 4. 根据权利要求1所述制备方法,其特征在于,所述pH值调节剂为硼砂、磷酸氢二钾、 氢氧化钠或氢氧化钾。 4. The production method according to claim 1, wherein said pH adjusting agent is borax, potassium hydrogen phosphate, sodium or potassium hydroxide.
  5. 5. 权利要求1-4任一所述制备方法得到的氟橡胶,其特征在于,其分子量为80万以上, 分子量分布在1. 2~3. 0之间,氟含量大于40%,特性粘度大于5. 0。 Fluororubber obtained by the production method according to any one of claim 1-4 having an intrinsic viscosity, wherein, having a molecular weight of 800,000 or more, a molecular weight distribution of 1.2 to 3. 0, a fluorine content of greater than 40%, is greater than 5.0.
  6. 6. 权利要求5所述氟橡胶作为涂料增稠剂的用途。 5 6. The fluororubber claims as a paint thickener.
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