CN116144008A - 一种稳定剂及其在制备含氟聚合物中的应用 - Google Patents
一种稳定剂及其在制备含氟聚合物中的应用 Download PDFInfo
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 21
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
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- -1 chlorotrifluoroethylene, trifluoroethylene, fluorovinyl ether Chemical compound 0.000 claims description 7
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 claims description 5
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- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 claims description 3
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- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 claims 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 abstract description 8
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 4
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- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
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- RFJVDJWCXSPUBY-UHFFFAOYSA-N 2-(difluoromethylidene)-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane Chemical compound FC(F)=C1OC(F)(F)C(F)(C(F)(F)F)O1 RFJVDJWCXSPUBY-UHFFFAOYSA-N 0.000 description 1
- QSOCFKJCICIFSB-UHFFFAOYSA-N 4,4,5,5-tetrafluoro-2,2-bis(trifluoromethyl)-1,3-dioxolane Chemical compound FC(F)(F)C1(C(F)(F)F)OC(F)(F)C(F)(F)O1 QSOCFKJCICIFSB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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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
- 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
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- 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
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
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- 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
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
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Abstract
本发明涉及含氟聚合物制备技术领域,尤其涉及一种稳定剂及其在制备含氟聚合物中的应用。所述稳定剂具有如下结构式:(CR1R2CR3R4O)a+(CR1R2CR3R4CR5R6O)b;其中,a、b为正整数;R1~R6各自独立地选自如下基团:H、F、含氟或不含氟的烷基或烷氧基,且碳原子数不超过3。本发明提供的稳定剂可显著增强聚合体系的稳定性,弥补了全氟辛酸替代品乳化能力不足、无法生产高分子量含氟聚合物的短板;同时,在降低成本、减少物料浪费的基础上,进一步保证了生产的连续平稳运行,推动了含氟分散聚合技术的进步。
Description
技术领域
本发明涉及含氟聚合物制备技术领域,尤其涉及一种稳定剂及其在制备含氟聚合物中的应用。
背景技术
含氟单体在分散聚合时,为了在水性介质中不会因链转移而阻碍含氟单体的聚合反应,通常会使用含氟表面活性剂,其中全氟辛酸(PFOA)及其盐类(如铵盐、钠盐)在含氟表面活性剂中的应用最为广泛,其重要用途是作为含氟功能性高分子材料制造中的助剂。近年来,在PFOA得到广泛应用的同时,其潜在的对环境和健康影响的问题却逐渐暴露出来,其生产和使用也受到越来越严格的限制。但是在分散聚合中,含氟表面活性剂的使用是必不可少的,只能寻求合适的替代品。
从分子结构而言,用于替代PFOA的含氟表面活性剂既要具有优异的表面性能,以满足憎水憎油和高表面活性的要求,又要具有低毒、易降解等特性,以满足环保和健康要求。目前,随着对全氟辛烷磺酰基化合物的限制越来越严格,针对PFOA替代品开发的技术路线主要是向开发全氟聚醚系列表面活性剂和开发短链的或含支链的氟碳类表面活性剂领域深入。
然而,这些替代品在应用上与全氟辛酸相比存在乳化能力不足的问题,尤其是在生产高分子量、反应速度快的含氟聚合物时,极易在反应器中形成显著量的未被分散的聚合物(也被称为破乳料),这些破乳料通常必须被当做废物丢弃,造成物料浪费和成本的提高。
鉴于此,特提出本发明。
发明内容
本发明的目的在于提供一种稳定剂,该稳定剂具有低生物蓄积性、低毒性和较高的表面活性作用,尤其适用于含氟单体的分散聚合;本发明的另一目的在于提供该稳定剂的应用。
具体地,本发明提供以下技术方案:
本发明提供一种稳定剂,其具有如下结构式:
(CR1R2CR3R4O)a+(CR1R2CR3R4CR5R6O)b;
其中,a、b为正整数;R1~R6各自独立地选自如下基团:H、F、含氟或不含氟的烷基或烷氧基,且碳原子数不超过3。
本发明提供的上述稳定剂,由于特殊的结构特性,可以吸附在乳胶粒表面上,形成具有一定厚度的水化层,该水化层可以阻碍乳胶粒相互碰撞而发生聚并,对分散聚合体系可以起到稳定作用,从而防止聚合反应过程中未被分散的聚合物(破乳料)的产生。
为了进一步提高稳定剂的稳定效果,本发明对其分子量和HLB值进行了优化,具体如下:
作为优选,所述稳定剂的平均分子量为1000~16000。
作为优选,所述稳定剂的HLB值为3.5~30。
本发明还提供以上所述的稳定剂在制备含氟聚合物中的应用。
本发明提供的稳定剂尤其适用于采用分散法制备含氟聚合物;具体而言,将稳定剂应用于包含引发剂和分散剂的含水介质中,采用至少一种含氟单体,通过聚合反应获得含氟聚合物的含水分散体。
进一步地,本发明提供的稳定剂可用于制备均聚聚四氟乙烯(PTFE)及改性PTFE分散体;其中,均聚聚四氟乙烯(PTFE)是指由高纯四氟乙烯单体聚合得到的高分子聚合物,不存在显著的共聚单体;改性PTFE是指TFE与低浓度第二单体共聚得到的共聚物,所得聚合物的熔点不显著低于PTFE的熔点,此类共聚单体的浓度优选小于1重量%,更优选小于0.5重量%,最优选采用至少约0.05重量%的最小量,以获得显著的改性效果。适宜的共聚改性单体包括含氟烯烃和含氟乙烯基醚,如全氟丙烯(HFP)或全氟烷基乙烯基醚(PAVE),优选全氟乙基乙烯基醚(PEVE)和全氟丙基乙烯基醚(PPVE),还可使用三氟氯乙烯(CTFE)、全氟丁基乙烯(PFBE)等单体进行改性。
本发明同时提供一种含氟聚合物的制备方法,包括:以至少一种含氟单体为聚合单体,在以上所述的稳定剂的作用下,进行分散聚合。
作为优选,以聚合体系中水的质量为基准,所述稳定剂的用量为0.1~100ppm;按照上述用量添加向含氟分散聚合反应体系中添加稳定剂,效果更佳。
作为优选,所述含氟单体选自四氟乙烯(TFE)、六氟丙烯(HFP)、氟乙烯(VF)、偏氟乙烯、偏二氟乙烯(VDF)、三氟氯乙烯(CTFE)、三氟乙烯、氟代乙烯基醚、全氟-2,2-二甲基-1,3-二氧杂环戊烯(PDD)、全氟-2-亚甲基-4-甲基-1,3-二氧戊环(PMD)中的一种或几种。
进一步地,所述氟代乙烯基醚为全氟烷基乙烯基醚(PAVE);优选为全氟丙基乙烯基醚(PPVE)、全氟乙基乙烯基醚(PEVE)、全氟甲基乙烯基醚(PMVE)、全氟丁基乙烯中的一种或几种。
作为优选,所述聚合单体选自:四氟乙烯和六氟丙烯的混合物、四氟乙烯和全氟丙基乙烯基醚的混合物、四氟乙烯、六氟丙烯和偏氟乙烯的混合物、偏氟乙烯和六氟丙烯的混合物、偏氟乙烯和四氟乙烯的混合物、四氟乙烯和全氟丁基乙烯的混合物。
本发明还提供一种含氟聚合物,由以上所述的制备方法制得。
作为优选,所述含氟聚合物为聚四氟乙烯、聚三氟氯乙烯或聚偏氟乙烯。
本发明的有益效果在于:
本发明提供的稳定剂可显著增强聚合体系的稳定性,弥补了全氟辛酸替代品乳化能力不足、无法生产高分子量含氟聚合物的短板;同时,在降低成本、减少物料浪费的基础上,进一步保证了生产的连续平稳运行,推动了含氟分散聚合技术的进步。
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。
实施例1
本实施例提供一种稳定剂,其为丙二醇嵌段聚醚L64,并具有如下结构式:
(CH2CH2O)a+(CH2CH2CH2O)b;
其中,a,b为正整数,平均分子量在2900左右。
实施例2
本实施例提供一种含氟聚合物的制备方法,具体如下:
向50L卧式反应釜中加入30L去离子水,固体石蜡1500g,实施例1的丙二醇嵌段聚醚L64 0.03g,CF3CF2CF2OCF(CF3)COOH 40g,开启搅拌转速60r/min,进行氮气置换至氧含量小于30ppm,加入四氟乙烯单体至反应釜压力0.5MPa,升温至反应釜温度80℃,投料保持反应釜内压力2.30MPa,用计量泵加入过硫酸铵0.05g,进行反应,反应速度平稳,经过3h左右的反应,当反应体系固含量达到33%,终止反应,得到聚合物乳液44.776kg,在聚合后的乳液中未产生未被分散的聚合物。
对比例1
本对比例提供一种含氟聚合物的制备方法,具体如下:
向50L卧式反应釜中加入30L去离子水,固体石蜡1500g,CF3CF2CF2OCF(CF3)COOH40g,开启搅拌转速60r/min,进行氮气置换至氧含量小于30ppm,加入四氟乙烯单体至反应釜压力0.5MPa,升温至反应釜温度80℃,投料保持反应釜内压力2.30MPa,用计量泵加入过硫酸铵0.05g,进行反应,反速度太快,降温困难,经过2h左右的反应,反应速度明显变慢,终止反应,得到聚合物乳液42.857kg,在聚合后的乳液中存在未被分散的聚合物0.625kg,反应釜壁和搅拌上存在少量附着物。
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。
Claims (10)
1.一种稳定剂,其特征在于,其具有如下结构式:
(CR1R2CR3R4O)a+(CR1R2CR3R4CR5R6O)b;
其中,a、b为正整数;R1~R6各自独立地选自如下基团:H、F、含氟或不含氟的烷基或烷氧基,且碳原子数不超过3。
2.根据权利要求1所述的稳定剂,其特征在于,所述稳定剂的平均分子量为1000~16000。
3.根据权利要求1或2所述的稳定剂,其特征在于,所述稳定剂的HLB值为3.5~30。
4.权利要求1-3任一项所述的稳定剂在制备含氟聚合物中的应用。
5.一种含氟聚合物的制备方法,其特征在于,包括:以至少一种含氟单体为聚合单体,在权利要求1-3任一项所述的稳定剂的作用下,进行分散聚合。
6.根据权利要求5所述的制备方法,其特征在于,以聚合体系中水的质量为基准,所述稳定剂的用量为0.1~100ppm。
7.根据权利要求5或6所述的制备方法,其特征在于,所述含氟单体选自四氟乙烯、六氟丙烯、氟乙烯、偏氟乙烯、偏二氟乙烯、三氟氯乙烯、三氟乙烯、氟代乙烯基醚、全氟-2,2-二甲基-1,3-二氧杂环戊烯、全氟-2-亚甲基-4-甲基-1,3-二氧戊环中的一种或几种。
8.根据权利要求7所述的制备方法,其特征在于,所述氟代乙烯基醚为全氟烷基乙烯基醚;优选为全氟丙基乙烯基醚、全氟乙基乙烯基醚、全氟甲基乙烯基醚、全氟丁基乙烯中的一种或几种。
9.根据权利要求5-8任一项所述的制备方法,其特征在于,所述聚合单体选自:四氟乙烯和六氟丙烯的混合物、四氟乙烯和全氟丙基乙烯基醚的混合物、四氟乙烯、六氟丙烯和偏氟乙烯的混合物、偏氟乙烯和六氟丙烯的混合物、偏氟乙烯和四氟乙烯的混合物、四氟乙烯和全氟丁基乙烯的混合物。
10.一种含氟聚合物,其特征在于,由权利要求5-9任一项所述的制备方法制得。
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