CN110506084A - 用于制造包含氟聚合物颗粒的水性胶乳的方法 - Google Patents
用于制造包含氟聚合物颗粒的水性胶乳的方法 Download PDFInfo
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- CN110506084A CN110506084A CN201880024717.6A CN201880024717A CN110506084A CN 110506084 A CN110506084 A CN 110506084A CN 201880024717 A CN201880024717 A CN 201880024717A CN 110506084 A CN110506084 A CN 110506084A
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- 238000000034 method Methods 0.000 title claims abstract description 41
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 42
- 239000004816 latex Substances 0.000 title claims description 39
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- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims description 2
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
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- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 2
- YFZCNXJOYHYIGC-UHFFFAOYSA-N (2,2,2-trichloroacetyl) 2,2,2-trichloroethaneperoxoate Chemical compound ClC(Cl)(Cl)C(=O)OOC(=O)C(Cl)(Cl)Cl YFZCNXJOYHYIGC-UHFFFAOYSA-N 0.000 description 1
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- FKTXDTWDCPTPHK-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)[C](F)C(F)(F)F FKTXDTWDCPTPHK-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
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- HFNSTEOEZJBXIF-UHFFFAOYSA-N 2,2,4,5-tetrafluoro-1,3-dioxole Chemical compound FC1=C(F)OC(F)(F)O1 HFNSTEOEZJBXIF-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- LIZVXGBYTGTTTI-UHFFFAOYSA-N 2-[(4-methylphenyl)sulfonylamino]-2-phenylacetic acid Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C(O)=O)C1=CC=CC=C1 LIZVXGBYTGTTTI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- JYCQQPHGFMYQCF-UHFFFAOYSA-N 4-tert-Octylphenol monoethoxylate Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCO)C=C1 JYCQQPHGFMYQCF-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- QTZRATLYJFAPPV-UHFFFAOYSA-N C(OC(C)(C)OOCCCC)(O)=O.C(C)(C)(C)OOC(C)(C)C Chemical compound C(OC(C)(C)OOCCCC)(O)=O.C(C)(C)(C)OOC(C)(C)C QTZRATLYJFAPPV-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- QBHRYXFREPYPPU-UHFFFAOYSA-N O1COC=C1.[F] Chemical compound O1COC=C1.[F] QBHRYXFREPYPPU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- RMYQWLNPMCOISL-UHFFFAOYSA-N benzoyl benzenecarboperoxoate;n,n-diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 RMYQWLNPMCOISL-UHFFFAOYSA-N 0.000 description 1
- ZAVUGVPMYAZPGN-UHFFFAOYSA-N benzoyl benzenecarboperoxoate;n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 ZAVUGVPMYAZPGN-UHFFFAOYSA-N 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
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- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical compound C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000003292 glue Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
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- 239000008240 homogeneous mixture Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
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- 238000010128 melt processing Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- IXDAOYYROAXYLL-UHFFFAOYSA-N tert-butyl 2-ethylhexoxy carbonate Chemical class CCCCC(CC)COOC(=O)OC(C)(C)C IXDAOYYROAXYLL-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
Classifications
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers 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
- C08F114/18—Monomers containing fluorine
- C08F114/26—Tetrafluoroethene
-
- 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
- C08F14/26—Tetrafluoroethene
-
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Abstract
本发明涉及一种用于制造可熔融加工的氟聚合物的方法,涉及通过所述方法可获得的该可熔融加工的氟聚合物并且涉及所述可熔融加工的氟聚合物在各种应用中的用途。
Description
技术领域
本发明涉及一种用于制造可熔融加工的氟聚合物的方法,涉及通过所述方法可获得的该可熔融加工的氟聚合物并且涉及所述可熔融加工的氟聚合物在各种应用中的用途。
背景技术
可熔融加工的氟聚合物是本领域已知的,其被赋予高的机械抗性和高的耐化学性两者以便适当用于多种应用。
在可熔融加工的氟聚合物之中,已经受到对解决使用领域的越来越多的关注的一类的特定材料(其中需要优异的机械强度和耐化学性的组合)是一类四氟乙烯(TFE)、偏二氟乙烯(VDF)以及第三共聚单体的三聚物。
在这一领域,US 8997797(大金工业株式会社(DAIKIN INDUSTRIES,LTD.))7/04/2015披露了适用于制造立管的具有在170℃下的高结晶度和高储能模量的氟聚合物,所述氟聚合物由衍生自四氟乙烯(TFE)、偏二氟乙烯(VDF)以及除了四氟乙烯和偏二氟乙烯之外的烯键式不饱和单体的共聚单元组成。在这些三聚物之中,特别提及(j)TFE和VDF与0.1%至5.0%摩尔的衍生自(全)氟烷基乙烯单体(例如CH2=CH-C4F9;CH2=CH-C6F13)的重复单元的三聚物以及(jj)TFE和VDF与0.1%至0.8%摩尔的衍生自具有式CF2=CF-ORf 1的(全)(氟)烷基乙烯基醚(其中Rf 1是C1-3烷基或C1-3氟烷基)的重复单元的三聚物。所有示例的工作实施例涉及通过在约35℃的温度下,在水/全氟化烷烃溶剂的共混物的存在下,在有机过氧化物引发下悬浮聚合制造的聚合物。此类方法不适用于提供稳定的氟聚合物分散体/胶乳:其结果由粗的不规则颗粒的浆料组成。
WO 2016/099913(戈尔公司(W.L.GORE))23/06/2016涉及某些由核/壳PTFE状材料制成的成形零件,这些核/壳PTFE状材料具有至少三个熔点,更确切地在50℃与300℃之间的第一吸热、在320℃与350℃之间的第二吸热、以及在350℃与400℃之间的第三吸热,此第三吸热为大约380℃。在具体实例(实例1)中,描述了通过在氟化表面活性剂的存在下乳液聚合制造TFE/VDF共聚物。在开始时,将VDF引入反应器,并且然后进一步添加TFE。然后,一旦引发聚合,进料TFE(单独地);在已经转化12kg的TFE之后,再次开始进料VDF。获得的整个核/壳聚合物被描述为具有27.9%摩尔(19.9%wt)的VDF含量以及DSC示出的多个熔点的胶乳,这些熔点具体是177.73℃、341.83℃以及369.19℃,第一个是VDF的准均聚物的代表,并且最后一个是TFE的准均聚物的代表。
JP2017/057379(大金工业株式会社(Daikin Industries))涉及一种用于在表面活性剂和水性介质的存在下,在可以在0与9.8MPaG(98巴)之间变化的压力下使四氟乙烯和偏二氟乙烯聚合的制造方法,其中该表面活性剂可以选自下组,该组由以下各项组成:
(A)由下式表示的含氟烯丙基醚化合物:CX2=CFCF2-O-(CF(CF3)CF2O)n-CF(CF3)-Y,其中每个X相同或不同并且表示F或H,n表示0或者1至10的整数,Y表示-SO3M或-COOM并且M表示H、NH或碱金属;
(B)具有7至20个碳原子的直链1-烷磺酸、具有7至20个碳原子的直链2-烷磺酸、具有7至20个碳原子的直链1,2-烷二磺酸及其盐;
(C)至少一种选自下组的非氟化的表面活性剂,该组由以下各项组成:聚乙烯基膦酸、聚丙烯酸、聚乙烯基磺酸及其盐;
(D)具有2-100个具有式-CH2CH2O-或-CH2CH2CH2O-的重复单元的表面活性剂;
(E)以下项的组合:(i)选自由非氟化的表面活性剂和具有小于400的分子量的氟化的表面活性剂组成的组的至少一种表面活性剂和(ii)包含氟聚氧亚烷基链和官能团醚的官能的氟聚醚;以及
(F)含未被活化的烃的表面活性剂。关于选项(E),作为小于400的分子量的氟化的表面活性剂(其可以与官能的全氟聚醚组合使用)的可能的实施例,列举了使用环状氟表面活性剂。
总的来说,尽管如此,在所有实例中,使用反应性烯丙基氟表面活性剂CH2=CFCF2-O-(CF(CF3)CF2O)-CF(CF3)-COONH4。
尽管在本领域中已经进行了各种尝试来制造TFE和VDF的共聚物,可能地包括其他共聚物,但在本领域中存在对通过有效的且有成本效益的工艺(具有更高的聚合动力学)制造呈包含给定尺寸的颗粒的胶乳的形式的这些共聚物的方法的持续需要。
发明内容
现已出人意料地发现,本发明的方法有利地使得能够以有效的方式容易地提供TFE和VDF的聚合物。
特别地,已经发现,本发明的方法有利地在相对低的压力下进行,同时实现高聚合速率连同在由其提供的水性胶乳中的高固体含量,以及连同受控的粒度。
还已经发现,本发明的水性胶乳可以是配制的,例如与其他水性胶乳混合并共凝结,从而提供适用于各种应用、尤其涂料应用的均匀混合物。
在第一实例中,本发明涉及一种用于制造包含氟聚合物[聚合物(F)]颗粒的水性胶乳的方法,该氟聚合物基本上由以下项组成:
-按摩尔计从60%至85%、优选按摩尔计从65%至80%的衍生自四氟乙烯(TFE)的重复单元,
-按摩尔计从15%至40%、优选按摩尔计从20%至35%的衍生自偏二氟乙烯(VDF)的重复单元,以及
-任选地,按摩尔计从0%至10%的衍生自至少一种不同于四氟乙烯(TFE)和偏二氟乙烯(VDF)的氟化单体的重复单元,
其中所述重复单元的摩尔量是相对于所述聚合物(F)中的重复单元的总摩尔数,
所述聚合物(F)具有包括在170℃与300℃之间的熔点(Tm),其中根据ASTM D 3418标准方法通过差示扫描量热法(DSC)确定熔点,
所述方法包括通过在包含至少一种表面活性剂[表面活性剂(F)]的水性聚合介质中进行乳液聚合使TFE、VDF以及任选的所述氟化单体聚合,该表面活性剂具有式(II):
其中X1、X2和X3彼此相同或不同,独立地选自由H、F和任选地包含一个或多个链状或非链状氧原子的C1-C6(全)氟烷基组成的组,L是键或二价基团,RF是二价的氟化C1-C3桥联基团,并且Y是阴离子官能团,并且所述方法包括进料TFE和VDF的气态共混物用于维持包括在6巴与20巴之间的聚合压力。
在第二实例中,本发明涉及一种水性胶乳,该水性胶乳包含:
(A)至少一种聚合物(F),其包含:
-按摩尔计从60%至85%、优选按摩尔计从65%至80%的衍生自四氟乙烯(TFE)的重复单元,以及
-按摩尔计从15%至40%、优选按摩尔计从20%至35%的衍生自偏二氟乙烯(VDF)的重复单元,
-任选地,按摩尔计从0%至10%、优选按摩尔计从0%至5%的衍生自至少一种不同于四氟乙烯(TFE)和偏二氟乙烯(VDF)的氟化单体的重复单元,
其中所述重复单元的摩尔量是相对于所述聚合物(F)中的重复单元的总摩尔数,以及
(B)至少一种如上详述的表面活性剂[表面活性剂(F)]
其中该水性胶乳中的聚合物(F)呈具有如根据ISO 13321测量的从55nm至300nm的平均初级颗粒尺寸的初级颗粒的形式。
本发明的聚合物(F)有利地是可熔融加工的。术语“可熔融加工的”在此旨在表示可以通过常规的熔融加工技术加工的氟聚合物。
本发明的聚合物(F)具有包括在170℃与300℃之间、优选在200℃与280℃之间的熔点(Tm),其中根据ASTM D 3418标准方法通过差示扫描量热法(DSC)确定熔点。
出于本发明的目的,术语“氟化单体”旨在表示包含至少一个氟原子的烯键式不饱和单体。
如果氟化单体包含至少一个氢原子,则将其指定为含氢的氟化单体。
如果氟化单体不含氢原子,则将其指定为全(卤)氟化单体。
氟化单体可进一步包含一个或多个其他卤素原子(Cl、Br、I)。
合适的氟化单体的非限制性实例值得注意地包括以下项:
-C3-C8全氟烯烃,如六氟丙烯(HFP);
-C2-C8氢化的氟烯烃,如氟乙烯、1,2-二氟乙烯以及三氟乙烯;
-具有式CH2=CH-Rf0的全氟烷基乙烯,其中Rf0是C1-C6全氟烷基;
-氯代-和/或溴代-和/或碘代-C2-C6氟烯烃,如三氟氯乙烯;
-具有式CF2=CFORf1的(全)氟烷基乙烯基醚,其中Rf1是C1-C6氟烷基或全氟烷基,例如CF3、C2F5、C3F7;
-CF2=CFOX0(全)氟-氧烷基乙烯基醚,其中X0是C1-C12烷基、C1-C12氧烷基或具有一个或多个醚基团的C1-C12(全)氟氧烷基,如全氟-2-丙氧基-丙基;
-具有式CF2=CFOCF2ORf2的(全)氟烷基乙烯基醚,其中Rf2是C1-C6氟烷基或全氟烷基,例如CF3、C2F5、C3F7,或具有一个或多个醚基团的C1-C6(全)氟氧烷基,如-C2F5-O-CF3;
-具有式CF2=CFOY0的官能的(全)氟-氧烷基乙烯基醚,其中Y0是C1-C12烷基或(全)氟烷基、C1-C12氧烷基或具有一个或多个醚基团的C1-C12(全)氟氧烷基,并且Y0包括羧酸或磺酸基团(以其酸、酰基卤或盐的形式);以及
-氟间二氧杂环戊烯,优选全氟间二氧杂环戊烯。
本发明的聚合物(F)典型地进一步包含衍生自至少一种具有式(I)的全氟烷基乙烯基醚(PAVE)的重复单元:
CF2=CF-O-Rf (I)
其中Rf是C1-C6烷基或C1-C6(全)氟烷基。
本发明的聚合物(F)优选地包含按摩尔计从0.1%至5%、优选按摩尔计从1%至5%、更优选按摩尔计从1.5%至3.5%的衍生自至少一种具有式(I)的全氟烷基乙烯基醚(PAVE)的重复单元:
CF2=CF-O-Rf (I)
其中Rf是C1-C6烷基或C1-C6(全)氟烷基,
其中所述重复单元的摩尔量是相对于所述聚合物(F)中的重复单元的总摩尔数。
本发明的聚合物(F)优选地基本上由以下项组成:
-按摩尔计从60%至80%、优选按摩尔计从65%至78%的衍生自四氟乙烯(TFE)的重复单元,
-按摩尔计从15%至35%、优选按摩尔计从20%至30%的衍生自偏二氟乙烯(VDF)的重复单元,以及
-按摩尔计从0.1%至5%、优选按摩尔计从1%至5%、更优选按摩尔计从1.5%至3.5%的衍生自至少一种具有式(I)的全氟烷基乙烯基醚(PAVE)的重复单元:
CF2=CF-O-Rf (I)
其中Rf是C1-C6烷基或C1-C6(全)氟烷基,其中所述重复单元的摩尔量是相对于所述聚合物(F)中的重复单元的总摩尔数。
具有式(I)的全氟烷基乙烯基醚(PAVE)典型地选自下组,该组由以下各项组成:具有式CF2=CF-O-CF3的全氟甲基乙烯基醚(PMVE)、具有式CF2=CF-O-CF2-CF3的全氟乙基乙烯基醚(PEVE)以及具有式CF2=CF-O-CF2-CF2-CF3的全氟丙基乙烯基醚(PPVE),更优选地是选自PMVE和PPVE。
如所述,表面活性剂(F)是具有式(II)的环状氟化合物:
其中X1、X2和X3彼此相同或不同,独立地选自由H、F和任选地包含一个或多个链状或非链状氧原子的C1-C6(全)氟烷基组成的组,L是键或二价基团,RF是二价的氟化C1-C3桥联基团,并且Y是阴离子官能团。
在式(II)中,阴离子官能团Y优选地选自下组,该组由具有下式的那些组成:
其中Xa是H、一价金属(优选碱金属)或具有式-N(R’n)4的铵基团,其中R’n在每次出现时相同或不同,是氢原子或C1-C6烃基(优选烷基)。
最优选地,阴离子官能团Y是如上定义的具有式(3”)的羧酸根。
根据第一变体,表面活性剂(F)是具有式(III)的环状氟化合物:
其中X1、X2、X3、RF、以及Y具有如上定义的相同含义。
更优选地,本发明的此第一实施例的此第一变体的环状氟化合物具有式(IV):
其中X1、X2、X3、RF、以及Xa具有如上定义的相同含义。
根据第二变体,表面活性剂(F)是具有式(V)的环状氟化合物:
其中RF与Xa具有如上定义的相同含义,X*1、X*2彼此相同或不同,独立地是氟原子、-R’f、或-OR’f,其中R’f是C1-C3全氟烷基;RF 1是F或CF3,并且k是从1至3的整数。
更优选地,本发明的此第一实施例的表面活性剂(F)是具有式(VI)的环状氟化合物:
其中Xa具有如上定义的相同的含义,并且特别地其中Xa是NH4。
本发明的方法产生包含聚合物(F)的颗粒的水性胶乳。表述“水性胶乳”在此根据其通常含义使用,即旨在表示包含均匀分散在其中的聚合物(F)的初级颗粒的水性介质。
由本发明的方法产生的包含聚合物(F)的颗粒的水性胶乳包含呈具有如根据ISO13321测量的55nm至300nm的平均初级颗粒尺寸的初级颗粒的形式的所述聚合物(F)。总体上,所述水性胶乳中的聚合物(F)的平均初级颗粒尺寸如根据ISO 13321所测量的包括在55nm与300nm之间、优选在120nm与280nm之间、最优选在150与250nm之间。
为了本发明的目的,“平均初级颗粒尺寸”旨在表示通过水性乳液聚合可获得的聚合物(F)的初级颗粒的平均尺寸。
为了本发明的目的,聚合物(F)的“初级颗粒”旨在是与初级颗粒的团聚体可区分的,这些团聚体可以是例如通过胶乳的凝结获得的。包含聚合物(F)的初级颗粒的水性胶乳有利地是通过水性乳液聚合可获得的。聚合物(F)的初级颗粒的团聚体典型地是通过聚合物(F)制造的回收和调节步骤如水性聚合物(F)胶乳的浓缩和/或凝结并且随后进行干燥并且均化,从而提供聚合物(F)粉末可获得的。
因此,通过本发明方法可获得的水性胶乳旨在是与通过将聚合物(F)粉末分散在水性介质中制备的水性浆料可区分的。分散在水性浆料中的聚合物(F)粉末的平均粒度典型地是如根据ISO 13321测量的大于1.0μm。
通过本发明的方法可获得的水性胶乳有利地具有均匀分散在其中的至少一种聚合物(F)的初级颗粒,这些初级颗粒具有如根据ISO 13321测量的包括在55nm与300nm之间、优选在120nm与280nm之间的平均初级颗粒尺寸。
本发明的方法包括进料TFE和VDF的气态共混物用于维持包括在6巴与20巴之间、优选在10巴与18巴之间、优选在11巴与16巴之间的聚合压力。
本领域技术人员将尤其考虑所使用的自由基引发剂来选择聚合温度。这就是说,通常认为总体上需要超过50℃的聚合温度以实现最佳效率。因此,本发明的方法总体上包括在包括在50℃与135℃之间、优选在55℃与130℃之间的温度下聚合。
虽然自由基引发剂的选择没有特别限制,应理解适用于水性乳液聚合的水溶性自由基引发剂将是优选的。
在能够引发和/或加速本发明的方法中的聚合过程的水溶性自由基引发剂之中,将优选的是无机自由基引发剂,其包括但不限于过硫酸盐如过硫酸钠、过硫酸钾和过硫酸铵,高锰酸盐如高锰酸钾。
另外,可以使用有机自由基引发剂,并且这些有机自由基引发剂包括但不限于以下各项:乙酰环己过磺酸;过氧二碳酸二乙酰基酯;过氧二碳酸二烷基酯,如过氧二碳酸二乙基酯、过氧二碳酸二环己基酯、过氧二碳酸二-2-乙基己基酯;过新癸酸叔-丁酯;2,2’-偶氮双(4-甲氧基-2,4-二甲基戊腈);过新戊酸叔-丁酯;过氧化二辛酰;过氧化二月桂酰;2,2’-偶氮双(2,4-二甲基戊腈);叔丁基偶氮-2-氰基丁烷;过氧化二苯甲酰;叔丁基-过-2乙基己酸酯;过马来酸叔丁酯;2,2’-偶氮双(异丁腈);双(叔丁基过氧)环己烷;叔丁基过氧异丙基碳酸酯;过乙酸叔丁酯;2,2’-双(叔丁基过氧)丁烷;二枯基过氧化物;二叔戊基过氧化物;二叔丁基过氧化物(DTBP);对甲烷氢过氧化物;蒎烷氢过氧化物;枯烯氢过氧化物;以及叔丁基氢过氧化物。
其他合适的自由基引发剂值得注意地包括卤化的自由基引发剂,如基于氯烃的以及基于氟烷的酰基过氧化物如三氯乙酰基过氧化物、双(全氟-2-丙氧基丙酰基)过氧化物、[CF3CF2CF2OCF(CF3)COO]2、全氟丙酰基过氧化物、(CF3CF2CF2COO)2、(CF3CF2COO)2、{(CF3CF2CF2)-[CF(CF3)CF2O]m-CF(CF3)-COO}2(其中m=0-8)、[ClCF2(CF2)nCOO]2、以及[HCF2(CF2)nCOO]2(其中n=0-8);全氟烷基偶氮化合物,如全氟偶氮异丙烷、[(CF3)2CFN=]2、(其中是具有1-8个碳的直链或支链的全氟碳基团);稳定的或受阻的全氟烷自由基,如六氟丙烯三聚体自由基、[(CF3)2CF]2(CF2CF2)C·自由基以及全氟烷。
还可以使用包含形成氧化还原对的至少两种组分如二甲基苯胺-过氧化苯甲酰、二乙基苯胺-过氧化苯甲酰和二苯胺-过氧化苯甲酰的氧化还原体系作为自由基引发剂来引发聚合过程。
在无机自由基引发剂之中,过硫酸铵是特别优选的。
在有机自由基引发剂之中,具有高于50℃的自加速分解温度(SADT)的过氧化物是特别优选的,例如像:二叔丁基过氧化物(DTBP)、二叔丁基过氧化异丙基碳酸酯、叔丁基(2-乙基己基)过氧化碳酸酯、叔丁基过氧化-3,5,5-三甲基己酸酯。
可以将如上定义的一种或多种自由基引发剂以基于水性聚合介质的重量的有利地范围按重量计从0.001%至20%的量添加到本发明方法的水性聚合介质中。
根据某些实施例,在本发明的方法中,水性聚合介质可以进一步包含至少一种非官能的全氟聚醚(PFPE)油。
“非官能的全氟聚醚(PFPE)油”在此旨在表示包含(全)氟聚氧亚烷基链[链(Rf)]和非官能的端基的全氟聚醚(PFPE)油。
该非官能的PFPE油的非官能端基总体上选自具有1至3个碳原子的氟(卤)烷基,任选地包含一个或多个不同于氟的卤素原子或氢原子,例如CF3-、C2F5-、C3F6-、ClCF2CF(CF3)-、CF3CFClCF2-、ClCF2CF2-、ClCF2-。
非官能的PFPE油具有有利地包括在400与3000之间、优选在600与1500之间的数均分子量。
该非官能的PFPE油更优选地选自下组,该组由以下各项组成:
(1’)从苏威苏莱克斯公司(Solvay Solexis S.p.A.)以商标名和可商购的非官能的PFPE油,所述PFPE油总体上包含至少一种符合在此以下的式的任一个的PFPE油:
CF3-[(OCF2CF2)m-(OCF2)n]-OCF3
m+n=40-180;m/n=0.5-2
CF3-[(OCF(CF3)CF2)p-(OCF2)q]-OCF3
p+q=8-45;p/q=20-1000
(2’)从大金工业株式会社(Daikin)以商标名可商购的非官能的PFPE油,所述PFPE总体上包含至少一种符合在此以下的式的PFPE:
F-(CF2CF2CF2O)n-(CF2CF2CH2O)j-CF2CF3
j=0或>0的整数;n+j=10-150
(3’)从杜邦公司(Du Pont de Nemours)以商标名可商购的非官能的PFPE油,所述PFPE总体上包含至少一种符合在此以下的式的六氟丙烯环氧化物的低分子量的、氟封端的均聚物:
F-(CF(CF3)CF2O)n-CF2CF3
n=10-60
该非官能PFPE油甚至更优选地选自具有如上描述的式(1’)的那些。
本发明的方法典型地在链转移剂的存在下进行。
该链转移剂总体上选自在氟化单体的聚合中已知的那些,如乙烷,具有从3至10个碳原子的酮、酯、醚或脂肪醇,例如像丙酮、乙酸乙酯、二乙醚、甲基叔丁基醚、异丙醇;具有从1至6个碳原子的、任选地含有氢的氯(氟)烃,例如像氯仿、三氯氟甲烷;双(烷基)碳酸酯,其中该烷基具有从1至5个碳原子,例如像双(乙基)碳酸酯、双(异丁基)碳酸酯。该链转移剂可以在开始时、在聚合期间连续地或以不连续的量(逐步)进料至水性介质中,连续的或逐步的进料是优选的。
在本领域中已经描述了如上详述的水性乳液聚合方法(参见例如US 4990283(奥塞蒙特公司(AUSIMONT S.P.A.))5/02/1991,US 5498680(奥塞蒙特公司)12/03/1996以及US 6103843(奥塞蒙特公司)15/08/2000)。
本发明的水性胶乳优选地包含按重量计从20%至30%的至少一种聚合物(F)。
本发明的水性胶乳可以根据本领域已知的任何技术进行上行浓缩(up-concentrate)。
通常,通过添加至少一种非离子的氢化表面活性剂[表面活性剂(NS)]进一步配制本发明的水性胶乳。
合适的表面活性剂(NS)的非限制性实例值得注意地包括长链取代的酚烷氧基化物(例如辛基酚乙氧基化物)和脂肪族脂肪醇烷氧基化物,特别是长链(C11-C13)脂肪族醇,该长链(C11-C13)脂肪族醇被烷氧基化以包含以总体上6至15个单元、优选6至10个单元的量的衍生自环氧乙烷和/或环氧丙烷的重复单元。
如根据EN 1890标准(方法A:按重量计1%的水溶液)测量的,该表面活性剂(NS)总体上具有有利地50℃或更高、优选地55℃或更高的浊点。
该表面活性剂(NS)优选地选自由以商标名X和可商购的非离子的氢化表面活性剂组成的组。
在第四实例中,本发明涉及本发明的聚合物(F)在各种应用中的用途。
本发明的聚合物(F)特别适用于油气应用和汽车应用。
在第五实例中,本发明涉及本发明的水性胶乳在各种应用中的用途。
本发明的水性胶乳特别适用于涂料应用。
现在将参考以下实例更详细地说明本发明,这些实例的目的仅仅是说明性的并且不限制本发明的范围。
用于制造聚合物(F-1)的通用程序
在配备有挡板和在180rpm下工作的搅拌器的AISI 316钢制立式高压釜中,引入64升的脱矿质水。然后使温度达到80℃的反应温度并且当达到此温度时,引入600克的如上定义的具有式(VI)(其中Xa=NH4)的环状表面活性剂的34%w/w水溶液、以及2巴的偏二氟乙烯。
随后,通过压缩机添加以摩尔标称比为60∶40的TFE-VDF的气态混合物,直至达到12巴的压力。
然后,进料500ml的按重量计3%的过硫酸钠(NaPS)的水溶液作为引发剂。通过进料上述的TFE-VDF混合物来维持聚合压力恒定。当进料10000g的混合物时,将反应器在室温下冷却,排出胶乳。然后将胶乳冷冻48小时并且一旦解冻,将凝结的聚合物用脱矿质水洗涤并且在80℃下干燥48小时。
用于制造聚合物(F-2)的通用程序
在配备有挡板和在180rpm下工作的搅拌器的AISI 316钢制立式高压釜中,引入64升的脱矿质水。然后使温度达到80℃的反应温度并且当达到此温度时,引入600克的如上定义的具有式(VI)(其中Xa=NH4)的环状表面活性剂的34%w/w水溶液、以及2巴的偏二氟乙烯。随后添加0.1巴的乙烷和0.15巴的PMVE。
随后,通过压缩机添加以摩尔标称比为69∶30∶1的TFE-VDF-PMVE的气态混合物,直至达到12巴的压力。
然后,进料600ml的按重量计3%的过硫酸钠(NaPS)的水溶液作为引发剂。通过进料上述的TFE-VDF-PMVE混合物来维持聚合压力恒定。当进料10000g的混合物时,将反应器在室温下冷却,排出胶乳。然后将胶乳冷冻48小时并且一旦解冻,将凝结的聚合物用脱矿质水洗涤并且在80℃下干燥48小时。
用于制造聚合物(F-3)的通用程序
在配备有挡板和在570rpm下工作的搅拌器的AISI 316钢制立式高压釜中,引入3.5升的脱矿质水。然后使温度达到80℃的反应温度并且引入选定量的如上定义的具有式(VI)(其中Xa=NH4)的环状表面活性剂的34%w/w水溶液、以及2巴的VDF。
随后,通过压缩机添加以摩尔标称比为60∶40的TFE-VDF的气态混合物,直至达到12巴的压力。
然后,进料500ml的按重量计3%的过硫酸钠(NaPS)的水溶液作为引发剂。通过进料上述的TFE-VDF混合物来维持聚合压力恒定。当进料1000g的混合物时,将反应器在室温下冷却,排出胶乳。
水性胶乳中的聚合物(F-3)的平均初级颗粒尺寸是如根据ISO 13321测量的267nm。
然后将胶乳冷冻48小时并且一旦解冻,将凝结的聚合物用脱矿质水洗涤并且在160℃下干燥24小时。
用于制造聚合物(F-4)、(F-5)、(F-6)以及(F-7)的通用程序
在配备有挡板和在570rpm下工作的搅拌器的AISI 316钢制立式高压釜中,引入3.5升的脱矿质水。然后使温度达到80℃的反应温度并且添加选定量的如上定义的具有式(VI)(其中Xa=NH4)的环状表面活性剂的34%w/w水溶液。引入表1中报告的选定的压力变化的VDF、PMVE和乙烷。
随后,通过压缩机添加以以下摩尔标称比的TFE-VDF-PMVE的气态混合物,直至达到12巴的压力:
聚合物(F-4):TFE(69.0%mol)-VDF(29.4%mol)-PMVE(1.6%mol),
聚合物(F-5):TFE(68.6%mol)-VDF(29.0%mol)-PMVE(2.4%mol),
聚合物(F-6):TFE(77.0%mol)-VDF(20.0%mol)-PMVE(3.0%mol),
聚合物(F-7):TFE(69.0%mol)-VDF(30.0%mol)-PMVE(1.0%mol)。
然后,进料选定量的按重量计3%的过硫酸钠(NaPS)的水溶液作为引发剂。通过进料上述的TFE-VDF-PMVE混合物来维持聚合压力恒定。当进料1000g的混合物时,将反应器在室温下冷却,将胶乳排出、冷冻48小时并且一旦解冻,将凝结的聚合物用脱矿质水洗涤并且在160℃下干燥24小时。
工艺条件在表1中列出。
表1
1:基于转化的单体/产生的聚合物;2:VDF的初始分压。
第二熔融温度的测量
根据ASTM D 3418标准方法通过差示扫描量热法(DSC)确定熔点。记录在定义为第二加热期间所观察到的吸热峰的第二熔融温度并在此被称为该聚合物的熔点(Tm)。
关于本发明的聚合物(F-1)、(F-2)、(F-3)、(F-4)、(F-5)、(F-6)以及(F-7)的结果在此以下表2中列出:
表2
用于制造聚合物(F-8)的通用程序
在配备有挡板和在570rpm下工作的搅拌器的AISI 316钢制立式高压釜中,引入3.5升的脱矿质水。然后使温度达到80℃的反应温度并且添加选定量的如上定义的具有式(VI)(其中Xa=NH4)的环状表面活性剂的34%w/w水溶液。引入表1中报告的选定的压力变化的VDF和乙烷。
随后,通过压缩机添加以表3中报告的摩尔标称比的TFE-VDF的气态混合物,直至达到20巴的压力。然后,进料选定量的按重量计3%的过硫酸钠(NaPS)的水溶液作为引发剂。通过进料上述的TFE-VDF同时在规则的间隔下添加PPVE单体维持聚合压力恒定,直至达到表3中指示的总量。
当进料1000g的混合物时,将反应器在室温下冷却,将胶乳排出、冷冻48小时并且一旦解冻,将凝结的聚合物用脱矿质水洗涤并且在160℃下干燥24小时。
如通过NMR测量的获得的聚合物(F-8)的组成是聚合物(F-8)(693/99):TFE(69.6%mol)-VDF(27.3%mol)-PPVE(2.1%mol),具有熔点Tm=218℃以及MFI=5g/10’。
重复产生聚合物(F-8)的程序用于通过引入在表3的第二列中指示的成分的量制造(F-9)。如通过NMR测量的获得的聚合物(F-8)的组成是聚合物(F-8)(693/100):TFE(68%mol)-VDF(29.8%mol)-PPVE(2.2%mol),具有熔点Tm=219℃以及MFI=1.5g/10’。
重复产生聚合物(F-8)的程序用于通过引入在表3的第三列中指示的成分的量制造聚合物(F-10)。如通过NMR测量的获得的聚合物(F-10)的组成是聚合物(F-10)(693/67):TFE(71%mol)-VDF(28.5%mol)-PPVE(0.5%mol),具有熔点Tm=249℃以及MFI=5g/10’。
表3
表2
(F-8) | (F-9) | (F-10) | |
颗粒尺寸[nm] | 186 | 204 | 196 |
T<sub>m</sub>[℃] | 218 | 219 | 249 |
Claims (12)
1.一种用于制造包含氟聚合物[聚合物(F)]颗粒的水性胶乳的方法,该氟聚合物基本上由以下项组成:
-按摩尔计从60%至85%、优选按摩尔计从65%至80%的衍生自四氟乙烯(TFE)的重复单元,
-按摩尔计从15%至40%、优选按摩尔计从20%至35%的衍生自偏二氟乙烯(VDF)的重复单元,以及
-任选地,按摩尔计从0%至10%的衍生自至少一种不同于四氟乙烯(TFE)和偏二氟乙烯(VDF)的氟化单体的重复单元,
其中所述重复单元的摩尔量是相对于所述聚合物(F)中的重复单元的总摩尔数,
所述聚合物(F)具有包括在170℃与300℃之间的熔点(Tm),其中根据ASTM D 3418标准方法通过差示扫描量热法(DSC)确定熔点,
所述方法包括通过在包含至少一种表面活性剂[表面活性剂(F)]的水性聚合介质中进行乳液聚合使TFE、VDF以及任选的所述氟化单体聚合,该表面活性剂具有式(II):
其中X1、X2和X3彼此相同或不同,独立地选自由H、F和任选地包含一个或多个链状或非链状氧原子的C1-C6(全)氟烷基组成的组,L是键或二价基团,RF是二价的氟化C1-C3桥联基团,并且Y是阴离子官能团,并且所述方法包括进料TFE和VDF的气态共混物用于维持包括在6巴与20巴之间的聚合压力。
2.根据权利要求1所述的方法,所述方法在包括在50℃与135℃之间、优选在55℃与130℃之间的温度下进行,和/或其中该方法包括进料TFE和VDF的气态共混物用于维持包括在10巴与18巴之间、优选在11巴与16巴之间的聚合压力。
3.根据权利要求1或2所述的方法,其中,该表面活性剂(F)是具有式(V)的环状氟化合物:
其中RF与Xa具有如上定义的相同含义,X*1、X*2彼此相同或不同,独立地是氟原子、-R’f、或-OR’f,其中R’f是C1-C3全氟烷基;RF 1是F或CF3,并且k是从1至3的整数。
4.根据权利要求1至3中任一项所述的方法,其中,该聚合物(F)进一步包含衍生自至少一种不同于四氟乙烯(TFE)和偏二氟乙烯(VDF)的氟化单体的重复单元。
5.根据权利要求1至4中任一项所述的方法,其中,该聚合物(F)进一步包含衍生自至少一种具有式(I)的全氟烷基乙烯基醚(PAVE)的重复单元:
CF2=CF-O-Rf (I)
其中Rf是C1-C6烷基或C1-C6(全)氟烷基。
6.根据权利要求5所述的方法,其中,该聚合物(F)进一步包含按摩尔计从0.1%至5%、优选按摩尔计从1%至5%、更优选按摩尔计从1.5%至3.5%的衍生自至少一种具有式(I)的全氟烷基乙烯基醚(PAVE)的重复单元,其中所述重复单元的摩尔量是相对于所述聚合物(F)中的重复单元的总摩尔数。
7.根据权利要求1至6中任一项所述的方法,其中,该聚合物(F)包含以下项,优选地由以下项组成:
-按摩尔计从60%至80%、优选按摩尔计从65%至78%的衍生自四氟乙烯(TFE)的重复单元,
-按摩尔计从15%至35%、优选按摩尔计从20%至30%的衍生自偏二氟乙烯(VDF)的重复单元,以及
-按摩尔计从0.1%至5%、优选按摩尔计从1%至5%、更优选按摩尔计从1.5%至3.5%的衍生自至少一种具有式(I)的全氟烷基乙烯基醚(PAVE)的重复单元:
CF2=CF-O-Rf (I)
其中Rf是C1-C6烷基或C1-C6(全)氟烷基,
其中所述重复单元的摩尔量是相对于所述聚合物(F)中的重复单元的总摩尔数。
8.根据权利要求5至7中任一项所述的方法,其中,该具有式(I)的全氟烷基乙烯基醚(PAVE)选自下组,该组由以下各项组成:具有式CF2=CF-O-CF3的全氟甲基乙烯基醚(PMVE)、具有式CF2=CF-O-CF2-CF3的全氟乙基乙烯基醚(PEVE)以及具有式CF2=CF-O-CF2-CF2-CF3的全氟丙基乙烯基醚(PPVE)。
9.一种通过根据权利要求1至8中任一项所述的方法可获得的水性胶乳。
10.一种水性胶乳,该水性胶乳包含:
(A)至少一种聚合物(F),其包含:
-按摩尔计从60%至85%、优选按摩尔计从65%至80%的衍生自四氟乙烯(TFE)的重复单元,以及
-按摩尔计从15%至40%、优选按摩尔计从20%至35%的衍生自偏二氟乙烯(VDF)的重复单元,
-任选地,按摩尔计从0%至10%、优选按摩尔计从0%至5%的衍生自至少一种不同于四氟乙烯(TFE)和偏二氟乙烯(VDF)的氟化单体的重复单元,
其中所述重复单元的摩尔量是相对于所述聚合物(F)中的重复单元的总摩尔数,以及
(B)至少一种具有式(II)的表面活性剂[表面活性剂(F)]:
其中X1、X2和X3彼此相同或不同,独立地选自由H、F和任选地包含一个或多个链状或非链状氧原子的C1-C6(全)氟烷基组成的组,L是键或二价基团,RF是二价的氟化C1-C3桥联基团;
其中该水性胶乳中的聚合物(F)呈具有如根据ISO 13321测量的从55nm至300nm的平均初级颗粒尺寸的初级颗粒的形式。
11.根据权利要求9或10所述的水性胶乳在油气应用和汽车应用中的用途。
12.根据权利要求9或10所述的水性胶乳在涂料应用中的用途。
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WO2016028582A1 (en) * | 2014-08-22 | 2016-02-25 | 3M Innovative Properties Company | Fluorothermoplastic polymer compositions |
JP2017057379A (ja) * | 2015-09-18 | 2017-03-23 | ダイキン工業株式会社 | フルオロポリマーの製造方法 |
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CN115073647A (zh) | 2022-09-20 |
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US11414506B2 (en) | 2022-08-16 |
CN110494516A (zh) | 2019-11-22 |
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US11066501B2 (en) | 2021-07-20 |
KR20190129913A (ko) | 2019-11-20 |
US20200377633A1 (en) | 2020-12-03 |
EP3609965A1 (en) | 2020-02-19 |
CN110520451B (zh) | 2022-04-29 |
JP2023088978A (ja) | 2023-06-27 |
CN110520451A (zh) | 2019-11-29 |
EP3609966A1 (en) | 2020-02-19 |
JP2020516719A (ja) | 2020-06-11 |
KR20190130135A (ko) | 2019-11-21 |
JP2023088938A (ja) | 2023-06-27 |
WO2018189090A1 (en) | 2018-10-18 |
KR20190133185A (ko) | 2019-12-02 |
US11859033B2 (en) | 2024-01-02 |
CN110494516B (zh) | 2022-11-04 |
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