CN1219741C - 制造光可固化的卤代氟化丙烯酸酯的新颖方法 - Google Patents
制造光可固化的卤代氟化丙烯酸酯的新颖方法 Download PDFInfo
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- CN1219741C CN1219741C CNB998128317A CN99812831A CN1219741C CN 1219741 C CN1219741 C CN 1219741C CN B998128317 A CNB998128317 A CN B998128317A CN 99812831 A CN99812831 A CN 99812831A CN 1219741 C CN1219741 C CN 1219741C
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
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- AYCANDRGVPTASA-UHFFFAOYSA-N 1-bromo-1,2,2-trifluoroethene Chemical group FC(F)=C(F)Br AYCANDRGVPTASA-UHFFFAOYSA-N 0.000 description 1
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- 230000010933 acylation Effects 0.000 description 1
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- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
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- 239000012043 crude product Substances 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
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- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- SPRIOUNJHPCKPV-UHFFFAOYSA-N hydridoaluminium Chemical compound [AlH] SPRIOUNJHPCKPV-UHFFFAOYSA-N 0.000 description 1
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- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 229940046063 potassium chlorate Drugs 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 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
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 239000011697 sodium iodate Substances 0.000 description 1
- 235000015281 sodium iodate Nutrition 0.000 description 1
- 229940032753 sodium iodate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/34—Halogenated alcohols
- C07C31/42—Polyhydroxylic acyclic alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
- C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
-
- 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
- C08F8/00—Chemical modification by after-treatment
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Abstract
公开一种制造卤代氟化烯烃单体的方法，该方法包括：(a)使氟化乙烯基单体与乙烯基共聚单体的反应产物的第一聚合物进行脱氢卤化，形成第二聚合物；(b)用氧化剂处理所述第二聚合物，形成由α，ω-二羧酸或其酯衍生物构成的氧化产物；(c)用还原剂处理所述的氧化产物，形成由α，ω-二醇构成的还原产物。较好的第一聚合物具有下式：-[CH2CYZ(CF2CFX)n]m-，其中，X和Y为F、Cl或Br；X和Y可以相同或不同；Z为H、F、Cl、Br、含约1-10个碳原子的烷基或全氟烷基；n为大于1的整数；m是约2-105的整数。或者，α，ω-二羧酸和α，ω-二醇还可衍生为三元醇、四元醇或其它多元醇，它们可直接用作缩合单体或转化为丙烯酸酯，在自由基光引发剂存在下光固化为透明聚合物，这种聚合物可用作光波导材料。
Description
发明领域
本发明涉及卤代氟化单体；具体而言涉及制造卤代氟化单体的方法。
现有技术领域描述
通过光固化市售含C、H、O和N原子的多官能丙烯酸酯，制造光波导结构已为人们了解。然而，这种结构由于其C-H键固有的吸附，在近红外区的光损耗很高。用C-F键取代C-H可降低光损耗，但制得的光聚合物的折射率会变得很低，不符合要求。解决这一问题的一种方法一直是用较重卤原子如氯和溴(已知这两种原子都能提高折射率)部分取代氟化亚烷基部分的氟原子。
许多情况下，以前制造卤素取代的氟化丙烯酸酯的方法是非常麻烦的。因需要提供一种改进的方法，制造用于相关应用的改性氟化单体，这种单体可光固化，形成具有低的光损耗和提高了的粘合力的光波导结构。此外，要求如果这样的改性氟化单体具有接近传统光纤的折射率值，也是符合要求的。
发明概述
本发明提供了一种制造卤代氟化多官能单体的方法，该方法包括下列步骤：(a)使氟化乙烯基单体与乙烯基共聚单体的反应产物的第一聚合物发生脱氢卤化，形成第二聚合物；(b)用氧化剂处理第二聚合物，形成由α，ω-二羧酸或其酯衍生物构成的氧化产物；(c)用还原剂处理所述的氧化产物，形成由α，ω-二醇构成的还原产物。较好的，该第一聚合物结构如下：-[CH2CYZ(CF2CFX)n]m-，其中，X和Y为F、Cl或Br；X和Y可以相同或不同；Z为H、F、Cl、Br、或含约1-10个碳原子的烷基或全氟烷基；n为大于1的整数；m是约2-105的整数。中间体α，ω-二羧酸或其酯衍生物和α，ω-二醇化合物可直接用作聚合单体，或它们可进一步合成为三元、四元和其它多元醇，它们也可以用作聚合单体。或者，这些多元醇还可以进一步衍生为丙烯酸酯，这类丙烯酸酯可光固化，形成可用作光波导材料的透明聚合物。
本文中揭示和要求的方法为经济有利，并能有效实施。而且，根据本发明方法制得的新颖的卤代氟化单体与现有技术的卤代氟化单体相比，具有优良的光波导特性。
较好实施方案的描述
由下面的步骤代表制造本发明的卤代氟化多官能单体的方法：
1.脱氢卤化
2.氧化
3.还原
4.衍生化
5.丙烯酰化
合适的原料是有-[CH2CYZ(CF2CFX)n]m-结构的聚合物，其中，X和Y为F、Cl或Br；X和Y可以相同或不同；Z为H、F、Cl、Br、或含约1-10个碳原子的烷基或全氟烷基；n为大于1的整数，较好约为2-50，约2-10最好；m是2-约105的整数，最是约10-104。这种聚合物的平均分子量约为500-1×106，较好的约为1000-1×105。共聚氟化乙烯基单体CF2＝CFX和另一种含至少两个氢原子的乙烯基共聚单体CH2＝CYZ可获得这些聚合物，其中，X、Y、Z按照前面定义。合适的氟化乙烯基单体包括四氟乙烯、氯三氟乙烯和溴三氟乙烯。合适的乙烯基共聚单体包括偏二氟乙烯、氟乙烯、氯乙烯、偏二氯乙烯、溴乙烯和1-氯-1-氟乙烯。最合适的聚合物是氯三氟乙烯(CF2＝CFCl)与偏二氟乙烯(CH2＝CF2)的共聚物，可以ACLAR_树脂从AlliedSignal Inc.购得。
单体CF2＝CFX的序列长度决定了最终产物的大小。由于大多数共聚物-[CH2CYZ(CF2CFX)n]m-是通过自由基法制得，CF2＝CFX的序列长度通常并不是一个确定数，而是在一定数值周围的分布。因此，由本发明获得的单体物质是包含在一定数值周围的n分布的结构类似物的混合物。
本发明中，制造卤代氟化多官能单体的方法的第一步是原料的脱氢卤化。如本文所用的，可以用加热或化学方法引发脱氢卤化过程。可以在约100-500℃，在常压或真空下，使用催化剂或不用催化剂，进行加热引发的脱氢卤化。热脱氢卤化宜在约300-450℃，约10-50乇真空下进行。如果使用催化剂，催化剂一般约为聚合物量的1-20％，催化剂包括多价金属的无机盐或氧化物。较好的催化剂包括硫酸铜、氯化铜、硫酸钡、硫酸镁、硫酸锰、氧化钡、氧化铜、氧化镁、氧化锰、氧化锌和氧化矾。热脱氢卤化过程可在溶液、悬浮液中进行，更好是以本体进行。
或者，用化学方法引发脱氢卤化，如果这样，需要一种碱化合物。合适的碱化合物可以是有机化物或无机化物，包括伯、仲和叔胺；金属氢氧化物和碱金属烷氧化物。较好的碱化合物包括三烷基胺、氢氧化钠、氢氧化钾、叔丁醇钠或叔丁醇钾和甲醇钠或甲醇钾。化学脱氢卤化过程可在溶液、悬浮液中或本体进行。
如本领域所知，在有机化学中，脱氢卤化是一种标准方法。具体而言，含氯三氟乙烯和偏二氟乙烯单体单元的氟弹性体中的脱氢卤化法是已知的，例如可参阅Paciorek等，Jour.Polymer Science，45：405-413(1960)。本发明的一个特有特征是在脱氢卤化过程中形成HX和HY(X和Y都是卤素)，产生有下式的不饱和聚合物，-[CA＝CEU(CF2CFX)oVCG＝CM]m-。这种聚合物实际是下列结构的混合物：
-[CH＝CZ(CF2CFX)nCH＝CZ]m-，
-[CH＝CZ(CF2CFX)n-1CF2CF＝CH]m-，
-[CF＝CHCYZ(CF2CFX)n-1CF2CF＝CF]m-，和
-[CF＝CHCYZ(CF2CFX)nCH＝CZ]m-，
其中，X和Y为为F、Cl或Br；X和Y可以相同或不同；Z为H、F、Cl、Br、或含约1-10个碳原子的烷基或全氟烷基；n为大于1的整数，较好约为2-50，约2-10最好；m是2-约105的整数，最好是约10-104；A和G为H或F；A和G可以相同或不同；E和M为H或Z，E和M可以相同或不同；o为n或n-1；U为CYZ或没有；V为CF2或没有。该混合物中四种组分的分布取决于消除HX和HY的相对难易。
之后，在脱氢卤化步骤中形成的双键被氧化为α，ω-二羧酸和其酯衍生物。碳-碳双键氧化，尤其是部分氟化的双键的氧化在化学领域是已知的；例如可参阅Hudilcky等，Chemistry of Organic Fluorine Compounds II，p.321，AmericanChem.Soc.，Washington，DC，1995。合适的氧化剂包括氧、臭氧、过硫酸钠或过硫酸钾、高锰酸钠或高锰酸钾、四氧化钌、次氯酸钠或次氯酸钾、氯酸钠或氯酸钾、碘酸钠或碘酸钾、高锰酸四烷基铵、重铬酸钠或重铬酸钾和氧化铬。较好的氧化剂包括臭氧、过硫酸钠或过硫酸钾、高锰酸钠或高锰酸钾、高锰酸四烷基铵、次氯酸钠或次氯酸钾、重铬酸钠或重铬酸钾。氧化反应可以在室温至约300℃的温度范围，在溶液、悬浮液或本体中进行。较好的氧化条件是在约150℃的溶液反应。根据氧化条件，氧化产物可以是α，ω-二羧酸或其酯衍生物。因此，可由下式代表氧化产物：RO2CU(CF2CFX)oVCO2R，氧化产物包括下列化合物的混合物：RO2C(CF2CFX)nCO2R；RO2CCYZ(CF2CFX)nCO2R；RO2C(CF2CFX)n-1CF2CO2R和RO2CCYZ(CF2CFX)n-1CF2CO2R；其中，R为H或含约1-10个碳原子的烷基，U、V、X、Y、Z、n和o按照前面定义。α，ω-二羧酸或其酯衍生物本身是聚合单体，可用于制造特定的聚酯、聚酰胺和其它聚合物。
前面描述的制造α，ω-二羧酸或其酯衍生物的方法远没有现有技术方法繁复，例如在美国专利08/842,783中描述了现有技术的方法，该专利所揭示的内容在此引用作为参考。现有技术中制备有卤代氟化骨架的α，ω-二羧酸或其酯衍生物的方法一般有下列步骤：
1.调聚反应
2.水解
其中，X为Cl或Br；n为1-10；Y为H、F、Cl、CF3或CH3。采用现有技术方法制得的卤代氟化α，ω-二羧酸或其酯衍生物一般可采用本领域已知的方法，被衍生为多醇，最终成为丙烯酸酯。
而本发明中，有卤代氟化亚烷基骨架的α，ω-二羧酸或其酯衍生物还可以采用本领域技术人员已知的常规有机方法，还原为α，ω-二醇。由此形成的α，ω-二醇可由下式表示：HOCH2U(CF2CYZ)oVCH2OH，其中，U、V、Y、Z、n和o按照前面定义。合适的还原剂包括硼烷、9-硼杂二环[3.3.1]壬烷(9-BBN)、氢硼化锂或氢硼化钠、氢化锂铝、氢化二烷基铝、氢化铝、氢化锂和氢硼化烷基锂。较好的还原剂是氢化铝、氢硼化钠或硼烷。对α，ω-二羧酸酯，RO2CU(CF2CFX)oVCO2R，最好的还原剂是氢化铝；可参阅美国专利08/842,783，该专利所揭示的内容在此引用作为参考。
有卤代氟化亚烷基链的α，ω-二醇本身可以是聚合单体，可用于制造特定的聚酯、聚碳酸酯和其它聚合物。
有卤代氟化亚烷基骨架的α，ω-二醇可以进一步衍生为三元醇、四元醇或其它多官能醇，它们可以直接用作缩合单体。这样的转化为本领域已知；可参阅Turri等，Jour.Polymer Science：Part A：Polymer Chemistry，34：3263(1963)。
或者，采用已知的方法，所述二醇、三元醇和四元醇还可以衍生为相应的二、三和四丙烯酸酯。这些二、三和四丙烯酸酯可由下式表示：
CH2＝CWC(O)OCH2U(CF2CFX)oVCH2OC(O)CW＝CH2；
其中，U、V、X、Y、Z、n和o按照前面定义，W为H、F、Cl、CH3或CF3。由此形成的二、三和四丙烯酸酯可以在自由基光引发剂存在下热聚合或光固化，形成可用作光波导材料的透明聚合物。
由下面的实施例更好地理解本发明。用于说明本发明的原理和实施的具体方法、条件、材料、比例和报道的数据为示例，不构成对本发明范围的限制。
实施例1
将30份ACLAR_420树脂(从AlliedSignal Inc.购得)悬浮在包括300份异丙醇和20份氢氧化钾的溶液中，用氢氧化钾作碱进行化学引发的脱氢卤化。ACLAR_420是氯三氟乙烯(CTFE)和偏二氟乙烯(VF2)的共聚物，该聚合物中含15摩尔％的VF2，其分子量为1×104。回流6-8小时后，将该混合物倒入500份水中，并用200份乙醚萃取三次，除去乙醚层(乙醚后处理)。产物进行分析，红外分析表明在3350-2800波数(cm-1)由于C-H键(C-H)有一个强峰，在1650-1580波数(cm-1)由于C＝C键(C＝C)有一个强峰，在1200-1050波数(cm-1)由于C-F键(C-F)有一个很强峰。以CF3COOH作为标准的19F NMR分析出的[δ]在30-50ppm有一个宽峰，这证实该化合物中存在CF2和CF。元素分析表明该化合物包括：C＝30.10％；Cl＝16.60％和F＝44.59％。
实施例2
通过将20份上述产物溶解在300份丙酮中，用冰浴将制得的溶液冷却至1-5℃进行实施例1的化学脱氢卤化产物的氧化。之后，加入约18份高锰酸钾，直到获得紫色，溶液再搅拌1小时，加入50份水，在溶液中鼓泡二氧化硫气体，直到获得透明颜色。除去丙酮，获得17份最终产物，该产物包括淡黄色液体。最终产物的特征如下：IR(膜，cm-1)＝3500-2800(很强，OH)，1770-1730(很强，C＝O)，1210-1100(很强，C-F)；19F NMR[δ(CF3COOH作为标准)ppm]＝30-50(宽峰，CF2和CF)；元素分析(％)：C＝28.52；Cl＝17.20；F＝41.12；平均分子量(按蒸气压渗透压测定法测定“VPO”)＝617。
实施例3
用三乙胺作为碱进行化学引发的脱氢卤化。室温下，将在20份二甲基甲酰胺中的10份ACLAR_420树脂(分子量为3×105)加到8份三乙胺中。该混合物加热到60℃达2小时，然后倒入500份水中。沉淀物用水和甲醇清洗，制得9份脱氢卤化的聚合物。
实施例4
通过将10份实施例3的聚合物悬浮在200份丙酮中，并冷却至1-5℃，氧化实施例3的脱氢卤化聚合物。之后，加入约9份高锰酸钾，直到获得紫色，溶液再搅拌1小时，加入50份水，在溶液中鼓泡二氧化硫气体，使褪色。除去丙酮，获得10.6份淡黄色液体的产物，该产物的IR和19-NMR特性与实施例2相似。平均分子量(VPO)＝651。
实施例5
用硫酸铜作为催化剂，搅拌下，在20乇真空和350-400℃下加热28份ACLAR_420树脂和1份硫酸铜，进行热引发的脱氢卤化。蒸馏液的特性如下：
IR(膜，cm-1)＝1790(强，-CF＝CF-)，1360(强)，1320(强)，1200-1100(很强，C-F)，970(强)，900(强)；19F NMR[δ(CF3COOH为标准)ppm]＝29-36(宽)，37.5-40(宽)，43.0(宽)。
实施例6
采用实施例2描述的步骤，将13.5份实施例5的脱氢卤化产物氧化为液体二酸。产物的特性如下：
IR(膜，cm-1)＝2700-3250(强，O-H)，1750-1780(强，C＝O)，1120-1180(很强，C-F)，960(强)；19F NMR[δ(CF3COOH为标准)ppm]：29-34(宽)，35-37(宽)，39(中等)；1H NMR[δ，ppm]：8.5(强，COOH)；元素分析(％)：C：27.11；Cl：120.63；F：45.45；平均分子量(VPO)＝651。
实施例7
用硫酸铜作为催化剂，在20乇真空，加热至350-400℃，搅拌30份ACLAR_3000树脂和1.5份硫酸铜，进行ACLAR_3000树脂的热引发脱氢卤化。ACLAR_3000树脂是氯三氟乙烯(CTFE)和偏二氟乙烯(VF2)的共聚物，该聚合物中含3.5摩尔％的VF2，具有高分子量级别。蒸馏液的特性如下：
IR(膜，cm-1)＝1770(强，-CF＝CF-)，1370(强)，1300(强)，1200-1100(很强，C-F)，970(强)；19F NMR[δ(CF3COOH为标准)ppm]＝10.0(中等，ClCF2)，12.0(高，-CF＝CF-)，30(中等，CF2)，38.5(中等，CF2＝)，50(中等，CF2)。
实施例8
采用实施例2描述的步骤，将15份实施例7的脱氢卤化产物氧化为液体二酸。获得7.1份液体产物。产物的特性如下：
IR(膜，cm-1)＝2700-3250(强，O-H)，1750-1780(强，C-O)，1120-1180(很强，C-F)，960(强)；19F NMR[δ(CF3COOH为标准)ppm]：10.5(中等，ClCF2)，30.0(中等，CF2)，30.0(中等，CF2)，49.5(中等，CF2)；元素分析(％)：C＝24.38；Cl＝23.38；F＝42.21；平均分子量(VPO)＝610。
实施例9
将在100份干甲醇中含44份从实施例2获得的二酸和1份浓硫酸的混合物回流8小时，酯化实施例2的二酸。将该混合物倒入300份水中，并用30份乙醚萃取三次。除去乙醚，获得41份粗二酯。硅胶柱色谱提纯(Merck#60)后，收集到33份二酯。由GC-MS、1H NMR和GC用标准样品对该产物进行分析，为CH3OC(O)(CF2CFCl)nCF2CO2CH3(n＝3，4，5，6)和CH3OC(O)CF2(CF2CFCl)mCF2CO2CH3(m＝2，3，4，5，6)的混合物。
实施例10
于0℃搅拌下，向200份在四氢呋喃的0.91M AlH3中，缓慢加入在50份四氢呋喃中的16.5份实施例9中获得的二酯混合物，使其还原为二醇。1小时后，用10分1∶1的四氢呋喃和水的混合物小心水解过量的氢化物，进行醚后处理和蒸馏，获得14份二醇混合物。该产物的特性与指出的结构一致。
实施例11
混合80份实施例10中所述的二醇混合物与55份三乙胺和100份二氯甲烷，并冷却到0℃，使二醇衍生为丙烯酸酯。在氮气氛下，在该溶液中缓慢加入在100份二氯甲烷中的55份新蒸馏的烯丙酰氯，同时搅拌。再继续搅拌24小时，温度回到室温，用水处理，并用乙醚后处理。通过硅胶柱色谱(Merck#60)，用石油醚和乙酸乙酯混合物(50∶1)洗脱，提纯获得的粗产物。提纯后的二丙烯酸酯混合物的特性与指出的结构一致。
实施例12
混合32.2份实施例10中所述的二醇混合物与35.4份烯丙酰氯和0.1份4-甲氧基苯酚使二醇衍生为二丙烯酸酯。在90℃(油浴)回流8小时。真空蒸馏回收过量的烯丙酰氯，为二丙烯酸酯的残余物用活性碳脱色。在0.1μ的滤器上除去少量聚合物。二丙烯酸酯的产率为90％。特性与指出的结构一致
实施例13
于50℃混合实施例11中的二丙烯酸酯混合物与2.0％(重量)苯并二甲酮(Irgacure 651)为均匀组合物，该组合物经0.2微米的PTFE膜加压过滤，将实施例11的二丙烯酸酯成形为透明薄膜。该组合物被旋转涂布在一石英板上，形成2微米厚的液体层，在氮气中，在中压汞UV灯下辐照5秒，获得坚韧的固体透明薄膜。
已详细地描述了本发明，应理解这些细节不构成限制，本领域的技术人员在权利要求书限定的本发明范围之内，可进一步变动和修改。
Claims (19)
1.一种制造卤代氟化多官能单体的方法，该方法包括下列步骤：
(a)使氟化乙烯基单体与乙烯基共聚单体的反应产物的第一聚合物进行脱氢卤化，形成第二聚合物；
(b)用氧化剂处理所述第二聚合物，形成由α，ω-二羧酸或其酯衍生物构成的氧化产物；
(c)用还原剂处理所述的氧化产物，形成由α，ω-二醇构成的还原产物；
(d)将所述还原产物转化为丙烯酸酯。
2.如权利要求1所述的方法，其特征在于所述第一聚合物由-[CH2CYZ(CF2CFX)n]m-表示，式中，X和Y为F、Cl或Br；X和Y可以相同或不同；Z为H、F、Cl、Br、含1-10个碳原子的烷基或全氟烷基；n为大于1的整数；m是2-105的整数。
3.如权利要求1所述的方法，其特征在于所述还原产物还可以衍生为三元醇、四元醇或其它多元醇。
4.如权利要求3所述的方法，其特征在于所述三元醇、四元醇或其它多元醇可转化为丙烯酸酯。
5.如权利要求1所述的方法，其特征在于所述第一聚合物的平均分子量为500-1×106。
6.如权利要求1所述的方法，其特征在于所述第一聚合物的平均分子量为1000-1×105。
7.如权利要求1所述的方法，其特征在于所述第一聚合物具有如下结构：-[CH2CYZ(CF2CFX)n]m-，其中，X和Y为F、Cl或Br；X和Y可以相同或不同；Z为H、F、Cl、Br、含1-10个碳原子的烷基或全氟烷基；n为大于1的整数；m是2-105的整数。
8.如权利要求7所述的方法，其特征在于对所述第一聚合物，n为2-50。
9.如权利要求7所述的方法，其特征在于对所述第一聚合物，n为2-10。
10.如权利要求7所述的方法，其特征在于对所述第一聚合物，m为2-105。
11.如权利要求7所述的方法，其特征在于对所述第一聚合物，m为10-104。
12.如权利要求1所述的方法，其特征在于通过共聚有式CF2＝CFX的氟化乙烯基单体和有式CH2＝CYZ的乙烯基共聚单体可获得所述第一聚合物，其中，X和Y为F、Cl或Br；X和Y可以相同或不同；Z为H、F、Cl、Br、含1-10个碳原子的烷基或全氟烷基。
13.如权利要求1所述的方法，其特征在于所述第一聚合物可通过共聚氯三氟乙烯和偏二氟乙烯制得。
14.如权利要求1所述的方法，其特征在于所述脱氢卤化是采用包括加热或碱的方法来引发。
15.如权利要求1所述的方法，其特征在于所述第二聚合物具有下式：-[CA＝CEU(CF2CFX)oVCG＝CM]m-，其中，X和Y为为F、Cl或Br；X和Y可以相同或不同；Z为H、F、Cl、Br、或含1-10个碳原子的烷基或全氟烷基；n为大于1的整数；m是2-105的整数；A和G为H或F，A和G可以相同或不同；E和M为H或Z，E和M可以相同或不同；o为n或n-1；U为CYZ或没有；V为CF2或没有。
16.如权利要求1所述的方法，其特征在于所述氧化剂是高锰酸钾。
17.如权利要求1所述的方法，其特征在于所述氧化产物具有下式：RO2CU(CF2CFX)oVCO2R，其中，R为H或含1-10个碳原子的烷基化合物；X和Y为F、Cl或Br，X和Y可以相同或不同；Z为H、F、Cl、Br或有1-10个碳原子的烷基或全氟烷基；U为CYZ或没有；V为CF2或没有；n为大于1的整数；m是2-105的整数；o为n或n-1。
18.如权利要求1所述的方法，其特征在于所述还原产物具有下式：HOCH2U(CF2CYZ)oVCH20H，Y为F、Cl或Br；Z为H、F、Cl、Br或有1-10个碳原子的烷基或全氟烷基；U为CYZ或没有；V为CF2或没有；n为大于1的整数；m是2-105的整数；o为n或n-1。
19.如权利要求1所述的方法，其特征在于所述还原剂是氢化铝。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/190,194 US6166156A (en) | 1998-11-12 | 1998-11-12 | Method for making photocurable halofluorinated acrylates |
| US09/190,194 | 1998-11-12 |
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| Publication Number | Publication Date |
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| CN1335829A CN1335829A (zh) | 2002-02-13 |
| CN1219741C true CN1219741C (zh) | 2005-09-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB998128317A Expired - Fee Related CN1219741C (zh) | 1998-11-12 | 1999-11-09 | 制造光可固化的卤代氟化丙烯酸酯的新颖方法 |
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| Country | Link |
|---|---|
| US (1) | US6166156A (zh) |
| EP (2) | EP1129058B1 (zh) |
| JP (1) | JP2002529548A (zh) |
| CN (1) | CN1219741C (zh) |
| AU (1) | AU1911500A (zh) |
| CA (1) | CA2350539A1 (zh) |
| DE (1) | DE69919017D1 (zh) |
| WO (1) | WO2000027782A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105315126B (zh) * | 2015-08-18 | 2018-01-23 | 巨化集团技术中心 | 一种2,3,3,3‑四氟丙烯制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6555288B1 (en) * | 1999-06-21 | 2003-04-29 | Corning Incorporated | Optical devices made from radiation curable fluorinated compositions |
| US6654188B2 (en) * | 2001-12-12 | 2003-11-25 | Lightspan, Llc | Compositions and devices for thermo optically controlled switching and filtering |
| JP4222120B2 (ja) * | 2002-10-07 | 2009-02-12 | Ｊｓｒ株式会社 | 光導波路形成用感光性樹脂組成物および光導波路 |
| WO2004092105A1 (en) * | 2003-04-16 | 2004-10-28 | Hwan-Kyu Kim | Novel uv-curable perfluorinated, multifunctionalized acrylates monomers, copolyacrylates and their synthetic methods for photonic devices |
| US8691915B2 (en) | 2012-04-23 | 2014-04-08 | Sabic Innovative Plastics Ip B.V. | Copolymers and polymer blends having improved refractive indices |
| FR3069544B1 (fr) * | 2017-07-28 | 2020-05-15 | Arkema France | Procede de preparation d'un film de polymere fluore reticule |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2806866A (en) * | 1957-09-17 | Hoocxcfcix | ||
| US2806865A (en) * | 1954-08-27 | 1957-09-17 | Kellogg M W Co | New fluorine-containing compounds and method of preparation thereof |
| FR1190705A (fr) * | 1957-12-11 | 1959-10-14 | Minnesota Mining & Mfg | Polychlorofluoro alcools |
| US3147314A (en) * | 1960-02-29 | 1964-09-01 | Du Pont | Carboxy terminated copolymers of vinylidene fluoride-hexafluoropropene |
| US4122288A (en) * | 1977-11-16 | 1978-10-24 | Uop Inc. | Hydrolysis of alkyl substituted dihalobenzene compounds |
| US4356296A (en) * | 1981-02-25 | 1982-10-26 | The United States Of America As Represented By The Secretary Of The Navy | Fluorinated diacrylic esters and polymers therefrom |
| JPS59117503A (ja) * | 1982-12-24 | 1984-07-06 | Kureha Chem Ind Co Ltd | 新規な含フツ素単量体の製造法 |
| DE3570931D1 (en) * | 1984-08-10 | 1989-07-13 | Siemens Ag | Thermostable polymer system, cross-linkable by irradiation, for microelectronic use |
| IT1212111B (it) * | 1985-03-06 | 1989-11-08 | Montefluos Spa | Procedimento per preparare fluoroelastomeri insaturi. |
| US5238974A (en) * | 1986-08-06 | 1993-08-24 | Mitsubishi Rayon Company Ltd. | Plastic cladding composition for silica or glass core optical fiber, and silica or glass core optical fiber prepared therefrom |
| US4820588A (en) * | 1986-08-29 | 1989-04-11 | Minnesota Mining And Manufacturing Company | Shaped articles of polyfluoropolyethers having pendant perfluoroalkoxy groups |
| US5024507A (en) * | 1990-05-10 | 1991-06-18 | Polaroid Corporation | Photopolymerizable composition for cladding optical fibers |
| AU650559B2 (en) * | 1991-08-23 | 1994-06-23 | Toray Industries, Inc. | Curable fluorinated acrylate composition |
| JPH06279537A (ja) * | 1993-03-29 | 1994-10-04 | Japan Synthetic Rubber Co Ltd | カルボキシル基含有フッ素重合体の製造方法 |
| US5733981A (en) * | 1996-08-26 | 1998-03-31 | Minnesota Mining And Manufacturing Company | Aqueous dehydrofluorination method |
| KR100697473B1 (ko) * | 1996-09-18 | 2007-03-21 | 익스플루오르 리서치 코포레이션 | 퍼플루오로카본 치환된 메탄올의 제조 방법 |
| JPH10158376A (ja) * | 1996-11-27 | 1998-06-16 | Asahi Glass Co Ltd | 含フッ素ポリエステル |
| US6323361B1 (en) * | 1997-04-17 | 2001-11-27 | Corning Inc. | Photocurable halofluorinated acrylates |
-
1998
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- 1999-11-09 EP EP04077165A patent/EP1475362A1/en not_active Withdrawn
- 1999-11-09 CN CNB998128317A patent/CN1219741C/zh not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105315126B (zh) * | 2015-08-18 | 2018-01-23 | 巨化集团技术中心 | 一种2,3,3,3‑四氟丙烯制备方法 |
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| Publication number | Publication date |
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| WO2000027782A1 (en) | 2000-05-18 |
| DE69919017D1 (de) | 2004-09-02 |
| EP1129058B1 (en) | 2004-07-28 |
| US6166156A (en) | 2000-12-26 |
| AU1911500A (en) | 2000-05-29 |
| CA2350539A1 (en) | 2000-05-18 |
| CN1335829A (zh) | 2002-02-13 |
| EP1475362A1 (en) | 2004-11-10 |
| EP1129058A1 (en) | 2001-09-05 |
| JP2002529548A (ja) | 2002-09-10 |
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