CN1006891B - 制备可硫化氟弹性体的方法及其产品 - Google Patents
制备可硫化氟弹性体的方法及其产品Info
- Publication number
- CN1006891B CN1006891B CN86104545A CN86104545A CN1006891B CN 1006891 B CN1006891 B CN 1006891B CN 86104545 A CN86104545 A CN 86104545A CN 86104545 A CN86104545 A CN 86104545A CN 1006891 B CN1006891 B CN 1006891B
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- mole
- bromine
- vinyl ether
- ether
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Links
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title description 3
- -1 Perfluoro divinyl ether Chemical compound 0.000 claims abstract description 17
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 229920001973 fluoroelastomer Polymers 0.000 claims description 23
- 125000001246 bromo group Chemical group Br* 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 7
- 125000001118 alkylidene group Chemical group 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- ATDGTVJJHBUTRL-UHFFFAOYSA-N cyanogen bromide Chemical compound BrC#N ATDGTVJJHBUTRL-UHFFFAOYSA-N 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 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
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- JMGNVALALWCTLC-UHFFFAOYSA-N 1-fluoro-2-(2-fluoroethenoxy)ethene Chemical compound FC=COC=CF JMGNVALALWCTLC-UHFFFAOYSA-N 0.000 claims 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims 3
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 15
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- 229920002449 FKM Polymers 0.000 abstract 2
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 abstract 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 239000003505 polymerization initiator Substances 0.000 abstract 1
- 229960000834 vinyl ether Drugs 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- 229920002313 fluoropolymer Polymers 0.000 description 6
- 239000004811 fluoropolymer Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000003856 thermoforming Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PITQFWWNUHMYIC-UHFFFAOYSA-N 1-tert-butyl-4-(4-tert-butylcyclohexyl)peroxycyclohexane Chemical compound C1CC(C(C)(C)C)CCC1OOC1CCC(C(C)(C)C)CC1 PITQFWWNUHMYIC-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-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
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- ULWDYECGHQQXMV-UHFFFAOYSA-N 3-ethyl-3-(3-ethyloctan-3-ylperoxy)octane Chemical compound C(C)C(CCCCC)(CC)OOC(CCCCC)(CC)CC ULWDYECGHQQXMV-UHFFFAOYSA-N 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
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 101001128819 Tityus serrulatus Bradykinin-potentiating peptide T Proteins 0.000 description 1
- BCERDJSSIBQDCD-UHFFFAOYSA-L [Fe+2].[O-]S(=O)(=O)OOS([O-])(=O)=O Chemical compound [Fe+2].[O-]S(=O)(=O)OOS([O-])(=O)=O BCERDJSSIBQDCD-UHFFFAOYSA-L 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 238000000926 separation method Methods 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000006337 tetrafluoro ethyl group Chemical group 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 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
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F214/222—Vinylidene fluoride with fluorinated vinyl ethers
Abstract
制造可硫化氟弹性体的方法包括:35~80摩尔%1,1-二氟乙烯,15~35摩尔%六氟丙烯,0~30摩尔%从氟链烯烃和/或全氟乙烯醚中选择的另一共聚单体,和0.01-1摩尔%具如下通式的乙烯基醚反应:
CF2Br~(Rf)n-O~CF=CF2
在氟弹性中存在已知的聚合引发剂和少量的链转移剂,这链转移剂有如下化学通式:R-(CF2Br)m。
式中n为1或0,m为1或2。
Description
本发明是关于一种制造可硫化氟弹性体的方法及其产品。
氟弹性体,特别是以1,1-二氟乙烯、六氟丙烯和其它单体,如乙烯基氟化物,四氟乙烯等为基础的含氟聚合物,可用于不同的领域,这是由于它们有很好的耐化学品和耐热性能,和具特征性的耐气候性及对光线的最佳稳定性。
这些产品可分成两类。第一类是属于高分子量的聚合物,另一类属于中至低分子量的聚合物。
属于第一类的产品主要是用于制备浇注的片材,制造用于金属表面贴合的材料或一般用于模压加工。
属于第二类的产品很适用于热成形加工,如注压或挤压加工。
已清楚地知道分子量分布是决定于聚合过程及有关的反应条件,例如,以上描述的单体聚合作用若在水基乳状液中并含有水溶性引发剂,温度范围为40-150℃,一般规律是生成一种高分子量含氟聚合物,其分子量分布不适用于热成形加工。
对于减低水基乳液聚合的含氟聚合物分子量,已提出了若干方法,其中包括了采用较高反应温度或是自由基引发剂的用量大于其准确需用量。
这些体系证明不很有效,这是由于调节分子量分布很困难,并且发生削弱成品热稳定性的副作用。
由于以上的理由,可调节和保持含氟聚合物分子量为中-低值的唯
一有效方法是在反应步骤中用适当的链转移剂。
在此情况下也不得不面对一些缺点,因为其中有一些产物使反应动力学减缓而趋向于抑制聚合反应。其它一些产物只在特别的过程如高压过程中有效,还有一些趋向是阻碍与1,1-二氟乙烯的聚合作用。
最后又提出以溴或碘为基础的链长调节剂,它能成功地容许分子量调节而不至于引起以上提及的缺点。
然而应认识到这样的重要性,特别在氟弹性体方面,热成形不是唯一要面对的问题,因为这些产品还应具有高级特性和化学-物理性质,这对其最终目的用途也是很重要的。
实际上,经过过氧化物过程硫化的氟弹性体在技术文献中是已知的,因为这些材料具有很优热稳定性和在高温的耐化学品特性,它们已在工业界广泛使用。
鉴于以上特性,它们是用于特别的用途中,首要的是与高化学侵蚀性和苛刻的温度条件下的有机和无机流体接触。
应用例子如用于特别液体的泵的膜片,象用于内燃机油泵的膜片,阀座,止回阀,软管,垫片,以及特别的垫片如油垫片等。
在所有这些方面氟弹性体受到重视,是因为它们的化学特性和耐热特性,并能应用易行的工艺,如挤压方法加工,并可制造简单或复杂外形和轮廓的物件。
除此之外,这些产品要能用于工业用途所必须具备的机械特性,最主要是抗拉强度,模量及极限伸长率等项。
因此氟弹性体是必须具有耐化学品及耐热性能、机械强度和机加工特性和/或有尽量高的可加工能性。
申请人现已发现一种方法,该方法使氟弹性体易于加工并且在其已硫化状态能达到很优机械性质和耐热、耐化学品特性。
本发明用于制造可硫化氟弹性体的方法包括:由35-80摩尔%的1,
1-二氟乙烯、15-35摩尔%的六氟丙烯、0-30摩尔%的另一选自氟链烯烃和/或全氟乙烯基醚的共聚单体和0.01-1摩尔%如下式的溴化氟乙烯基醚进行反应:
CF2Br-(Rf)n-O-CF=CF2(1)
式中Rf为含有1至9个碳原子的氟化亚烷基,n为1或0,在进行反应时存在有用于氟弹性体的聚合引发剂和一种如下式的链转移剂:
R-(CF2Br)m
式中m为1或2,当m是1,R可以是溴或含有一个与仲碳原子结合的溴原子的具有2至4个碳原子的全氟烷基;当m是2,R是含有一个与仲碳原子结合的溴原子的具有不超过4个碳原子的亚烷基。
按各组分总量计,通式(2)的链转移到剂用量范围为0.001-1摩尔%。
通式(2)的链转移剂在本发明的实施方案中最好是用CF2Br2。
通式(2)的溴化链转移剂,与其它已知的溴化链转移剂比较,可使其在聚合反应中发生分支的可能性减至最低程度。
事实上,申请人已在实验中发现,不同的含溴的氟化化合物利用作为链转移剂在制备氟弹性体中有不同的表现。特别是,申请人发现所有包括至少有2个溴原子与单一个伯碳原子结合,或至少有一个溴原子与仲碳原子或叔碳原子结合的氟化化合物,都是活泼的链转移剂。相反地,只有如-CF2Br基的含氟化合物有溴,其活性大大降低。
为了说明的目的,申请人利用以下的链转移剂进行单体的聚合反应:
CF2Br2、CF3-CFBr2、CBr4、CF3-CFBr-CF2Br和CF2Br-CF2Br;
同时发现,使用CF2Br、CF3-CFBr2、CBr4、CF3-CFBr-CF2Br比使用CF2Br-CF2Br,或不使用任何链转移剂时,门尼粘度大大减低。CF3-CFBr2和CBr4链转移剂
导致所制氟弹性体的聚合物链含有溴原子,它又引起进一步的分支作用。当使用诸如CF2=CFBr之类的共聚单体时,亦可使聚合物链上存在有溴原子。在此情况下,在聚合过程中亦发生分支作用:事实上,应用Varian XL-200分光仪用19F于188.22兆赫进行N.M.R.分析表明,-CF2CF2-Br和-CH2-CF2-Br基团的存在量与引用的该共聚单体中所含的量不相上下。存在的这些基团清楚地指出在聚合反应中,大量的溴用于链转移,接着发生分支作用。
从共聚单体CF2=CF-Br得到的氟弹性体在溶剂中的可溶性很差,这证实了上面的说法。
依照本发明的制造方法,应用1,1-二氟乙烯和六氟丙烯时,可以产生共聚作用的其它共聚单体的量为0-30摩尔%。
以上提及的其他共聚单体可以是含氟链烯烃,如四氟乙烯、氯三氟乙烯、乙烯基氟化物等,和/或全氟乙烯基醚,如全氟甲基乙烯基醚、全氟乙基乙烯基醚、全氟丙基乙烯基醚等。
具通式(1)的溴化氟乙烯基醚是已知技术文献中的产物,这些产物可以从其中的任何方法得到,特别是美国专利4,275,226所披露的方法。
其中以CF2Br-CF2-O-CF=CF2最好。
共聚反应可按已知的技术文献进行。例如在1979,Kirk Othmer的Encyclopaedia of Chemical Technology第8卷,500页中得知。
这共聚作用是在水基乳状液中及有自由基引发剂存在下进行的,而自由基引发剂是选自无机过氧化物,如过硫酸铵和过硫酸钾;氧化还原体系,如过硫酸盐-亚硫酸氢盐,铁-过硫酸盐;有机过氧化物,如过氧化苯甲酰,二枯基过氧化物,双(4-叔丁基环己基)过氧二碳酸酯,
二叔丁基过氧化物,二-异丙基过氧二碳酸酯,二乙基己基过氧二碳酸酯,乙酰环己基-磺酰过氧化物,叔丁基过氧新戊酸酯,2,4-二氯过氧化苯甲酰,异丁基过氧化物,辛酰基过氧化物,氟化过氧化物,氟化过酸酐等。
任何一种已知的含氟乳化剂均可用于本发明的方法中,如氟化的羧酸皂。
该反应是在40°-150℃温度及压力不超过10兆帕条件下进行。
按本发明的可硫化氟弹性体是新颖的,本发明另一目的是可硫化的溴化氟弹性体,其组成如下:
(A)35-80摩尔%来自1,1-二氟乙烯单体的单元;
(B)15-35摩尔%来自六氟丙烯的单元;
(C)0-30摩尔%选自氟链烯烃和/或全氟乙烯基醚单体的单元;
(D)0.01-1摩尔%来自具如下通式的单体的溴化氟乙烯基醚:CF2Br-(Rf)m-O-CF=CF2
式中Rf为含有1至9个碳原子的氟化亚烷基,n为1或0,其中溴是只含在-CF2Br基中和/或少量含在-CH2-Br基中。
本发明的氟弹性体特征是在聚合物链中不含与仲碳原子结合的溴原子。由于没有这样的溴原子,使得在聚合步骤中产生分支聚合物的可能性减至最低,并使氟弹性体能溶解于用于含氟聚合物的已知溶剂,并具有更佳可加工性。
本发明的氟弹性体可以用交联剂硫化,所用交联剂如过氧有机化合物与诸如三烯丙基异氰脲酸酯之类桥联剂配合使用。
硫化步骤的操作条件实质上可采用含氟聚合物和/或氟弹性体常用的条件。如前面提到的Kirk Othmer书中所叙述。
作为过氧有机化合物,可提到的如2,5-二甲基-2,5-二(叔丁基过氧化物)己烷和3-己炔的相应衍生物。
在硫化过程中,可以将用于此类过程的常用添加剂加入该共聚物中,如金属氧化物,如氧化镁和/或氧化铅;金属氢氧化物,如氢氧化钙;其它填充料,如炭黑,染料,抗氧剂,稳定剂等。
本发明已公开的氟弹性体具有最佳的可加工特性,使之特别适用于热成形过程,如压延、注压和挤压过程,也适于制造复杂形状和轮廓的制件。
此外,经硫化的共聚物或制品具有很好的耐化学品及耐热特性,很优的机械性质和最佳的压缩永久变形特性。
下面的实例将更好地说明本发明并描述具体操作方法,但本发明并不限于下面的实例。
实例1
在含有3.5升水的5升压热釜中,在80℃及1.8兆帕压力连续送入气态单体混合物,该混合物含有50%体积的1,1-二氟乙烯,24.8%的六氟丙烯,24.8%的四氟乙烯和0.4%的2-溴四氟乙基全氟乙烯基醚(CF2BrCF2-OCF=CF2)。
作为引发剂,使用的是过硫酸铵(8克);作为链转移剂,使用的是CF2Br2(5.3克);70分钟后,停止聚合作用。将乳状液排出然后用含有5克/升Al2(SO4)3·8H2O的水溶液使之凝结,再分离产品,用清水洗涤,然后于60℃干燥24小时。从而得到1400克有如起始物质单体混合物同样成分的聚合物,门尼粘度1+4,100℃(ASTM D1646)是63,在甲基乙基酮中于30℃的特性粘度是0.45。
将该样品放入圆筒混合机中,用以下硫化配方进行复配:
氟弹性体 重量份数 100
Luperco 101 XL*″ 3
三烯丙基异氰脲酸酯 ″ 3
氧化镁 ″ 5
MT 黑 ″ 30
巴西棕榈蜡 ″ 1
*Lupero是由2,5-二甲基-2,5-二(叔丁基过氧化物)己烷组成
以上的聚合物配制物是用Monsanto流变计,依照ASTM D2705在180℃,arc5,100赫测定的,不用预热,以下是所得的结果:
最小扭矩 14
Ts10 1分36秒
Ts50 3分24秒
最大扭矩(5分钟后) 72
聚合物经在170℃压制硫化10分钟制成O形环和薄板形状,初压力为2.5兆帕,终压力为17.5兆帕,接着在8小时中从100℃渐渐升高温度至250℃,并在250℃进行24小时后硫化。
以下是所得的机械特性:
100%模量*5.3兆帕
极限抗拉强度*17.0兆帕
极限伸长率*21.0%
硬度**72.0肖氏A
压缩永久变形(O型环)***38.0%
*ASTM D 412-80
**ASTM D 1415-8
***ASTM D 395-78
(ASTM:美国材料试验学会标准)
经硫化的样品经过抗化学品试验,在BP Olex(SF油)在150℃经历21天。
结果如下:
100%模量改变 0%
极限抗拉强度改变 -11%
极限伸长率改变 -18%
硬度改变 -1肖氏A
Claims (9)
1、一种制造可硫化氟弹性体的方法,包括用35~80摩尔%的1,1-二氟乙烯、15~35摩尔%的六氟丙烯、0-30摩尔%的选自氟链烯烃和/或全氟乙烯基醚的另一共聚单体和0.01-1摩尔%如下式表示的溴氟烷基氟乙烯基醚进行反应:
式中Rf为含有1至9个碳原子的氟化亚烷基,n为1或0,进行反应时存在有用于氟弹性体的已知聚合引发剂和一种如下式的链转移剂:
式中m为1或2,当m=1,R可以是溴或含有一个与仲碳原子结合的溴原子的具有2至4个碳原子的全氟烷基;当m=2,R为含有一个与仲碳原子结合的溴原子的具有不超过4个碳原子的亚烷基。
2、按照权利要求1所述的方法,其中该溴氟烷基氟乙烯基醚是
3、按照权利要求1和2所述的方法,其中该链转移剂的用量相对于各组分的总摩尔量在0.001-1摩尔%范围。
4、按照权利要求1、2和3所述方法中的任何一项,其中该链转移剂是CF2Br2
5、按照权利要求1、2、3和4所述方法中任一项,其中该氟链烯烃是选自四氟乙烯,氯三氟乙烯和乙烯基氟化物。
6、按照权利要求1、2、3、4和5所述方法中任一项,其中该全氟乙烯基醚是选自全氟甲基乙烯基醚、全氟乙基乙烯基醚,全氟丙基乙烯基醚。
7、一种具如下组成的可硫化的溴化氟弹性体:
(A)35-80摩尔%来自1,1-二氟乙烯的单体单元,
(B)15-35摩尔%来自六氟丙烯的单体单元,
(C)0-30摩尔%选自氟链烯烃和/或全氟乙烯基醚的单体单元,
(D)0.01-1摩尔%来自具下式的溴氟烷基氟乙烯基醚的单体单元:
式中Rf为含有1至9个碳原子氟化亚烷基,n为1或0,其中溴是专门含在-CF2Br基中和少量是含在-CH2Br基中,其特征在于其中不含与聚合物链上仲碳原子相结合的溴原子。
8、按照权利要求7所述的可硫化氟弹性体,其中的氟链烯烃是选自四氟乙烯、氯三氟乙烯和乙烯基氟化物。
9、按照权利要求7和8所述的可硫化氟弹性体,其中的全氟乙烯基醚是选自全氟甲基乙烯基醚、全氟乙基乙烯基醚、全氟丙基乙烯基醚。
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US3069401A (en) * | 1960-02-23 | 1962-12-18 | Du Pont | Copolymers of hexafluoropropylene vinylidene fluoride and aliphatic, chain transfer agents |
NL127087C (zh) * | 1964-10-21 | 1900-01-01 | ||
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US4000356A (en) * | 1972-06-19 | 1976-12-28 | Dynamit Nobel Aktiengesellschaft | Process for the preparation of thermoplastically workable fluoro-olefin polymers |
IT1019846B (it) * | 1974-08-09 | 1977-11-30 | Montedison Spa | Procedimento di preparazione di copolimeri elastomerici del fluoruro di vinilidene ad elevate carat teristiche e copolimeri elastomeri ci cosi ottenuti |
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US4123603A (en) * | 1977-05-31 | 1978-10-31 | E. I. Du Pont De Nemours And Company | Fluoroelastomer composition |
US4275226A (en) * | 1978-08-25 | 1981-06-23 | Asahi Glass Company, Ltd. | Process for producing fluorovinyl ether |
JPS5657811A (en) * | 1979-10-17 | 1981-05-20 | Daikin Ind Ltd | Preparation of liquid fluorine-containing polymer |
US4474700A (en) * | 1981-07-02 | 1984-10-02 | E. I. Du Pont DeNemours and Company | β-Substituted polyfluoropropionate salts and derivatives |
US4564662A (en) * | 1984-02-23 | 1986-01-14 | Minnesota Mining And Manufacturing Company | Fluorocarbon elastomer |
US4524197A (en) * | 1984-08-28 | 1985-06-18 | E. I. Du Pont De Nemours And Company | Process for making vinylidene fluoride containing fluoroelastomers |
US4529759A (en) * | 1984-12-07 | 1985-07-16 | E. I. Du Pont De Nemours And Company | Peroxide-curable brominated or iodinated fluoroelastomer composition containing an N,N,N',N'-tetrasubstituted 1,8-diaminonaphthalene |
-
1985
- 1985-07-08 IT IT21472/85A patent/IT1187684B/it active
-
1986
- 1986-07-07 CA CA000513220A patent/CA1281150C/en not_active Expired - Lifetime
- 1986-07-07 DE DE8686109245T patent/DE3674854D1/de not_active Expired - Lifetime
- 1986-07-07 AU AU59816/86A patent/AU594691B2/en not_active Ceased
- 1986-07-07 ES ES8600165A patent/ES2001014A6/es not_active Expired
- 1986-07-07 US US06/882,724 patent/US4745165A/en not_active Expired - Lifetime
- 1986-07-07 EP EP86109245A patent/EP0211251B1/en not_active Expired
- 1986-07-08 KR KR1019860005483A patent/KR940000016B1/ko not_active IP Right Cessation
- 1986-07-08 CN CN86104545A patent/CN1006891B/zh not_active Expired
- 1986-07-08 JP JP61158906A patent/JPH0745554B2/ja not_active Expired - Lifetime
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EP0211251A2 (en) | 1987-02-25 |
KR940000016B1 (ko) | 1994-01-05 |
AU594691B2 (en) | 1990-03-15 |
EP0211251A3 (en) | 1988-08-31 |
CA1281150C (en) | 1991-03-05 |
DE3674854D1 (de) | 1990-11-15 |
ES2001014A6 (es) | 1988-04-16 |
IT8521472A0 (it) | 1985-07-08 |
AU5981686A (en) | 1987-01-15 |
US4745165A (en) | 1988-05-17 |
JPH0745554B2 (ja) | 1995-05-17 |
EP0211251B1 (en) | 1990-10-10 |
CN86104545A (zh) | 1987-02-04 |
KR870001243A (ko) | 1987-03-12 |
JPS6236407A (ja) | 1987-02-17 |
IT1187684B (it) | 1987-12-23 |
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