CS273783B1 - Polymers of chlorofluoroalkyl)-2-propenoates and method of their preparation - Google Patents
Polymers of chlorofluoroalkyl)-2-propenoates and method of their preparation Download PDFInfo
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- propenoates
- chlorofluoroalkyl
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- 229920000642 polymer Polymers 0.000 title claims abstract description 15
- -1 chlorotetrafluoroethyl Chemical group 0.000 claims abstract description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 229920001519 homopolymer Polymers 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims 1
- 125000004775 chlorodifluoromethyl group Chemical group FC(F)(Cl)* 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- FFAFQBAXGXPQFG-UHFFFAOYSA-N (2-chloro-2,2-difluoroethyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)Cl FFAFQBAXGXPQFG-UHFFFAOYSA-N 0.000 description 2
- OOUSDMSJNKEAJO-UHFFFAOYSA-N (2-chloro-2,3,3,3-tetrafluoropropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(Cl)C(F)(F)F OOUSDMSJNKEAJO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZQQJOXFNHDSIAQ-UHFFFAOYSA-N (3-chloro-2,2,3,3-tetrafluoropropyl) 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCC(C(F)(F)Cl)(F)F ZQQJOXFNHDSIAQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- KWSLNKPYNZTHLJ-UHFFFAOYSA-N 2-chloro-2,2-difluoroethanol Chemical compound OCC(F)(F)Cl KWSLNKPYNZTHLJ-UHFFFAOYSA-N 0.000 description 1
- BQMDKTJDFSUWPK-UHFFFAOYSA-N 2-methyl-2-phenyldiazenylpropanenitrile Chemical compound N#CC(C)(C)N=NC1=CC=CC=C1 BQMDKTJDFSUWPK-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 238000001015 X-ray lithography Methods 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 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
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical group [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
(57) Polymery (chlorfluoralkyl)-2-propenoátů jsou tvořené homopolymery a kopolymery (chlorfluoralkyl)-2-propenoátů obecného v vzorce(57) Polymers of (chlorofluoroalkyl) -2-propenoates are composed of homopolymers and copolymers of (chlorofluoroalkyl) -2-propenoates of the general formula:
CH2 = CX - C00 - CH2 - , kde X je vodík nebo methyl, R| je chlordifluormethyl (CFjCl), chlortetrafluorethyl (C7CIF4) , 1,2-dichlortrifluorethyl (CF2CICFCI), trichlordifluorethyl (C2CI3F9), 1,1-dichlortrifIuorethyl (CF3CCI2), chlortrifluorethyl (C2HC1F^), dichlordifluorethyl (C9HC12F2), případně jejich kopolymery s alkyl-2-propenoáty obecného vzorce ch2 = CX - coor2 , kde X má vpředu uvedený význam a R2 je alifatický, cykloalifatický nebo aromatickoalifatický alkyl obsahující 1 až 8 atomů uhlíku. Lze je použít jako citlivé pozitivní elektronové rezisty.CH 2 = CX - C00 - CH 2 - wherein X is hydrogen or methyl, R | is chlorodifluoromethyl (CF3Cl), chlorotetrafluoroethyl (C7CIF4), 1,2-dichlorotrifluoroethyl (CF2CICFCI), trichlorodifluoroethyl (C2Cl3F9), 1,1-dichlorotrifluoroethyl (CF3CCl2), chlorotrifluoroethyl (C2HC1F12), their dichlorodifluoroethyl -2-propenoates of general formula ch 2 = CX-coor 2 , wherein X is as defined above and R 2 is aliphatic, cycloaliphatic or aromaticaliphatic alkyl having 1 to 8 carbon atoms. They can be used as sensitive positive electron resists.
273 783 (11) (13) Bl (51) Int. Cl.5 273 783 (11) (13) Bl (51) Int. Cl. 5
C 08 F 20/24 G 03 F 7/26 ί - - ϊC 08 F 20/24 G 03 F 7/26 ί - - ϊ
CS 273783 8181
Oblast použití fluorovaných polymerů je díky jejich speciálním vlastnostem velmi široká. Kromě již tradičních aplikací využívajících jejich vysoké tepelné a chemické odolnosti se uplatnily i ve zdravotní protetice, optoelektronice a mikroelektronice. Jedná se převážně o aplikace, ve kterých je relativně vysoká cena polymerů vyvážena jejich vysokou užitnou hodnotou. V optoelektronice se využívá nízké hodnoty indexu lomu fluorovaných polymerů v kombinaci s vysokou chemickou odolností a elasticitou při nízkých teplotách. V mikroelektronice při aplikaci ve formě rezistů je s výhodou využívána jejich vysoká citlivost vůči ionizujícímu záření.The field of application of fluorinated polymers is very wide due to their special properties. In addition to the traditional applications utilizing their high thermal and chemical resistance, they have also been used in medical prosthetics, optoelectronics and microelectronics. These are mainly applications in which the relatively high cost of polymers is balanced by their high utility value. Optoelectronics uses low refractive index values of fluorinated polymers in combination with high chemical resistance and low temperature elasticity. In microelectronics, when applied in the form of resistors, their high sensitivity to ionizing radiation is advantageously used.
V literatuře je popsána celá řada homopolymerů a kopolymerů fluorovaných monomerů obsahujících v molekule jeden nebo více atomů fluoru. Z hlediska litografických vlastností byly sledovány některé fluorované polymery, přičemž velká pozornost byla věnována derivátům kyseliny akrylové, resp. methakrylové. Patentové nároky zahrnují širokou paletu methakrylátú fluorovaných alkanolů (Paleta 0., Dědek V., Sborník VŠCHT Praha, S15, 69 /1906/).A variety of homopolymers and copolymers of fluorinated monomers containing one or more fluorine atoms per molecule are described in the literature. Some fluorinated polymers were observed from the point of view of lithographic properties, with great attention being paid to derivatives of acrylic acid, resp. methacrylic. The claims include a wide variety of methacrylates of fluorinated alkanols (Palette 0, Dědek V., Proceedings of ICT Prague, S15, 69 (1906)).
Je uvedeno použití polymerů 2-propenoátů, které obsahují buď fluorovaný alkyl a jsou vhodné pro aplikaci v elektronové litografii nebo chlorovaný alkyl sterové skupiny, které jsou vhodné jako rentgenové rezisty se zvýšenou citlivostí.The use of 2-propenoate polymers containing either fluorinated alkyl and suitable for use in electron beam lithography or chlorinated alkyl ster groups, which are suitable as X-ray resists with increased sensitivity, is disclosed.
Doposud však nebyly popsány polymery na bázi 2-propenoátů, které by splňovaly podmínky univerzální aplikace jak v elektronové tak i v rentgenové litografii s vysokou citlivostí.However, 2-propenoate-based polymers that meet the requirements of universal application in both electron and X-ray lithography with high sensitivity have not been described.
Výše uvedený nedostatek odstraňují polymery (chlorfluoralkyl)-2-propenoátů podle vynálezu tvořené homopolymery a kopolymery (chlorfluoralkyl)-2-propenoátů obecného vzorce ch2 = cx - cooch2r1 , kde X je vodík nebo methyl, R^ je chlordifluormethyl (CFjCl), chlortetrafluorethyl (C^CIF^), 1,2-dichlortrifluorethyl (CF2C1CFC1), 1,1-dlchlortrifluorethyl (CF^CCip, trichlordifluorethyl (CjCl^Fp, chlortrifluorethyl (CjHCIFj), dichlordifluorethy1 (C2HC12F2), případně jejich kopolymery s alkyl-2-propenoáty obecného vzorce ch2 = CX - coor2 , kde X má vpředu uvedený význam a R2 je alifatický, cykloalifatický nebo aromatickoalifatický alkyl obsahující 1 až 8 atomů uhlíku.The above-mentioned drawback is overcome by the (chlorofluoroalkyl) -2-propenoate polymers of the invention consisting of homopolymers and (chlorofluoroalkyl) -2-propenoate copolymers of the formula ch 2 = cx-cooch 2 r 1 , where X is hydrogen or methyl, R 6 is chlorodifluoromethyl (CF 3 Cl) ) chlortetrafluorethyl (C ^ ^ cIF), 1,2-dichlortrifluorethyl (CF 2 C1CFC1), 1,1-dlchlortrifluorethyl (CF ^ CCIP, trichlordifluorethyl (CjCl ^ Fp chlortrifluorethyl (CjHCIFj) dichlordifluorethy1 (C 2 HC1 2 F 2 or their copolymers with alkyl-2-propenoates of the formula ch 2 = CX-coor 2 , wherein X is as defined above and R 2 is an aliphatic, cycloaliphatic or aromatic-aliphatic alkyl having 1 to 8 carbon atoms.
Výše uvedené polymery jsou připravovány radikálovou polymerlzací iniciovanou tepelným nebo fotolytickým rozkladem přítomných iniciátorů. Jako iniciátory jsou s výhodou použity alifatické nebo aromaticko-alifatické azonitrily a peroxidické iniciátory jako dibenzoylperoxid apod.The above polymers are prepared by free-radical polymerization initiated by thermal or photolytic decomposition of the initiators present. Aliphatic or aromatic-aliphatic azonitriles and peroxide initiators such as dibenzoyl peroxide and the like are preferably used as initiators.
Výše uvedené (chlorfluoralkyl)-2-propenoáty lze s výhodou připravit acylaci odpovídajících chlorfluoralkanolů chloridem kyseliny akrylové či methakrylové.The aforementioned (chlorofluoroalkyl) -2-propenoates can advantageously be prepared by acylating the corresponding chlorofluoroalkanols with acrylic or methacrylic acid chloride.
Volbou polymeračnich podmínek a kopolymerizací (chlorfluoralkyl)-2-propenoátů s estery kyseliny akrylové či methakrylové lze regulovat hodnoty molárních hmotností a distribuci vznikajících polymerů. Pokud není použit monomer o vysoké čistotě, vzniká polymer s velmi širokou distribucí molárních hmotností (Mw/Mn = 8,4) v důsledku přítomnosti výšefunkčních monomerů. Složení kopolymerů (fluorchloralkyl)-2-propenoátů s methylmethakrylátem se jen velmi málo liší od složení polymerační násady. Rychlost polymerizaoe je znatelná závislá na složení polymerizační násady.By selecting polymerization conditions and copolymerizing (chlorofluoroalkyl) -2-propenoates with acrylic or methacrylic acid esters, the molar mass values and distribution of the resulting polymers can be controlled. If a high purity monomer is not used, a polymer with a very broad molecular weight distribution (M w / M n = 8.4) results from the presence of higher functional monomers. The composition of the copolymers of (fluorochloroalkyl) -2-propenoates with methyl methacrylate differs very little from that of the polymerization batch. The rate of polymerization is noticeable depending on the composition of the polymerization batch.
Připravené homo- a kopolymery výše uvedených (chlorfluoralkyl)-2-propenoátů lze použít například jako citlivé pozitivní elektronové rezisty. Hodnota citlivosti rezistů vůčiThe prepared homo- and copolymers of the above-mentioned (chlorofluoroalkyl) -2-propenoates can be used, for example, as sensitive positive electron resists. Resistance sensitivity value to
-6 -2 elektronovému záření se pohybovala v rozsahu Q = 3 až 10x10 C.cm a hodnoty kontrastu : se pohybují v rozmezí 1,3 až 3,3.-6 -2 electron radiation ranged from Q = 3 to 10x10 C.cm and contrast values: ranged from 1.3 to 3.3.
-'-Έ jř-'- Έ jř
CS 273783 Bl 2CS 273783 B1 2
Předmět vynálezu je objasněn následujícími příklady.The invention is illustrated by the following examples.
Přiklad 1Example 1
K roztoku 19,4 g chloridu 2-methyl-2-propenové kyseliny a 21,6 g 2-chlor-2,2-difluorethanolu v 60 ml diethyletheru byl přidáván za chlazení a míchání triethylamin v celkovém množství 18,9 g. Po ukončení reakce za 3 hodiny byla kašovitá směs smíchána s vodou, etherový roztok byl neutralizován, promyt vodou a vysušen pevným sušidlem. Po oddestilováni etheru ze směsi byl surový produkt rektifikován na náplňové koloně a produkt (2-chlor-2,2-difluorethyl)-2-methyl-2-propenoát, byl jímán v rozmezí 47 až 40 °C za tlaku 2,4 kPa ve výtěžku 24,3 g. Všechny operace byly prováděny v přítomnosti inhibitoru polymerizace.To a solution of 19.4 g of 2-methyl-2-propenoic acid chloride and 21.6 g of 2-chloro-2,2-difluoroethanol in 60 ml of diethyl ether was added, with cooling and stirring, triethylamine in a total amount of 18.9 g. After 3 hours of reaction, the slurry was mixed with water, the ether solution was neutralized, washed with water and dried with a solid desiccant. After distilling off the ether from the mixture, the crude product was rectified on a packed column and the product (2-chloro-2,2-difluoroethyl) -2-methyl-2-propenoate was collected at 47-40 ° C at 10 mm Hg All operations were carried out in the presence of a polymerization inhibitor.
Příklad 2 (2-chlor-2,3,3,3-tetrafluorpropyr)-2-methyl-2-propenoát byl pclymerizován v dioxanu při 60 °C po dobu 9 hodin za iniciace 2,2 '-azo-bis-isobutyronitrilu o koncentraci 2,5.10-3 mol.ll. Výsledný polymer měl po izolaci hodnotu Mw = 5,5.105 g.mol-1 a Mw/Mn = 2,9.Example 2 (2-chloro-2,3,3,3-tetrafluoropropyl) -2-methyl-2-propenoate was polymerized in dioxane at 60 ° C for 9 hours to initiate 2,2'-azo-bis-isobutyronitrile with concentration 2.5.10 -3 mol.ll. The resulting polymer, after isolation, had a Mw = 5.5x10 5 g.mol -1 and a Mw / M n = 2.9.
Příklad 3 (2-Chlor-2,2-difluorethyl)-2-propenoát byl polymerizován v roztoku dioxanu při teplon _4 _i tě 70 C po dobu 7 hodin za iniciace dibenzoylperoxidu o koncentraci 8.10 mol.lExample 3 (2-Chloro-2,2-difluoroethyl) -2-propenoate was polymerized in dioxane solution at a temperature of 4 ° C to 70 ° C for 7 hours with initiation of 8.10 mol.l dibenzoyl peroxide.
Získaný polymer měl po izolaci hodnotu Mw = 9,7.10^ g.mol-1 a Mw/Mn = 3,5.The obtained polymer had, after isolation, a value of M w = 9.7.10 µg.mol -1 and M w / M n = 3.5.
Příklad 4Example 4
Kopolymer (2-chlor-2,2-difluorethyl)-2-methyl-2-propenoátu s (methyl)-2-methyl-2-propenoátem obsahující 19,6 ’ί mol (methyl)-2-methyl-2-propenoátu a mající Mw = 9,3.105 (2-Chloro-2,2-difluoroethyl) -2-methyl-2-propenoate copolymer with (methyl) -2-methyl-2-propenoate containing 19,6 'mol of (methyl) -2-methyl-2-propenoate and having M w = 9.3 x 10 5
g.mol-1 a Μ /M = 2,07 byl připraven polymerizaci v roztoku dioxanu při teplotě 60 °C w n . -3 -i po dobu 250 minut za iniciace 2,2 -azo-bis-isobutyronitrilu o koncentraci 5.10 mol.lg.mol -1 and Μ / M = 2.07 was prepared by polymerization in dioxane solution at 60 ° C wn . -3-i for 250 minutes with initiation of 2,2-azo-bis-isobutyronitrile at a concentration of 5.10 mol.l
Příklad 5Example 5
Homopolymer (2,3-dichlor-2,3,3-trifluorpropyl)-2-methyl-2-propenoátu mající hodnoty Mw = 6,5.105 g.mol1 a Mw/Mn = 2,8 byl připraven způsobem uvedeným v příkladu 2.(2,3-Dichloro-2,3,3-trifluoropropyl) -2-methyl-2-propenoate homopolymer having M w = 6.5 x 10 5 g.mol 1 and M w / M n = 2.8 was prepared by in Example 2.
Příklad 6Example 6
Kopolymer (2-chlor-2,3,3,3-tetrafluorpropyl)-2-methyl-2-propenoátu s (methyl)-25(2-Chloro-2,3,3,3-tetrafluoropropyl) -2-methyl-2-propenoate copolymer with (methyl) -25
-methyl-2-propenoátem o obsahu 40,8 % mol (methyl)-2-methyl-2-propenoátu mající M = 8,5.10 ” o-methyl-2-propenoate having a content of 40,8 mol% of (methyl) -2-methyl-2-propenoate having a M = 8,5.10 "o
g.mol- a M,,/M_ = 3,1 byl připraven radikálovou polymerizaci v roztoku dioxanu při 60 DC w n . _3 _i při iniciaci 2,2 -azo-bis-isobutyronitrilu o koncentraci 1,5.10 mol.l Příklad 7gmol - and M ,, / M_ = 3.1 was prepared by radical polymerization in dioxane solution at 60 D C wn. 3 at the initiation of 2,2-azo-bis-isobutyronitrile at a concentration of 1.5.10 mol.l Example 7
Kopolymer (3-chlor-2,2,3,3-tetrafluorpropyl)-2-methyl-2-propenoátu a (2-chlor-2,3,3,3-tetrafluorpropyl)-2-methyl-2-propenoátu (70 % mol) mající Mw = 7.5.105 g.mol”''' a Mw/Mn = = 2,8 byl připraven způsobem uvedeným v příkladu 6.Copolymer of (3-chloro-2,2,3,3-tetrafluoropropyl) -2-methyl-2-propenoate and (2-chloro-2,3,3,3-tetrafluoropropyl) -2-methyl-2-propenoate (70 % mol) having M w = 7.5.10 5 g.mol -1 and M w / M n = 2.8 was prepared as described in Example 6.
Příklad 8Example 8
Roztok (2-chlor-2,2-difluorethyl)-2-methyl-2-propenoátu) v ethylbenzenu (1:2 obj.) obsahující fenylazoisobutyronitril (cQ = 5.10-2 mol/1) byl ozařován světlem z rtuíové luminiscenční výbojky (3x250 W) o vlnové délce 436 nm ze vzdálenosti 20 cm po dobu 2 hodin. Izolovaný polymer měl = 5,3.105 g.mol-''' a Mw/Mn = 2,36.A solution of (2-chloro-2,2-difluoroethyl) -2-methyl-2-propenoate) in ethylbenzene (1: 2 by volume) containing phenylazoisobutyronitrile (c Q = 5.10 -2 mol / l) was irradiated with light from a mercury luminescent lamp (3x250 W) with a wavelength of 436 nm from a distance of 20 cm for 2 hours. The isolated polymer had = 5,3.10 5 gmol - '''and M w / M n = 2.36.
Příklad 9Example 9
Kopolymery (2,2-dichlor-3,3,3-trifluorpropyl)-2-propenoátu s (óyklohexyl)-2-propenoátem a (benzyl)-2-methyl-2-propenoátem'obsahující 24,6 % mol (resp. 31,4 % mol) (2,2-dichlor-3,3,3-trifluorpropyl)-2-propenoátu byly připraveny radikálovou polymerizaci v roztoku toluenu při 60 °C v přítomnosti 2,2 '-azo-bis-isobutyronitrilu (15.10-2 mol.l-''').Copolymers of (2,2-dichloro-3,3,3-trifluoropropyl) -2-propenoate with (6-cyclohexyl) -2-propenoate and (benzyl) -2-methyl-2-propenoate containing 24.6 mol% (resp. 31.4 mol% of (2,2-dichloro-3,3,3-trifluoropropyl) -2-propenoate were prepared by free-radical polymerization in toluene solution at 60 ° C in the presence of 2,2'-azo-bis-isobutyronitrile (15.10. mol.l -2 - ''').
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS824488A CS273783B1 (en) | 1988-12-14 | 1988-12-14 | Polymers of chlorofluoroalkyl)-2-propenoates and method of their preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS824488A CS273783B1 (en) | 1988-12-14 | 1988-12-14 | Polymers of chlorofluoroalkyl)-2-propenoates and method of their preparation |
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| Publication Number | Publication Date |
|---|---|
| CS824488A1 CS824488A1 (en) | 1990-08-14 |
| CS273783B1 true CS273783B1 (en) | 1991-04-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS824488A CS273783B1 (en) | 1988-12-14 | 1988-12-14 | Polymers of chlorofluoroalkyl)-2-propenoates and method of their preparation |
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| CS (1) | CS273783B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013058336A1 (en) * | 2011-10-19 | 2013-04-25 | ダイキン工業株式会社 | Fluorine-containing composition and surface treatment agent |
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1988
- 1988-12-14 CS CS824488A patent/CS273783B1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013058336A1 (en) * | 2011-10-19 | 2013-04-25 | ダイキン工業株式会社 | Fluorine-containing composition and surface treatment agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CS824488A1 (en) | 1990-08-14 |
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