WO1994007936A1 - Partially-fluorinated polymers - Google Patents
Partially-fluorinated polymers Download PDFInfo
- Publication number
- WO1994007936A1 WO1994007936A1 PCT/GB1993/002064 GB9302064W WO9407936A1 WO 1994007936 A1 WO1994007936 A1 WO 1994007936A1 GB 9302064 W GB9302064 W GB 9302064W WO 9407936 A1 WO9407936 A1 WO 9407936A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polymer according
- polymer
- polymers
- perfluorocarbon
- repeating units
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
Definitions
- This invention relates to partially-fluorinated polymers that have chemically-incompatible segments; the polymers have interesting and varied properties, including liquid crystallinity.
- C 10 H 21 -C 10 F 21 An example of a molecule having two distinct parts that are mutually-immiscible is C 10 H 21 -C 10 F 21 , i.e. (perfluorodecyl)decane, as described by Twieg, Robolt J. Polym. Sci. Poly . Phys. Ed. .21:901(83), and Mahler, Guillon and S oulios, Mol. Cryst. Lig. Cryst. 2 . : 111-119 (1985) . That compound was prepared by the reaction of perfluorodecyl iodide with l-decene, followed by reduction; the amphiphilic product exhibited a smectic B liquid crystalline phase.
- EP-A-0352718 discloses partially-fluorinated polymers in which repeating units include a sequence of the formula
- X 1 and X 2 are polymer-forming linkages (e.g. COO
- Such polymers are prepared from dinitriles or ester-nitriles.
- the polymers are apparently those sold under the registered Trade Mark "Zonyl” as fluoro-surfactants that offer thermal and chemical stability superior to that of hydrocarbon surfactants.
- the polymers are also suitable for use as non-stick coatings.
- the repeating units (of which there may be any number, preferably at least 3, e.g. 3 to 30) of the novel polymers include perfluorocarbon and hydrocarbon chains each at least 4 carbon atoms long.
- the repeating units have, for example, the formula
- X 1 and X 2 are each as defined above or are absent (direct hc-fc carbon-carbon bonds)
- fc is the perfluorocarbon and he is the hydrocarbon chain.
- novel polymers may have optical characteristics similar to those of small molecular compounds, but are considerably more viscous. They may exhibit a eso phase, between crystalline and isotropic. They may form gels in organic solvents.
- novel polymers may be prepared by procedures that will be readily apparent to those skilled in the art.
- respective compounds of the formulae Y -hc-Y 1 are prepared by procedures that will be readily apparent to those skilled in the art.
- respective compounds of the formulae Y -hc-Y 1 are prepared by procedures that will be readily apparent to those skilled in the art.
- respective compounds of the formulae Y -hc-Y 1 are prepared by procedures that will be readily apparent to those skilled in the art.
- Y -fc-Y 2 wherein Y 1 and Y 2 are mutually-reactive functional groups that together form X 1 and X 2 , reacted together under polymerising conditions.
- the lodo polymer can be reduced with AIBN and Bu3SnH to remove the iodine.
- the tin hydride can be added to the reaction mixture and the polymer reduced in situ using the same procedure as above but not heating to 170'C in vacuo as the final step. Instead the mixture is cooled to 90'C and 5-10mls of toluene are added and 2.75g of Bu3SnH added slowly with stirring under N2. Further small amounts of AIBN are added (0.35g total) over 30 mins. and the mixture then heated for a further 3-4 hours. On cooling the solution had set to a white opaque gel.
- the product was purified by recrystallisation/ precipitation from a mixture of CHC13 with some MeOH (approx. 2:1) three times to remove tin residues etc.
- Microscope shows all have Incipient L.Cbehaviour. Grainy L.C.Texture.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A polymer whose repeating units comprise perfluorocarbon and hydrocarbon chains each at least 4 atoms long.
Description
PARTIALLY-FLUORINATED POLYMERS
This invention relates to partially-fluorinated polymers that have chemically-incompatible segments; the polymers have interesting and varied properties, including liquid crystallinity.
An example of a molecule having two distinct parts that are mutually-immiscible is C10H21-C10F21, i.e. (perfluorodecyl)decane, as described by Twieg, Robolt J. Polym. Sci. Poly . Phys. Ed. .21:901(83), and Mahler, Guillon and S oulios, Mol. Cryst. Lig. Cryst. 2.: 111-119 (1985) . That compound was prepared by the reaction of perfluorodecyl iodide with l-decene, followed by reduction; the amphiphilic product exhibited a smectic B liquid crystalline phase. Hόpken et al, "Integration of Fundamental Polymer Science Technology - 5", ed. Lemstra and Kleintjes, Elsevier Applied Sciences, describe amphiphilic allyl ethers and ethacrylates. Alcohols of the formula F(CF2)n(CH2)mOH, wherein n = 8, 10, 12 and m = 4, 6, 10, were converted to allyl ethers, and sequentially perfluorinated methacrylates were then prepared. The polymers exhibit a mesomorphic "Schlieren" texture.
Budovskaya et a!, Polymer Science USSR .32. (3):502- 506 (1990) , disclose comb-like polyfluoroalkyl (meth)acrylates having side-chains of the formula=COOCH2(CF2)nH, wherein n = 2, 4, 6, 8, 10, 12; the backbone comprises a single -CH2- group between the carbonate and the CH or CCH3 group to which the side- chains are bonded. The polymers are mesomorphic in structure, with a degree of ordering directly related to n; for n = 10, the formation of a liquid crystal state "is proved by an optical method".
EP-A-0352718 discloses partially-fluorinated polymers in which repeating units include a sequence of the formula
■*-X1-CH2CH2-Rf-CH2CH2--X2- wherein X1 and X2 are polymer-forming linkages (e.g. COO
SUBSTITUTE SHEET
or OOC for polyesters, CONH or NHCO for polyamideε) and Rf is a C i>0 perfluorinated divalent organic radical. Such polymers are prepared from dinitriles or ester-nitriles. The polymers are apparently those sold under the registered Trade Mark "Zonyl" as fluoro-surfactants that offer thermal and chemical stability superior to that of hydrocarbon surfactants. The polymers are also suitable for use as non-stick coatings.
Surprisingly, it has now been found that polymers having chemically-incompatible segments can be produced that clearly have liquid crystalline properties, as well as offering the properties associated with the polymers described above. The repeating units (of which there may be any number, preferably at least 3, e.g. 3 to 30) of the novel polymers include perfluorocarbon and hydrocarbon chains each at least 4 carbon atoms long. The repeating units have, for example, the formula
-X1-hc-X2-fc- wherein X1 and X2 are each as defined above or are absent (direct hc-fc carbon-carbon bonds) , fc is the perfluorocarbon and he is the hydrocarbon chain.
The novel polymers may have optical characteristics similar to those of small molecular compounds, but are considerably more viscous. They may exhibit a eso phase, between crystalline and isotropic. They may form gels in organic solvents.
The novel polymers may be prepared by procedures that will be readily apparent to those skilled in the art. For example, respective compounds of the formulae Y -hc-Y1
Y -fc-Y2 wherein Y1 and Y2 are mutually-reactive functional groups that together form X1 and X2, reacted together under polymerising conditions. Y1 is a substituent such as I or OH, or within he, e.g. a C=C bond. This procedure, and the invention as a whole, are illustrated in the following Examples. The reaction scheme is shown in the
SUBSTITUTE SHEET
Chart headed "Hydrocarbon-Fluorocarbon Polymers". Examples
The following two-step procedure was adopted in order to prepare a polymer of the invention in which repeating units have the formula -(CF2)6-(CH2) 1fJ-. An analogous procedure was adopted for other compounds of the invention.
SYNTHESIS of [-(CF2)6-CH2CHI(CH2)6CHICH2-]n FROM I-(CF2)6-I
The reaction
I-(CF2)6-I + =-(CH2)6)-= →[- (CF2) 6-CH2CHI(CH2) 6-CHICH2-]n
Polymer was performed as follows:
2.50g I-(CF2)6-I and 0.62g =-(CH2)6-= were added together in a small flask under N2 equipped with a bubbler to maintain a very small positive pressure and prevent the entry of air. The mixture was heated to approx. 80 ' C in an oil bath with stirring while AIBN was added continuously in small portions of about 0.05g every 10 mins. The purple colour of the mixture disappeared after about 20 mins. and the solution was clear. Heating continued for 2 hours while the solution became more and more viscous, then the temperature was increased to
100'C, 115'C and finally 145'C over a period of about an hour to enable stirring to continue and AIBN addition was then stopped. Finally the solution was heated to 170 ' C under vacuum to remove unreacted material and AIBN (sublimed) . The product was cooled and after several hours had set to a pale yellow translucent solid. AIBN = azobisobutyronitrile. Yield was approx. 96% IR shows only large C-H region and C-F.2800-3000 and 1100-1210 (strong)
H NMR (in CDC13) shows CHI, CH2 at 4.35m(l) , 2.84m(split) (2) , 1.80m(2) and 1.40m(4) .
SUBSTITUTE SHEET
GPC in CHC13 shows single distrib. with MW 10,000-20,000, D = 1.66. Elemental analysis, (Calc) %H 2.71 %C 28.30 (Found) %H 2.81 %C 28.38 (for DP = 21, terminal vinyls) . Notes MW
I-(CF2)6-I = 552, bp.115'C/100mm =-(ch2)6-= = 138, bp.l69'C
Synthesis of [- (CF2) 6-(CH2) 10-]n from lodo polymer
The lodo polymer can be reduced with AIBN and Bu3SnH to remove the iodine. The tin hydride can be added to the reaction mixture and the polymer reduced in situ using the same procedure as above but not heating to 170'C in vacuo as the final step. Instead the mixture is cooled to 90'C and 5-10mls of toluene are added and 2.75g of Bu3SnH added slowly with stirring under N2. Further small amounts of AIBN are added (0.35g total) over 30 mins. and the mixture then heated for a further 3-4 hours. On cooling the solution had set to a white opaque gel. The product was purified by recrystallisation/ precipitation from a mixture of CHC13 with some MeOH (approx. 2:1) three times to remove tin residues etc.
Yield after purification was approx. 1.80g, 91% (overall) IR shows only large C-H region and C-F.2800-3000 and 1110-1230 (broad, strong) H NMR (in CDC13) shows CH2 at 2.1111.(1), 1.67m(l) , 1.39m(3) with shoulder at 1.45. Elemental analysis, (Calc) %H 5.88 %C 49.40 (found) %H 5.98 %C 49.61 (for DP = 21, terminal vinyls)
Note, Bu3SnH = 291
SUBSTITUTE SHEET
94/07936
FLUORINATED MICROBLOCK POLYMERS
Analysis Data for Fluorined Polymers
SUBSTITUTE SHEET
REACTIONS;
POLYMER
F = (CF2) R = (CH2)
EXAMPLES
6 8 10
PROPERTIES
Microscope shows all have Incipient L.Cbehaviour. Grainy L.C.Texture.
SUBSTITUTE SHEET
Claims
1. A polymer whose repeating units comprise perfluorocarbon and hydrocarbon chains each at least 4
"4! V atoms long.
2. A polymer according to claim 1, wherein the repeating units have the formula
-X1-hc-X2-fc- wherein X1 and X2 are absent or are polymer-forming linkages (e.g. COO or OOC for polyesters, CONH or NHCO for polyamides) , fc is the perfluorocarbon and he is the hydrocarbon chain.
3. A polymer according to either preceding claim, wherein the perfluorocarbon chain has 6-20 C atoms.
4. A polymer according to any preceding claim, wherein the hydrocarbon chain has 6-30 C atoms.
5. A polymer according to any preceding claim, which has liquid crystalline properties.
6. A substrate coated with a polymer according to any preceding claim.
7. A process for preparing a polymer according to any of claims 1 to 5, which comprises reacting together corresponding compounds of the formulae
Y^hc-Y1 Y2-fc-Y2 wherein Y1 and Y2 are mutually-reactive functional groups (Y1 being on or within the he to which it is shown attached) that together form X1 and X2.
SUBSTITUTE SHEET
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9220951.9 | 1992-10-06 | ||
| GB929220951A GB9220951D0 (en) | 1992-10-06 | 1992-10-06 | Partially-fluorinated polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1994007936A1 true WO1994007936A1 (en) | 1994-04-14 |
Family
ID=10723005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB1993/002064 WO1994007936A1 (en) | 1992-10-06 | 1993-10-05 | Partially-fluorinated polymers |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB9220951D0 (en) |
| WO (1) | WO1994007936A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619466A (en) * | 2017-09-18 | 2018-01-23 | 苏州大学 | A kind of polymerization that fluorine-containing alternating polymer is prepared by photochemical catalyst |
| WO2018038132A1 (en) * | 2016-08-23 | 2018-03-01 | 国立大学法人お茶の水女子大学 | Fluorine-containing polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250300A (en) * | 1977-05-12 | 1981-02-10 | Daikin Kogyo Co., Ltd. | Fluorine-containing polyesters, and their production and use |
| EP0152065A2 (en) * | 1984-02-08 | 1985-08-21 | Daikin Industries, Limited | Omega-perfluoroalkyl-1,2-epoxyalkane copolymer and use thereof |
| US4587328A (en) * | 1985-03-21 | 1986-05-06 | Westinghouse Electric Corp. | Fire retardant water repellent impregnating resins |
| EP0352718A2 (en) * | 1988-07-25 | 1990-01-31 | E.I. Du Pont De Nemours And Company | Partially fluorinated compounds and polymers |
-
1992
- 1992-10-06 GB GB929220951A patent/GB9220951D0/en active Pending
-
1993
- 1993-10-05 WO PCT/GB1993/002064 patent/WO1994007936A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250300A (en) * | 1977-05-12 | 1981-02-10 | Daikin Kogyo Co., Ltd. | Fluorine-containing polyesters, and their production and use |
| EP0152065A2 (en) * | 1984-02-08 | 1985-08-21 | Daikin Industries, Limited | Omega-perfluoroalkyl-1,2-epoxyalkane copolymer and use thereof |
| US4587328A (en) * | 1985-03-21 | 1986-05-06 | Westinghouse Electric Corp. | Fire retardant water repellent impregnating resins |
| EP0352718A2 (en) * | 1988-07-25 | 1990-01-31 | E.I. Du Pont De Nemours And Company | Partially fluorinated compounds and polymers |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018038132A1 (en) * | 2016-08-23 | 2018-03-01 | 国立大学法人お茶の水女子大学 | Fluorine-containing polymer |
| CN107619466A (en) * | 2017-09-18 | 2018-01-23 | 苏州大学 | A kind of polymerization that fluorine-containing alternating polymer is prepared by photochemical catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9220951D0 (en) | 1992-11-18 |
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