SINGH RAJIV R (US)
SHAFER GREGORY J (US)
NAIR HARIDASSAN K (US)
SINGH RAJIV R (US)
SHAFER GREGORY J (US)
| EP1167397A1 | 2002-01-02 |
HOWELL J L ET AL: "New derivatives of poly-hexafluoropropylene oxide from the corresponding alcohol", JOURNAL OF FLUORINE CHEMISTRY, ELSEVIER, AMSTERDAM, NL, vol. 126, no. 3, March 2005 (2005-03-01), pages 281 - 288, XP004809240, ISSN: 0022-1139
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; UMEZAWA, JUNKO ET AL: "Preparation of fluorine-containing polyether oligomers", XP002468722, retrieved from STN Database accession no. 1994:410291
WHAT IS CLAIMED IS:
1 : A process for the preparation of an allyloxytrifluoropropene derivative represented by the formula:
CF 3 CH=CR 1 (OCH 2 CR=CH 2 )
wherein:
R 1 is selected from the group consisting of: hydrogen, fluoro, and allyloxy group represented by the formula:
-OCH 2 CR=CH 2
wherein R is selected from the group consisting of: hydrogen and methyl; and said process comprising the steps of: contacting
(i) a compound represented by the formula:
CF 3 CH=CR 2 R 3
wherein R 2 is selected from the group consisting of: hydrogen, chloro, and fluoro and wherein R 3 is chloro or fluoro; and
(ii) an allyl alcohol derivative represented by the formula:
HOCH 2 CR=CH 2
wherein R is selected from the group consisting of: hydrogen and methyl; wherein said contacting is carried out in the presence of a base and optionally a solvent at a temperature and length of time sufficient to produce said allyloxytrifluoropropene derivative.
2. The process of claim 1 , wherein R 1 is hydrogen.
3. The process of claim 1 , wherein R 1 is an allyloxy group represented by the formula:
-OCH 2 CR=CH 2
wherein R is hydrogen.
4. The process of claim 1 , wherein R 1 is an allyloxy group represented by the formula:
-OCH 2 CR=CH 2
wherein R is methyl.
5. The process of claim 1 , wherein said allyloxytrifluoropropene derivative is a mixture comprising:
CF 3 CH=CF(OCH 2 CR=CH 2 ) and CF 3 CH=C(OCH 2 CR=CH 2 ) 2
wherein R is selected from the group consisting of hydrogen and methyl.
6. The process of claim 1 , wherein said allyloxytrifluoropropene derivative is selected from the group consisting of CF 3 CH=CH(OCH 2 CH=CH 2 ) and CF 3 CH=C(OCH 2 CH=CH 2 ) 2
7. The process of claim 1 , wherein said allyloxytrifluoropropene derivative is selected from the group consisting of CF 3 CH=CH(OCH 2 C(CH 3 )=CH 2 ) and CF 3 CH=C(OCH 2 C(CH 3 )=CH 2 ) 2 .
8. The process of claim 1 , wherein said compound represented by the formula CFaCH=CFR 2 is selected from the group consisting of CF 3 CH=CHF, CF 3 CH=CF 2 , and CF 3 CH=CHCI.
9. The process of claim 8, wherein said contacting is carried out in a ratio of about 1 :1 of said compound represented by the formula CF 3 CH=CF 2 to said ally! alcohol derivative to produce an allyloxy derivative represented by the formula:
CF 3 CH=CF(OCH 2 CR=CH 2 )
wherein R is selected from the group consisting of: hydrogen and methyl.
10. The process of claim 8, wherein said contacting is carried out in a ratio of about 1 :2 of said compound represented by the formula CF 3 CH=CF 2 to said allyl alcohol derivative to produce an allyloxy derivative represented by the formula:
CF 3 CH=C(OCH 2 CR=CH 2 ) 2
wherein R is selected from the group consisting of: hydrogen and methyl.
11. The process of claim 1 , wherein said step of contacting is preferably carried out at a temperature from about 25 0 C to about 50 °C, at a pressure of about 0.5 atm to about 1 atm, and for a length of time from about 30 minutes to about 5 hours.
12. The process of claim 1 , wherein said step of contacting is carried out at a temperature from about 25 °C to about 35 0 C, at a pressure from about 1 atm, and for a length of time from about 30 minutes to about 2 hours.
13. The process of claim 1 , wherein R is hydrogen.
14. The process of claim 1 , wherein R is methyl.
15. An allyloxytrifluoropropene derivative represented by the formula:
CF 3 CH=C(OCH 2 CH=CH2)2
16. An allyloxytrifluoropropene derivative represented by the formula:
CF 3 CH=C(OCH 2 C(CH3)=CH2)2
17. An allyloxytrifluoropropene derivative represented by the formula:
CF 3 CH=CH(OCH 2 C(CHS)=CH 2 )
18. An allyloxytrifluoropropene derivative represented by the formula:
CF 3 CH=CF(OCH 2 CR=CH 2 )
wherein R is selected from the group consisting of: hydrogen and methyl.
19. A process for preparing a polymer comprising the step of: polymerizing:
(iii) an allyloxytrifluoropropene derivative selected from the group consisting of compounds represented by the formula:
CF 3 CH=CH(OCH 2 CR=CH 2 );
CF 3 CH=C(OCH 2 CR=CH 2 ) 2 ;
CF 3 CH=CF(OCH 2 CR=CH 2 ); and any mixtures thereof; wherein R is selected from the group consisting of: hydrogen and methyl; and optionally (iv) an ethylenically unsaturated comonomer; wherein said copolymerizing step is carried out in the presence of a catalytst, under conditions sufficient to produce said copolymer.
20. The process of claim 19, wherein said catalyst comprises methylphenylsilane and Cθ2(CO)β.
21. The process of claim 19, where said allyloxytrifluoropropene derivative is:
CF 3 CH=C(OCH 2 CH=CH2)2
22. A homopolymer prepared by the process of claim 19.
23. A copolymer prepared by the process of claim 19. |
ALLYLOXYTRIFLUOROPROPENES
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to a process for making allyloxytrifluoropropenes and homopolymers and copolymers thereof starting from fluoro olefins. More particularly, the present invention relates to a process for making compounds, such as, CF 3 CH=CHOCH 2 CH=CH 2 , CF 3 CH=CFOCH 2 CH=CH 2 , CF 3 CH=C(OCH 2 CH=CH 2 ) 2 and methallyl derivatives thereof from CF 3 CH=CHF or CF 3 CH=CF 2 and allyl or methallyl alcohol.
2. Description of the Prior Art
Compounds containing allyloxy group are typically used as monomers for preparing siloxane polymers or as a CF 3 building block. See, for example, Polymer Chemistry, (1995) 33(14), 2415-23, J. Polymer Sci. A: Polym. Chem (1997) 35, 1593-1604 and Chem. Commun., (1996), 57-58.
Uses of polymers derived from allyl ethers for UV curing, to films on various surfaces, for adhesives, coating, cladding and the like are described in J. Polym. Sci., Part A, Polym. Chem., 2002, 40, 2583-2590.
Allyloxypropene of the formula CF 3 CH 2 CFHOCH 2 -CH=CH 2 is used as a monomer for making siloxane polymers, as described in the German Patent DE 3,138,235 A1 and in J. Fluorine Chem., (2005), 126, 281-288.
Relatively little is known about allyloxypropene polymers in general. U.S. Patent No. 6,930,159 B1 describes some fluorinated allyl ether polymers. However, the structure of monomers used in the preparation of the polymers described in this patent is quite different from the allyloxypropene monomers described in the present invention.
Relatively little is known about allyloxypropenes described by the present invention. The only known example in this group is 1-allyloxy- 3,3,3-trifluoropropene of the formula CF 3 CH=CH(OCH 2 CH=CH 2 ) which is made from CF 3 CBr=CH 2 with a base and catalytic amount of water.
This reaction proceeds by an elimination-addition mechanism through the formation of trifluoromethylpropyne as an intermediate followed by the addition of allyl alcohol to the so formed trifluoromethylpropyne (See Chem. Commun., (1996), 57-58).
However, large-scale preparation of allyloxytrifluoropropenes using this approach requires the use of CF 3 CBr=CH 2 as a starting material, which is expensive and cumbersome to manufacture.
Compounds such as CF 3 CH=C(OCH 2 CH=CH 2 ) 2 with two allyloxy groups and polymers derived therefrom are unknown in the art.
Consequently, there is a need in industry to develop commercially feasible processes for making such compounds and exploring their properties and uses in various applications.
To achieve this objective, the present invention provides a process, which is practical and, as such, it is potentially useful commercially.
SUMMARY OF THE INVENTION
The present invention provides a process for the preparation of an allyloxytrifluoropropene derivative represented by the formula:
CF 3 CH=CR 1 (OCH 2 CR=CH 2 )
wherein:
R 1 is selected from hydrogen, fluoro, and allyloxy group represented by the formula:
-OCH 2 CR=CH 2
wherein R is hydrogen or methyl.
The process includes the steps of: contacting:
(i) a compound represented by the formula:
CF 3 CH=CR 2 R 3
wherein R 2 is selected from the group consisting of hydrogen, chloro, and fluoro and wherein R 3 is chloro or fluoro; and
(ii) an allyl alcohol derivative represented by the formula:
HOCH 2 CR=CH 2
wherein R is hydrogen or methyl; wherein the contacting is carried out in the presence of a base and optionally a solvent at a temperature and length of time sufficient to produce the allyloxytrifluoropropene derivative.
The present invention further provides allyloxytrifluoropropene derivatives, including compounds of the following formula: CF 3 CH=C(OCH 2 CH=CH 2 ) 2 ; CF 3 CH=C(OCH 2 C(CH 3 )=CH 2 ) 2 ; CF 3 CH=CH(OCH 2 C(CHS)=CH 2 ); and CF 3 CH=CF(OCH 2 CR=CH 2 ); wherein R is hydrogen or methyl.
The present invention still further provides process for preparing a polymer including the step of: polymerizing:
(iii) an allyloxytrifluoropropene derivative selected from compounds represented by the formula: CF 3 CH=CH(OCH 2 CR=CH 2 ); CF 3 CH=C(OCH 2 CR=CH 2 ) 2 ; CF 3 CH=CF(OCH 2 CR=CH 2 ); and any mixtures thereof; wherein R is hydrogen or methyl; and optionally (iv) an ethylenically unsaturated comonomer; wherein the copolymerizing step is carried out in the presence of a catalytst, preferably including methylphenylsilane and Co 2 (CO) 8 , under conditions sufficient to produce the copolymer.
The present invention also provides homopolymers and copolymers of these allyloxytrifluoropropene derivatives prepared by the polymerization process according to the present invention.
The process according to the present invention is practical and, as such, it is potentially useful commercially.
These and other benefits of the present invention will become more evident from detailed description of the preferred embodiments that follow.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
When CF 3 CH=CF 2 is reacted with allyl alcohol or methallyl alcohol at 25 0 C to 35 0 C with catalytic amount of a base, such as, Cs 2 CO 3 , in a polar solvent, quite unexpectedly, the major product formed was the fluoride substitution produce, rather than the expected product of addition to the carbon-carbon double bond, to form CF 3 CH=C(OCH 2 -CH=CH 2 ) 2 (IA).
Even with only catalytic amount of a base being present, both of the vinylidene fluorines in CF 3 CH=CF 2 can be replaced by allyloxy group. This is an unknown reaction of vinylidene fluorides and, as such, it is an unexpected reaction.
Temperature appears to play an important role in these reactions. At lower temperatures, such as, for example, at temperatures from about -20 0 C to about 5 0 C, one can predominantly obtain the addition product of the formal CF 3 CH 2 CF 2 OCH 2 -CH=CH 2 (IC).
In contrast, when a temperature from about 25 0 C to about 35 0 C is used, the major product formed is CF 3 CH=C(OCH 2 -CH=CH 2 ) 2 ( IA); the minor being CF 3 CH=CF(OCH 2 -CH=CH 2 ) (IB) (~ 5 to 20%) as shown in Scheme 1 below. Thus, under these experimental conditions, only trace amount of the expected addition product (IC) was seen.
This above reactions are depicted in the Scheme 1 below.
Scheme 1
CF 3 -CH=CF 2 + OH CH 2 CH=CH 2
IA IB (minor)
(major)
In large scale preparations, the volatiles generated in the reaction can be trapped in a cold trap/scrubber and thereafter neutralized and the HF generated can be neutralized via washing with aqueous NaOH solution.
Alternately, if the exclusive preparation of IA is desired, one can employ two equivalents of base to neutralize the HF generated during the reaction.
As mentioned before, the reparation of Compound HA CF 3 CH=CH(OCH 2 CH=CH2) has been reported in the literature using a method which employs CF 3 CBr=CH 2 as a starting material.
This approach is described in greater detail in Chem. Commun., 1996, 57-58 and is depicted in Scheme 2 herein below.
Scheme 2
HA
In the present invention, this problem can be overcome by the use of commercially available CF 3 CH=CHF with a base, as depicted in Scheme 3 below.
Scheme 3
Base
Alternately, CF 3 CH=CHCI can also be used in place of CF 3 CH=CHF which is commercially available. Typically, bases such as Cs 2 CO 3l K 2 CO 3 , and sodium or potassium tertiary butoxide can be used in Schemes 1 and 2.
The starting material CF 3 CH=CHF can be made in large scale from commercially available CF 3 CH 2 CF 2 H according to methods described in U.S. Patent No. 6,548,719 B1. CF 3 CH 2 CF 2 H is produced by and is available from Honeywell International, Inc., Morristown, NJ.
Preferably, CF 3 CH=CF 2 is formed from CF 3 CH 2 CF 2 H by chlorination followed by dehydrochlorination and CF 3 CH=CHF is formed from CF 3 CH 2 CF 2 H by dehydrofluorination.
The step of contacting is carried out at a temperature sufficient to produce the allyoxytrifluoropropene derivative. Contacting is preferably carried out at a temperature of about 25 °C to about 100 0 C, more preferably about 25 °C to about 50 0 C, and most preferably about 25 0 C to about 35 0 C.
The step of contacting is carried out at a pressure sufficient to produce the allyoxytrifluoropropene derivative. Contacting is preferably carried out at a pressure of about 0.5 to about 1 atm and most preferably about 1 atm.
The step of contacting is carried out for a length of time sufficient to produce the allyoxytrifluoropropene derivative. Contacting is preferably carried out for a length of time of about 5 minutes to about 300 hours, more preferably about 30 minutes to about 5 hours, still more preferably about 30 minutes to about 2 hours, and most preferably about 2 hours.
The step of contacting is preferably carried out at a temperature from about 25 0 C to about 50 °C, at a pressure of about 0.5 atm to about 1 atm, and for a length of time from about 30 minutes to about 5 hours.
More preferably, the step of contacting is carried out at a temperature from about 25 0 C to about 35 0 C, at a pressure from about 1 atm, and for a length of time from about 30 minutes to about 2 hours.
The process can be either a batch process or it can be a continuous process.
The reactor can further include a diluent, such as, a solvent or mixture of solvents. Preferably, polar, non-protic solvents, such as, acetonitrile, dimethylformamide (DMF) 1 dimethylsulfoxide (DMSO), are used as the reaction medium. However, other solvents, such as, mono- and di-ethers of glycols, mono- and di- esters thereof, glymes, diglymes, triglymes, and tetraglymes can also be employed.
The process can further include one or more of the following steps: (1 ) isolating the product from the reaction mixture by pouring the crude reaction mixture onto cold water at about 5 0 C whereby the product separates out the lower layer; and
(2) purifying the reaction product via distillation under reduced pressure to obtain the product in substantially pure form.
In operation, preferably at least 10 wt% of the reactants are converted to the product. More preferably, up to at least 80 wt% of the reactants are converted to the product, and most preferably, at least 90 wt% of the reactants are converted to the product. Accordingly, operation of the process of the present invention under high conversion conditions is preferred.
Polymerization can be carried out essentially the same way as the methods known and described in the art, such as, the methods described in J. Polymer ScL A: Polym. Chem. (1997) 35, 1593-1604 and U.S. Patent No. 6,930,159 B1. Thus, both monomers can be readily polymerized to form homopolymers under standard polymerization conditions known to a person skilled in the art.
Alternatively, these monomers can be also readily polymerized to copolymers if an ethylenically unsaturated comonomer is present.
Depending on the polymerization conditions, the polymers can be obtained as transparent or white powders.
The allyloxytrifluoropropenes according to the present invention are suitable for use as monomers in the preparation of polymers and copolymers, including preparation of coatings, and particularly UV cured coatings.
The following non-limiting examples are illustrative of the various embodiments of the present invention. It is within the ability of a person of ordinary skill in the art to select other variable from amongst the many known in the art without departing from the scope of the present invention. Accordingly, these examples shall serve to further illustrate the present invention, not to limit them.
Experimental Details:
Unless otherwise indicated, all parts and percentages are on a weight basis.
Example 1
1 ,1-Bis-allyloxy-3,3,3-trifluoropropene (CF 3 CH=C(OCH 2 CH=CH 2 )2):
To a stirred mixture of acetonitrile (100 ml_), allylalcohol, CH 2 =CHCH 2 OH, (20 g, 0.34 mol) and catalytic amount cesium carbonate (1.5 g, 4.6 mmol) was added, CFaCH=CF 2 (0.40 mol) via a gas sparger. The addition of CF 3 CH=CF 2 was such that the temperature of the reaction was not more than 36 0 C. After complete addition (30 minutes), the reaction mixture was stirred for 1 hour, poured into 400 mL cold water, mixed well and the upper layer was separated. Separated organic layer was mixed with water (400 mL), allowed to settle. The lower layer was separated, washed with water (50 ml), dried (MgSO4) and filtered to afford crude product CF 3 CH=C(OCH 2 CH=CH 2 ) 2 . Pure product was obtained on distillation under reduced pressure (50 to 55 °C/8-9 mm Hg) as a colorless liquid (25 g, 35% yield).
The structure of the product is consistent with the following spectroscopic data:
GC/MS data: m/e 208 (M + for C 9 HnF 3 O 2 );
19 F NMR (CDCI 3 ) δ = - 68.6 (3F, d, JHF = 8 Hz) ppm; and
1 H NMR (CDCI 3 ) δ = 5.87 (1H, m), 5.71 (1 H 1 m), 5.36-5.09 (4H 1 m), 4. 65 (2H, dt, J = 6 and 2 Hz), 3.2 (1 H, m), 2.6 (2H, m) ppm.
The other product formed in this reaction is CF 3 CH=CF(OCH 2 CH=CH 2 ).
Example 2
1-Allyloxy-3,3,3-trifluoropropene (CF 3 CH=CH(OCH 2 CH=CH 2 )):
To a stirred mixture of acetonitrile (240 mL), allylalcohol, CH 2 =CHCH 2 OH, (2Og, 0.34 mol) and sodium tertiarybutoxide (34.5 g, 0.36 mol) was added, CF 3 CH=CFH via a gas sparger. The addition CF 3 CH=CFH was such that the temperature of the reaction was not more than 35 0 C. After complete addition (about 45 minutes), the reaction mixture was stirred for 1 hour, poured into 400 mL cold water, mixed well and the upper layer was separated. Separated organic layer was mixed with water (400 mL), allowed to settle. The lower layer was separated, washed with water (50 ml), dried (MgSO 4 ) and filtered to afford 42 g product characterized to be CF 3 CH=CHOCH 2 CH=CH 2 , which was 86% pure, by GC. Pure product was obtained on distillation under reduced pressure (36 to 42 °C/68 mm Hg) to afford the pure product as a colorless liquid (32 g, yield = 62 %). The ratio of cis- to trans- isomer is 96:2.
The structure of the product is consistent with the following spectroscopic data:
GC/MS data: m/e 152 for M + (M = C 6 H 7 F 3 O);
NMR data for trans: 19 F NMR (CDCI 3 ), δ = - 59.1 (3F 1 m) ppm; and
1 H NMR (CDCI 3 ) δ = 7.03 (1 H, dq, overlaps J = 12 and 2 Hz), 5.92 (m, 1H), 5.28-5.40 (m, 2H), 5.0(1 H, dq, overlaps, J = 12 and 6 Hz) and 4.3 (2H, dm, J = 5 Hz) ppm.
Example 3
The reaction was carried out in the same manner as described in the Example 2 except that CF 3 CH=CHCI was used in place of CF 3 CH=CHF. CF 3 CH=CHOCH 2 CH=CH 2 was obtained in 50% yield.
Example 4
Polymerization of CF 3 CH=CH(OCH 2 CH=CH 2 ):
Polymerization was conducted essentially the same way as described in J. Polymer Sd A: Polym. Chem (1997) 35, 1593-1604.
To a clean vial containing a Teflon coated magnetic stirbar and a Teflon backed septa was added 15 mg ( 4.5 X 10 "5 mol ) of Co 2 (CO)β in an Argon-filled dry box. To this was added 2.6 ml_ of dry Toluene followed by 20 uL (1.1 x 10-4 mol) of dry diphenylsilane. This was mixed, and, after 15 minutes, the 1-allyloxy-3,3,3-trifluoropropene (0.65 ml_, 5.0 x 10 "3 mol) was added via syringe. The vial was placed on a hot plate at 110 0 C for 2 hrs while stirring. The reaction was quenched with a few drops of triethylamine (TEA) and then the polymer was precipitated in methanol. The polymer was then dried under vacuum at 80 0 C for overnight.
The remaining polymer was determined by 1 H, 19 F NMR to contain the CH 3 groups in the main chain with characteristic broad peaks associated alkyl CH groups and phenyl silyl peaks as endgroups along with characteristic CF 3 groups. The resulting polymer was shown by GPC using polystyrene standards to have a MW = 2,171 (weight average molecular weight) and Dp = 3.01 (degree of polymerization).
Example 5
Polymerization of CF 3 CH=C(OCH 2 CH=CH 2 ) 2 :
Polymerization is conducted in essentially the same manner as in Example 3, with the exception that CF 3 CH=C(OCH 2 CH=CH 2 ) 2 was used instead of i-allyloxy-S.S.S-trifluoropropene.
The present invention has been described with particular reference to the preferred embodiments. It should be understood that variations and modifications thereof can be devised by those skilled in the art without departing from the spirit and scope of the present invention. Accordingly, the present invention embraces all such alternatives, modifications and variations that fall within the scope of the appended claims.
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