CN101511763A - Allyloxy trifluoropropene - Google Patents

Abstract

Formula is CF₃CH＝CR¹(OCH₂CR＝CH₂) A process for the preparation of allyloxytrifluoropropene derivatives of (A), wherein R¹Is hydrogen, fluorine and is represented by the formula-OCH₂CR＝CH₂An allyloxy group shown wherein R is hydrogen and methyl, comprising contacting with (ii) a compound represented by the formula CF₃CH＝CR²R³A compound of formula (I) wherein R²Selected from hydrogen, chlorine and fluorine, wherein R³Are chlorine and fluorine; (ii) formula is HOCH₂CR＝CH₂Wherein R is selected from the group consisting of hydrogen and methyl; wherein the contacting is carried out in the presence of a base and optionally a solvent at a temperature and for a length of time sufficient to produce the allyloxytrifluoropropene derivative. Also provided is a method for producing the allyloxytrifluoropropene derivative polymer.

Description

Allyloxytrifluoropropene

Background of the invention

1. Field of invention

The present invention generally relates to processes for the preparation of allyloxytrifluoropropenes and homopolymers and copolymers thereof from fluoroolefins. More particularly, the present invention relates to the preparation of compounds from _CF3CH =CHF or _CF3CH = _CF2 and allyl or methallyl alcohol (eg _CF3CH = _CHOCH2CH = _CH2 , _CF3CH = CFOCH ₂ CH=CH ₂ , CF ₃ CH=C (OCH ₂ CH=CH ₂ ) ₂ and its methallyl derivatives) method.

2. Description of prior art

Compounds containing allyloxy groups are generally used as monomers for the preparation of siloxane polymers or as _CF3 structural units. See eg Polymer Chemistry, (1995) 33(14), 2415-23, J. Polymer Sci.A: Polym. Chem (1997) 35, 1593-1604 and Chem. Commun., (1996), 57-58.

Polymers derived from allyl ethers are described in J.Polym.Sci., Part A, Polym.Chem., 2002, 40, 2583-2590 for UV curing, for films on various surfaces, For use in adhesives, coatings, cladding, etc.

Allyloxypropene of the formula _{CF3CH2CFHOCH2} - _CH = _CH2 is used as a monomer for the preparation of siloxane polymers, such as German Patent DE3138235A1 and J. Fluorine Chem., (2005), 126 _, 281 -288 described.

Relatively little is known about allyloxypropylene polymers in general. US Patent No. 6930159B1 describes certain fluoroallyl ether polymers. However, the structure of the monomers used to prepare the polymer described in this patent is very different from the allyloxypropylene monomer described in the present invention.

Relatively little is known about the allyloxypropylenes described in this 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 derived from CF ₃ CBr = _CH2 and base and catalytic amount of water prepared.

The reaction proceeds by an elimination-addition mechanism by forming trifluoromethylpropene as an intermediate product and then adding allyl alcohol to the resulting trifluoromethylpropene (see Chem. Commun., (1996), 57-58 ).

However, the large-scale preparation of allyloxytrifluoropropene using this method requires the use of _CF3CBr = _CH2 as a starting material, which is expensive and cumbersome to prepare.

Compounds with two allyloxy groups such as CF ₃ CH═C(OCH ₂ CH═CH ₂ ) ₂ and polymers derived therefrom are unknown in the prior art.

Therefore, there is a need in industry to develop economically feasible processes for the preparation of this compound and to exploit its properties and use in various applications.

To this end, the present invention provides a viable and also potentially commercially useful method.

Contents of the invention

The present invention provides a process for the preparation of allyloxytrifluoropropene derivatives represented by the formula:

CF ₃ CH=CR ¹ (OCH ₂ CR=CH ₂ )

in:

^R is selected from hydrogen, fluorine and allyloxy represented by the following formula:

-OCH ₂ CR=CH ₂

wherein R is hydrogen or methyl.

The method includes the following steps:

brings (i) and (ii) into contact;

(i) a compound represented by the following formula:

CF ₃ CH=CR ² R ³

wherein R ^is selected from hydrogen, chlorine and fluorine, wherein ^R is chlorine or fluorine;

(ii) Allyl alcohol derivatives represented by the following 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 for a length of time sufficient to form 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 ;

_CF3CH =CH( _OCH2C ( _CH3 )= _CH2 ); and

CF ₃ CH=CF(OCH ₂ CR=CH ₂ );

wherein R is hydrogen or methyl.

The present invention still further provides the preparation method of polymer, comprises the following steps:

Aggregate (iii) and optionally (iv);

(iii) allyloxytrifluoropropene derivatives selected from compounds represented by the following formula:

_CF3CH =CH( _OCH2CR = _CH2 );

CF ₃ CH=C(OCH ₂ CR=CH ₂ ) ₂ ;

CF ₃ CH=CF(OCH ₂ CR=CH ₂ ); and

any mixture thereof;

wherein R is hydrogen or methyl;

(iv) ethylenically unsaturated comonomers;

wherein the copolymerization step is carried out in the presence of a catalyst (preferably comprising methylphenylsilane and _Co2 (CO) ₈ ) under conditions sufficient to form the copolymer.

The invention also provides homopolymers or copolymers of these allyloxytrifluoropropene derivatives prepared by the polymerization process according to the invention.

The method according to the present invention is feasible and has potential commercial use.

These and other advantages of the present invention will become more apparent from the following detailed description of the preferred embodiments.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

When CF ₃ CH=CF ₂ and allyl alcohol or methallyl alcohol are reacted at 25°C to 35°C using a catalytic amount of base (such as Cs ₂ CO ₃ ) in a polar solvent, the very unexpected formation Instead of the expected carbon-carbon double bond addition product, the main product is the fluorinated product, resulting in _CF3CH =C( _OCH2 -CH= _CH2 ) ₂ (IA).

Even in the presence of only a catalytic amount of base, both vinylidene fluorides in _CF3CH = _CF2 are replaced by allyloxy groups. This is an unknown reaction of vinylidene fluoride, and it was an unexpected reaction.

Temperature appears to play an important role in these reactions. At low temperatures, for example at _{temperatures from} about -20° _C to about 5°C, the addition product of the formula _{CF3CH2CF2OCH2} - _CH═CH2 (IC) is predominantly obtained.

In contrast, when a temperature of about 25°C to about 35°C is used, the major product formed is CF ₃ CH=C(OCH ₂ -CH=CH ₂ ) ₂ (IA); to a lesser extent CF ₃ CH=CF(OCH ₂ -CH=CH ₂ )(IB) (about 5-20%), as shown in Scheme 1 below. Therefore, only trace amounts of the expected addition product (IC) were seen under these experimental conditions.

The above reactions are depicted in Scheme 1 below.

plan 1

In large-scale preparations, the volatiles generated during the reaction can be trapped in a cold trap/scrubber and then neutralized, and the generated HF can be neutralized by washing with aqueous NaOH.

Alternatively, two equivalents of base can be used to neutralize the HF formed during the reaction if only IA is to be produced.

As mentioned earlier, the preparation of compound IIA _CF3CH =CH( _OCH2CH = _CH2 ) using a method using _CF3CBr = _CH2 as starting material has been reported in the literature.

This method is described in more detail in Chem. Commun., 1996, 57-58 and is depicted in Scheme 2 below.

Scenario 2

This problem can be overcome in the present invention using commercially available _CF3CH =CHF and a base, as shown in Scheme 3 below.

Option 3

Alternatively, commercially available _CF3CH =CHCl can also be used instead of _CF3CH =CHF. Typically, bases such _{as Cs2CO3} , _K2CO3 , and sodium or potassium tert-butoxide can be used in _Schemes 1 and 2.

The starting material _CF3CH =CHF can be prepared on _a large scale from commercially available _CF3CH2CF2H according to the method described in US Patent No. _6548719B1 . _CF3CH2CF2H is available from and prepared by Honeywell International, Inc. _{, Morristown} , NJ.

Preferably, _CF3CH = _CF2 is formed _{from CF3CH2CF2H} by chlorination followed by _{dehydrochlorination} , and _CF3CH =CHF is formed from _CF3CH2CF2H by _{dehydrofluorination .}

The contacting step is carried out at a temperature sufficient to form the allyloxytrifluoropropene derivative. Contacting is preferably performed at a temperature of from about 25°C to about 100°C, more preferably from about 25°C to about 50°C, most preferably from about 25°C to about 35°C.

The contacting step is carried out under a pressure sufficient to form the allyloxytrifluoropropene derivative. Contacting is preferably performed at a pressure of from about 0.5 to about 1 atm, most preferably about 1 atm.

The contacting step is performed for a length of time sufficient to form the allyloxytrifluoropropene derivative. Contacting is preferably performed for a period of time ranging from about 5 minutes to about 300 hours, more preferably from about 30 minutes to about 5 hours, more preferably from about 30 minutes to about 2 hours, most preferably about 2 hours.

This contacting step is preferably performed at a temperature of from about 25°C to about 50°C, at a pressure of from about 0.5 atm to about 1 atm, for a period of time ranging from about 30 minutes to about 5 hours.

More preferably, the contacting step is performed at a temperature of about 25°C to about 35°C, at a pressure of about 1 atm, for a period of time of about 30 minutes to about 2 hours.

The process can be a batch process or it can be a continuous process.

The reactor may further comprise a diluent, such as a solvent or a mixture of solvents. Preferably, polar aprotic solvents (eg acetonitrile, dimethylformamide (DMF), dimethylsulfoxide (DMSO)) are used as reaction medium. However, other solvents can also be used, such as mono- and diethers of ethylene glycol, their mono- or diesters, glyme, diglyme, triglyme and tetraglyme .

The method may further comprise one or more of the following steps:

(1) Precipitating the product from the reaction mixture by pouring the crude reaction mixture onto cold water at about 5° C., whereby the product is separated from the lower layer; and

(2) The reaction product was purified by distillation under reduced pressure to obtain a substantially pure product.

In operation, preferably at least 10 wt% of the reactants are converted to products. More preferably, up to at least 80 wt% of the reactants are converted to products, most preferably at least 90 wt% of the reactants are converted to products. Therefore, operation of the process of the invention at high conversion conditions is preferred.

Polymerization can be carried out in substantially the same manner as methods known and described in the prior art, such as described in J. Polymer Sci.A: Polym. Chem. (1997) 35, 1593-1604 and US Patent No. 6930159B1 method. Thus, both monomers can be readily polymerized to form homopolymers under standard polymerization conditions known to those skilled in the art.

Alternatively, if ethylenically unsaturated comonomers are present, these monomers can also be readily polymerized into copolymers.

Depending on the polymerization conditions, this polymer can be obtained as a transparent and white powder.

The allyloxytrifluoropropenes according to the invention are suitable as monomers in the preparation of polymers and copolymers, including the preparation of coatings, especially UV curable coatings.

The following non-limiting examples describe various embodiments of the invention. It is within the ability of one of ordinary skill in the art to select other variables from among the many known in the art without departing from the scope of the present invention.

Therefore, these examples will be used to further explain the present invention, not to limit it.

Experiment details:

All parts and percentages are by weight unless otherwise indicated.

Example 1

1,1-Diallyloxy-3,3,3-trifluoropropene (CF ₃ CH=C(OCH ₂ CH=CH ₂ ) ₂ ):

In stirring acetonitrile (100 mL), allyl alcohol, _CH2 = _CHCH2OH (20 g, 0.34 mol) and catalytic amount of cesium carbonate (1.5 g, 4.6 mmol), add _CF3CH =CF via gas sparger ₂ (0.40 mol). The addition of _CF3CH = _CF2 was such that the temperature of the reaction did not exceed 36°C. After complete addition (30 minutes), the reaction mixture was stirred for 1 hour, poured into 400 ml of cold water, stirred well and the upper layer was separated. The separated organic layer was mixed with water (400ml) and allowed to precipitate, the lower layer was separated, washed with water (50ml), dried ( _MgSO4 ) and filtered to afford the crude product _CF3CH =C( _OCH2CH = _CH2 ) ₂ . The pure product was obtained by distillation under reduced pressure (50-55 °C/8-9 mmHg) as a colorless liquid (25 g, 35% yield).

The structure of the product complies with the following spectral data for

GC/MS data: m/e 208 (M ⁺ C ₉ H ₁₁ F ₃ O ₂ );

¹⁹ F NMR (CDCl ₃ ) δ = -68.6 (3F, d, J _HF = 8 Hz) ppm; and

¹ H NMR (CDCl ₃ ) δ=5.87 (1H, m), 5.71 (1H, m), 5.36-5.09 (4H, m), 4.65 (2H, dt, J=6 and 2Hz), 3.2 (1H, m ), 2.6 (2H, m) ppm.

The other product formed in this reaction is _CF3CH =CF ( _OCH2CH = _CH2 ).

Example 2

1-allyloxy-3,3,3-trifluoropropene (CF ₃ CH=CH(OCH ₂ CH=CH ₂ )):

To stirring acetonitrile (240 mL), allyl alcohol, _CH2 = _CHCH2OH (20 g, 0.34 mol) and sodium tert-butoxide (34.5 g, 0.36 mol), _CF3CH =CFH was added via gas sparger. The addition of _CF3CH =CFH was such that the temperature of the reaction did not exceed 35°C. After complete addition (about 45 minutes), the reaction mixture was stirred for 1 hour, poured into 400 ml of cold water, stirred well, and the upper layer was separated. The separated organic layer was mixed with water (400ml) and allowed to precipitate, the lower layer was separated, washed with water (50ml), dried ( _MgSO4 ) and filtered to provide 42g of product characterized by _CF3CH = _CHOCH2CH = _CH2 , which was 86% pure by GC analysis. The pure product was obtained by distillation under reduced pressure (36-42° C./68 mmHg) to provide the pure product as a colorless liquid (32 g, yield = 62%). The ratio of cis and trans isomers is 96:2.

The structure of the product corresponds to the following spectral data:

GC/ _MS data _: m/e 152 for M ⁺ (M= _C6H7F3O );

NMR data for trans: ¹⁹ F NMR (CDCl ₃ ), δ = -59.1 (3F, m) ppm; and

¹ H NMR (CDCl ₃ ) δ = 7.03 (1H, dq, overlapping, J = 12 and 2 Hz), 5.92 (m, 1H), 5.28-5.40 (m, 2H), 5.0 (1H, dq, overlapping, 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 Example 2, except that _CF3CH =CHCl was used instead of _CF3CH =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 is carried out in substantially the same manner as described in J. Polymer Sci. A: Polym. Chem (1997) 35, 1593-1604.

In a dry box filled with argon, 15 mg (4.5 x 10 ^-5 mol) of Co ₂ (CO) ₈ were added to a clean vial containing a Teflon-coated magnetic stir bar followed by a Teflon-lined septum. 2.6 mL of dry toluene was added thereto, and then 20 µL (1.1×10 ⁻⁴ mol) of dry diphenylsilane was added. This was mixed and after 15 minutes 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° C. for 2 hours while stirring. The reaction was quenched with a few drops of triethylamine (TEA) and the polymer was precipitated in methanol. The polymer was then dried under vacuum at 80°C overnight.

The remaining mixture was determined by ¹ H, ¹⁹ F NMR to contain CH ₃ groups in the main chain, alkyl CH groups with characteristic broad peaks and phenylsilyl groups as terminal groups and characteristic CF ₃ groups. GPC using polystyrene standards showed that the resulting polymer had _Mw = 2171 (weight average molecular weight) and Dp = 3.01 (degree of polymerization).

Example 5

Polymerization of _CF3CH =C( _OCH2CH = _CH2 ) ₂ :

Polymerization was carried out in substantially the same manner as in Example 3, except that _CF3CH =C( _OCH2CH = _CH2 ) ₂ was used instead of 1-allyloxy-3,3,3-trifluoropropene.

The invention has been described with particular reference to the preferred embodiments. It should be understood that changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the present invention. Accordingly, the present invention includes all such alternatives, modifications and variations that fall within the scope of the appended claims.

Claims (23)

1. by the preparation method of the Allyloxytrifluoropropenes shown in the following formula:

CF ₃CH＝CR ¹(OCH ₂CR＝CH ₂)

Wherein:

R ¹Be selected from hydrogen, fluorine and by the allyloxy shown in the following formula:

-OCH ₂CR＝CH ₂

Wherein R is selected from hydrogen and methyl; And

Said method comprising the steps of:

Make (i) and (ii) contact;

(i) by the compound shown in the following formula:

CF ₃CH＝CR ²R ³

R wherein ²Be selected from hydrogen, chlorine and fluorine, wherein R ³Be chlorine or fluorine;

(ii) by the allyl alcohol derivative shown in the following formula:

HOCH ₂CR＝CH ₂

Wherein R is selected from hydrogen and methyl;

Wherein said contact is to carry out being enough in the presence of alkali and the non-essential solvent to generate under the temperature and time length of described Allyloxytrifluoropropenes derivative.

2. the process of claim 1 wherein R ¹Be hydrogen.

3. the process of claim 1 wherein R ¹For by the allyloxy shown in the following formula:

-OCH ₂CR＝CH ₂

Wherein R is a hydrogen.

4. the process of claim 1 wherein R ¹For by the allyloxy shown in the following formula:

-OCH ₂CR＝CH ₂

Wherein R is a methyl.

5. the process of claim 1 wherein that described Allyloxytrifluoropropenes derivative is to comprise CF ₃CH=CF (OCH ₂CR=CH ₂) and CF ₃CH=C (OCH ₂CR=CH ₂) ₂Mixture, wherein R is selected from hydrogen and methyl.

6. the process of claim 1 wherein that described Allyloxytrifluoropropenes derivative is selected from CF ₃CH=CH (OCH ₂CH=CH ₂) and CF ₃CH=C (OCH ₂CH=CH ₂) ₂

7. the process of claim 1 wherein that described Allyloxytrifluoropropenes derivative is selected from CF ₃CH=CH (OCH ₂C (CH ₃)=CH ₂) and CF ₃CH=C (OCH ₂C (CH ₃)=CH ₂) ₂

8. the process of claim 1 wherein described by formula CF ₃CH=CFR ²Shown compound is selected from CF ₃CH=CHF, CF ₃CH=CF ₂And CF ₃CH=CHCl.

9. the method for claim 8, wherein said contact is by formula CF with described ₃CH=CF ₂Shown compound and described allyl alcohol derivative are about that the ratio of 1:1 carries out, to generate by the allyloxy derivative shown in the following formula:

CF ₃CH＝CF(OCH ₂CR＝CH ₂)

Wherein R is selected from hydrogen and methyl.

10. the method for claim 8, wherein said contact is by formula CF with described ₃CH=CF ₂Shown compound and described allyl alcohol derivative are about that the ratio of 1:2 carries out, to generate by the allyloxy derivative shown in the following formula:

CF ₃CH＝C(OCH ₂CR＝CH ₂) ₂

Wherein R is selected from hydrogen and methyl.

11. the process of claim 1 wherein described contact step preferably under about 25 ℃～about 50 ℃ temperature, under the pressure of about 0.5atm～about 1atm, carry out about 30 minutes～about 5 hours time span.

12. the process of claim 1 wherein that the step of described contact is under the pressure under the about 25 ℃～about 35 ℃ temperature, at about 1atm, carries out about 30 minutes～about 2 hours time span.

13. the process of claim 1 wherein that R is a hydrogen.

14. the process of claim 1 wherein that R is a methyl.

15. by the Allyloxytrifluoropropenes derivative shown in the following formula:

CF ₃CH＝C(OCH ₂CH＝CH ₂) ₂。

16. by the Allyloxytrifluoropropenes derivative shown in the following formula:

CF ₃CH＝C(OCH ₂C(CH ₃)＝CH ₂) ₂。

17. by the Allyloxytrifluoropropenes derivative shown in the following formula:

CF ₃CH＝CH(OCH ₂C(CH ₃)＝CH ₂)。

18. by the Allyloxytrifluoropropenes derivative shown in the following formula:

CF ₃CH＝CF(OCH ₂CR＝CH ₂)

Wherein R is selected from hydrogen and methyl.

19. the preparation method of polymkeric substance may further comprise the steps:

Make (iii) and non-essential (iv) polymerization;

(iii) be selected from Allyloxytrifluoropropenes derivative by the compound shown in the following formula:

CF ₃CH＝CH(OCH ₂CR＝CH ₂)；

CF ₃CH＝C(OCH ₂CR＝CH ₂) ₂；

CF ₃CH=CF (OCH ₂CR=CH ₂); With

Its any mixture; Wherein R is selected from hydrogen and methyl;

(iv) ethylenic unsaturated comonomer;

Wherein said copolymerization step is to carry out being enough in the presence of the catalyzer to generate under the condition of described multipolymer.

20. the method for claim 19, wherein said catalyzer comprises aminomethyl phenyl silane and Co ₂(CO) ₈

21. the method for claim 19, wherein said Allyloxytrifluoropropenes derivative is:

CF ₃CH＝C(OCH ₂CH＝CH ₂) ₂。

22. homopolymer by the preparation of the method for claim 19.

23. multipolymer by the preparation of the method for claim 19.