Fluorine-containing organosilicon compound and process of producing the same

A fluorine-containing organosilicon compound having the formula (1): ##STR1## wherein X is a hydrolizable group, R.sup.1 is a monovalent organic group, R.sup.2 is a methyl group or a hydrogen atom, n is an integer of 1, 2 or 3, and m is an integer of 0 or 1, and a process of producing said compound. The compound may be used as a silane coupling agent capable of improving not only the strength of laminated sheets of polyester resin and glass and polyester resin concrete but also water and heat resistances.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a fluorine-containing organosilicon 
compound containing in the molecule a hydrolizable group bonded to a 
silicon and an acryloxyl or methacryloxyl group. 
2. Description of the Prior Art 
An organosilicon compound having the formula (4): 
##STR2## 
wherein X is a hydrolizable group, R.sup.6 is a monovalent organic group, 
R.sup.7 is a methyl group or a hydrogen atom and n is an integer of 1, 2 
or 3, for example, has a silicon-bonded hydrolizable group X-Si group that 
can react with glass, metal or silica and an acryloxyl or methacryloxyl 
group that can react with organic materials such as synthetic resins, and 
is known to be used in the prior art as a silane coupling agent for 
laminated sheets of polyester resin and glass for its high performance in 
improving the mechanical strength and electric properties. The compound is 
also known to be highly effective in improving the strength when added to 
polyester resin concrete. 
However, water resistance and heat resistance obtained by the prior art 
organosilicon compound were insufficient. 
SUMMARY OF THE INVENTION 
The present invention therefore aims at providing a novel organosilicon 
compound which, when added to synthetic resins or organic materials as a 
silane coupling agent, improves not only mechanical strength and electric 
properties but both water and heat resistances as well. 
In order to achieve the object of the invention, the present invention 
provides a fluorine-containing organosilicon compound having the formula 
(1): 
##STR3## 
wherein X is a hydrolizable group, R.sup.1 is a monovalent organic group, 
R.sup.2 is a methyl group or a hydrogen atom, n is an integer of 1, 2 or 
3, and m an integer of 0 or 1. 
The present invention also provides a process of producing a 
fluorine-containing organosilicon compound having the formula (1) above 
which comprises effecting addition-reaction of a fluorine-containing 
organic compound having the formula (2): 
##STR4## 
wherein R.sup.2 is a methyl group or a hydrogen atom, and m is an integer 
of 0 or 1, with a silane compound having the general formula (3): 
EQU X.sub.n (R.sup.1).sub.3-n SiH 
wherein X is a hydrolizable group, R.sup.1 is a monovalent organic group, n 
is an integer of 1, 2 or 3, in the presence of a transition metal or its 
compound. 
The fluorine-containing organosilicon compound according to the present 
invention is a novel compound that can be used as a coupling agent for 
laminated sheets of polyester resin and glass and to improve the strength 
of polyester resin concrete. It is expected to contribute to improving not 
only the mechanical strength and electric properties but also water and 
heat resistances.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
Fluorine-containing Organosilicon Compound 
The fluorine-containing organosilicon compound of the present invention 
contains a fluorine-containing group --C(CF.sub.3).sub.2 -- and is 
represented by the formula (1) above. 
Examples of the hydrolizable group X in the formula (1) include a halogen 
atom of fluorine, chlorine, bromine or iodine, an alkoxy group represented 
by --OR.sup.3 and an amino group expressed by --NR.sup.4 R.sup.5, wherein 
R.sup.3 is a monovalent organic group such as an alkyl group having 1 to 
10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl and n-butyl 
groups, a fluoroalkyl group having 2 to 15 carbon atoms such as 
trifluoroethyl group, an acetyl group, an acyl group such as propyonyl 
group, and an alkenyl group having 2 to 5 carbon atoms such as isopropenyl 
group. R.sup.4 and R.sup.5 are each a monovalent organic group which may 
be the same or different; for example an alkyl group having 1 to 10 carbon 
atoms such as methyl group, ethyl group or isopropyl group. 
Examples of monovalent organic compound R.sup.1 in the formula (1) 
specifically include an alkyl group having 1 to 10 carbon atoms such as 
methyl group, ethyl group and n-propyl group, an aryl group having 6 to 10 
carbon atoms such as phenyl group and toluyl group, and a fluoroalkyl 
group having 3 to 15 carbon atoms such as trifluoropropyl group. 
Production Process 
The fluorine-containing organosilicon compound of the present invention can 
be obtained by the process which comprises effecting addition-reaction of 
said fluorine-containing organic compound having the formula (2) above 
with a silane compound having the formula (3) above in the presence of a 
catalyst. 
The compound having the general formula (2) can be produced by, for 
example, reacting an alcohol having the formula (5): 
##STR5## 
wherein m is as defined above, with an acrylic acid or methacrylic acid in 
the presence of a dehydrating agent such as fuming sulfuric acid. It can 
also be obtained by reacting the alcohol represented by the formula (5) 
above with an alkyl lithium to produce a lithium alkoxide, which in turn 
is reacted with an acrylic chloride or methacrylic chloride. 
Examples of a catalyst used in the addition-reaction of the 
fluorine-containing organic compound of the formula (2) with the silane 
compound of the formula (3) include transition metals and their compounds 
such as a salt or complex, and more particularly, metals such as Pt, Rh 
and Pd. Examples of salts or complexes of the transition metals include an 
olefin modified complex of H.sub.2 PtCl.sub.6, alcohol modified complex of 
H.sub.2 PtCl.sub.6, vinyl-siloxane modified complex of H.sub.2 PtCl.sub.6, 
RhCl.sub.3, Rh(CH.sub.3 COCHCOCH.sub.3).sub.3, Rh(PPh.sub.3).sub.3 Cl, 
Rh(PPh.sub.3).sub.3 Br, Rh.sub.2 (AcO).sub.4, Rh(PPh.sub.3).sub.2 (CO)Cl, 
Rh(.eta..sup.4 --C.sub.7 H.sub.8)Cl, Rh(CH.sub.3 
COCHCOCH.sub.3)(CO).sub.2, Rh.sub.4 (CO).sub.12, Rh(CO).sub.16, 
Rh(PPh.sub.3).sub.3 (CO)H, (NH.sub.4).sub.2 PdCl.sub.6, (NH.sub.4).sub.2 
PdCl.sub.4, Pd(CH.sub.3 COCHCOCH.sub.3).sub.2, Pd(PhCN).sub.2 Cl2, 
Pd(PPh.sub.3).sub.2 Cl.sub.2, and Pd(PPh.sub.3).sub.4 wherein Ph is the 
phenyl group and Ac represents the acetyl group. 
For the synthesis of the fluorine-containing organosilicon compound 
according to the present invention, a silane compound having the formula 
(3) and a catalyst for addition-reaction are charged in a reaction vessel, 
and added dropwise with a fluorine-containing organic compound having the 
general formula (2) while maintaining the mixture at a prescribed 
temperature to give rise to addition-reaction. The reaction temperature is 
normally between 30.degree. and 150.degree. C., and more preferably 
between 60.degree. and 130.degree. C. Progress of the reaction can be 
monitored by measuring the amount of the starting materials consumed and 
the amount of the reaction product formed using chromatographic analysis 
method. Normally, the addition-reaction is completed in about 30 minutes 
to 48 hours. If the consumption of the starting materials stops before the 
completion of the addition-reaction, the reaction can be resumed by adding 
the catalyst. Upon completion, the reaction mixture can be distilled to 
isolate and purify the fluorine-containing organosilicon compound. There 
are no particular restrictions regarding the order of charging said silane 
compound, fluorine-containing organic compound and catalyst. It is 
therefore possible to drop the silane compound of the formula (3) to the 
reaction vessel in which the fluorine-containing organosilicon compound of 
the formula (2) and the catalyst for addition-reaction have been charged. 
It is also -possible to charge the fluorine-containing organic compound, 
silane compound and catalyst in a reaction vessel in advance, and the 
reaction vessel may be heated to a given temperature to carry out the 
addition-reaction. Because the addition-reaction is exothermic, care 
should always be taken in the reaction temperature control. 
It should also be noted that a polymerization inhibitor such as 
2,6-di-tert-butyl-p-cresol should preferably be used during the 
addition-reaction to prevent excessive polymerization reaction. 
Said silane compound and the fluorine-containing organic compound are used 
in such amounts that 0.8 to 2 mols, more preferably 1 to 1.5 mols, of the 
silane compound may be present per mol of the fluorine-containing organic 
compound. The catalyst is normally used in an amount ranging between 
1.times.10.sup.-6 to 1.times.10.sup.-2 mol, more preferably between 
1.times.10.sup.-5 to 1.times.10.sup.-3 mol. 
A solvent may be optionally used in the addition-reaction, but the reaction 
normally proceeds smoothly without a solvent. 
According to the present invention, a fluorine-containing organosilicon 
compound in which the hydrolizable group X is an alkoxy group represented 
by --OR.sup.3 (wherein R.sup.3 is as defined above) may be produced by 
reacting a fluorine-containing organosilicon compound of the invention 
wherein X is a halogen atom with an alcohol expressed by R.sup.3 OH 
(wherein R.sup.3 is as defined above) (so-called alkoxylation reaction). 
As this reaction generates hydrogen halide, it is preferable to use a 
scavenger such as tertiary amines, urea, metal alkoxides, orthoformates 
and epoxy compounds. 
According to the present invention, a fluorine-containing organosilicon 
compound in which the hydrolizable group X is an amino group represented 
by --NR.sup.4 R.sup.5 (wherein R.sup.4 and R.sup.5 are as defined above) 
may be obtained by reacting a fluorine-containing organosilicon compound 
of the present invention wherein X is a halogen atom with a secondary 
amine compound represented by NHR.sup.4 R.sup.5 (wherein R.sup.4 and 
R.sup.5 are as defined above). This reaction also generates hydrogen 
halide, but in this case, the starting material NHR.sup.4 R.sup.5 also 
acts as its scavenger. 
Use 
The fluorine-containing organosilicon compound of the present invention 
contains a hydrolizable group which is reactive with glass, metal or 
silica, and an acryloxyl group or methacryloxyl group which is reactive 
with an organic material such as synthetic resins, and further contains a 
fluorine-containing group. Thus, it can be used as a silane coupling agent 
for laminated sheets of polyester resin and glass to improve their 
mechanical strength and electric properties as well as water and heat 
resistances. By adding the compound of the present invention to polyester 
resin concrete, it not only improves the strength but water and heat 
resistances as well. 
EXAMPLES 
Example 1 
Into a 100 ml stainless steel resisting pressure vessel are charged 19.0 g 
(0.069 mol) of a fluorine-containing organic compound having the formula: 
##STR6## 
16.2 g (0.120 mol) of Cl.sub.3 SiH, 0.32 g (Pt: 3.2.times.10.sup.-5 mol) 
of 2-ethylhexanol modified complex of H.sub.2 PtCl.sub.6 (Pt 
concentration: 2 weight %) and 0.003 g of B.H.T 
(2,6-di-tert-butyl-p-cresol) as a polymerizaion inhibitor, and they were 
reacted by heating at 115.degree. C. for 16 hours. The reaction mixture 
was distilled in vacuum to obtain 14.7 g of a product at 
88.degree.-90.degree. C./4 mmHg (yield: 52%). 
The compound thus obtained was subjected to .sup.1 H-NMR, infrared 
absorption spectroscopy, element analysis and mass spectrometry. The 
results are shown below. 
The results given below indicate that the compound obtained is represented 
by the following formula: 
##STR7## 
(1) .sup.1 H-NMR; solvent CCl.sub.4, internal standard TMS 1.5 ppm (m, 4H, 
CH.sub.2, --CH.sub.2 --CH.sub.2, Si--CH.sub.2); 1.9 ppm (S, 3H, --CH.sub.3 
--); 2.5 ppm (m, 2H, --CH.sub.2 --C(CF.sub.3).sub.2); 5.7 ppm (s, 1H, 
##STR8## 
6.0 ppm (s, 1H, 
##STR9## 
(2) Infrared absorption spectroscopy; KBr method 1760 (cm.sup.-1) (C=0); 
1260, 1220, 1140, 1030 (cm.sup.-1); 590 (cm.sup.-1) (Si--Cl). 
(3) Element analysis: as C.sub.10 H.sub.11 O.sub.2 Cl.sub.3 F.sub.6 Si 
______________________________________ 
C(%) H(%) F(%) Si(%) 
______________________________________ 
Calculated 29.18 2.69 27.69 6.82 
Found 29.45 2.80 27.11 6.05 
______________________________________ 
(4) MS: 410 (M.sup.+). 
EXAMPLE 2 
Into a 50 ml flask equipped with a thermometer, a coiled condenser and a 
magnetic stirrer were charged 3.0 g (0.0941 mol) of methanol and 2.8 g 
(0.0466 mol) of urea. Droplets of the fluorine-containing organosilicon 
compound obtained in Example 1 and having the formula: 
##STR10## 
in an amount of 11.7 g (0.0285 mol) were gradually added to the mixture 
under nitrogen stream using a dropping funnel. The temperature inside the 
flask during dropping rose from 25.degree. C. to 35.degree. C. The 
reaction was continued for one hour under agitation, and a urea salt in a 
slurry form was separated. The residual mixture was distilled in vacuum to 
obtain 9.13 g of the reaction product at 100.degree.-101.degree. C./4 mmHg 
(yield: 80.4%). 
The compound thus obtained was subjected to .sup.1 H-NMR, infrared 
absorption spectroscopy, element analysis and mass spectrometry. The 
results are shown below. 
The results indicate that the compound obtained is represented by the 
following formula: 
##STR11## 
(1) .sup.1 H-NMR: solvent CCl.sub.4, internal standard TMS 0.7 ppm (m, 2H, 
CH.sub.2 --Si); 1.4 ppm (m, 2H, CH.sub.2 --CH.sub.2 --CH.sub.2); 1.9 ppm 
(s, 3H, C--CH.sub.3); 2.5 ppm (m, 2H, 
##STR12## 
(2) Infrared absorption spectroscopy; KBr method 2950 (cm.sup.-1); 2850 
(cm.sup.-1) [C--H(Si--OCH.sub.3)]; 1760 (cm.sup.-1) (C=0); 1320, 1260, 
1220, 1030, 820 (cm.sup.-1). 
(3) Element analysis: as C.sub.13 H.sub.20 O.sub.5 F.sub.6 Si 
______________________________________ 
C(%) H(%) F(%) Si(%) 
______________________________________ 
Calculated 39.20 5.06 28.61 7.05 
Found 39.96 5.57 28.09 7.51 
______________________________________ 
(4) MS: 398 (M.sup.+).