Fluoroalkylsubstituted cyclotrisiloxanes, their use for...

Details Fluoroalkylsubstituted cyclotrisiloxanes, their use for... Fluoroalkylsubstituted cyclotrisiloxanes, their use for...

1999-10-12

2001-09-18

Dawson, Robert (Department: 1712)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From silicon reactant having at least one...

C528S025000, C556S448000, C556S454000, C556S479000

Reexamination Certificate

active

06291623

ABSTRACT:

This invention concerns new fluoroalkylsubstituted cyclotrisiloxanes, new homopolymers and block coplymers derived from said cyclotrisiloxanes, and their preparation.
BACKGROUND OF THE INVENTION
The publications and other materials used herein to illuminate the background of the invention, and in particular, cases to provide additional details with respect to the practice, are incorporated by reference.
The only commercially available fluoroalkylsiloxane is poly(trifluoropropylmethylsiloxane). It is prepared via anionic or cationic ring opening polymerization of cyclotri(trifluoropropylmethylsiloxane). Crystalline fluoroalkylmethylpolysiloxane has been obtained from the monomer of pure cis-isomer.
1,2
Precursor of cyclotri(trifluoropropylmethylsiloxane) is trifluoropropylmethyldichlorosilane, prepared usually by platinum (H
2
PtCl
6
) catalyzed hydrosilation reaction between methyldichlorosilane and 3,3,3-trifluoropropene.
3
The reaction has also been applied to the preparation of bis(trifluoropropyl)dichlorosilane using dichlorosilane instead of methyldichlorosilane. Unlike non-fluorinated alkenes (ethene, propene) which give good yields between 60 and 79%
4,
3,3,3-trifluoropropene gives only low yields, 26 . . . 36% in preparation of disubstituted silicon.
5
Bis (1H, 1H, 2H-perfluorohexyl)dichlorosiloxane has been obtained in 42% overall yield via a two step process, where both Co
2
(CO)
8
and platinium cyclovinylmethylsiloxane complex were used for the hydrosilylation reaction between dichlorosilane and 1H, 1H, 2H-perfluorohexane.
6
High yields have been obtained via UV-light catalyzed radical reaction,
7,8,9
3-(Pentafluorophenyl)ethylmethyldichlorosilane has been prepared in 70% yield from methyldichlorosilane and pentafluorostyrene.
10
Cyclics having both dimethylsiloxy and 3-(pentafluorphenyl)ethylmethylsiloxane units were prepared by Matsui et al
11
via hydrosilation reaction between pentafluorostyrene and cyclics containing dimethylsiloxy and methylsiloxy units. Polymerization of these cyclic was catalyzed by tetramethylammonium hydroxide, polymer M
w
/M
n
=38,000/21,000 g/mol. See Scheme 1.
Matsui also prepared hetero cyclics of dimethyldichlorosilane and 3,3,3-trifluoropropylmethyldichlorosilane or 1H, 1H,2H,2H-perfluorodecylmethyldichlorosilane via co-hydrolysis in ether. Polymerization was carried out as in the previous case.
The European patent publication EP 0563902 by Dow Corning
12
describes a method for preparation of block co-copolymers from D
3
and D
3
-type cyclic monomers having 1H,1H,2H,2H-perfluoroalkylmethylsiloxane groups and/or vinylmethylsiloxane groups. See Scheme 2.
U.S. Pat. No. 4,814,418
13
describes a similar procedure, but instead of sequential addition of monomers, they add them simultaneously, resulting a non-block copolymer. The patent covers the use of cyclic trimers of {[F(CF
2
)
a
C
2
H
4
](CH
3
)SiO}
3
and {[H(CF
2
)
a
C
2
H
4
](CH
3
)SiO}
3
(a=1 . . . 16) with or without D
x
(x=3 . . . 6) and/or D
x
Mevi
(x=3 . . . 6, Vi=alkenyl group). The patent also claims higher molecular weight polymers by use of a phase transfer catalyst/initiator combination instead of initiator alone. Phase transfer catalyst is a quaternary ammonium or phosphonium salt and can be presented by the formulas R
4
N
+
X
−
or R
4
P
+
X
−
, where R is alkyl, cycloalkyl or phenyl group and X
−
is Cl
−
or Br
−
.
OBJECTS AND SUMMARY OF THE INVENTION
The aim of this invention is to provide novel fluoroalkylsubstituted cyclotrisiloxanes and novel polymers made thereof, either homopolymers made by anionic or cationic polymerization, or block copolymers made by anionic polymerization of said fluoroalkylsubstituted cyclotrisiloxanes.
Thus, according to one aspect, this invention concerns novel fluoroalkyl substituted cyclotrisiloxane of the formula (Ia) and (Ib)
wherein R is a lower alkyl of 1 to 4 carbon atoms and R
f
has the formula (CH
2
)
2
—(CR′
2
)
n
—CR′
3
, wherein all or some of the R′ substituents are F, the remaining R′ substituents being H, and n is an integer varying from 0 to 8, provided that R
f
cannot be (CH
2
)
2
—CF
3
in the compound of formula (Ib).
According to another aspect, this invention concerns a method for the preparation of a homopolymer, wherein said compound of formula (Ia) or (Ib) is subjected to anionic or cationic polymerisation in bulk or in a suitable solvent to give said homopolymer.
According to a further aspect, the invention concerns a method for the preparation of a block copolymer or random copolymer, wherein at least two of the compounds of formula (Ia), (Ib) and a cyclosiloxane (II),
wherein y is 3, 4 or 5 and all or some of the R
1
substituents are alkyl of 1 to 4 carbon atoms, vinyl or phenyl, or wherein one R
1
is R
f
as defined before and the remaining R
1
substituents are alkyl of 1 to 4 C-atoms, vinyl or phenyl,
are subjected to anionic or cationic polymerisation to give said block or random copolymer.
The invention concerns also the novel homopolymers, block copolymers and random copolymers.
DETAILED DESCRIPTION OF THE INVENTION
The most preferable compounds of formula Ia and Ib are those where each of the R′ substituents in (CH
2
)
2
—(CR′
2
)
n
—CR′
3
(R
f
) is F.
The polymerization can be carried out either in bulk or in a suitable solvent.
The cationic polymerization is preferably initiated by trifluoromethane sulfonic acid (triflic acid).
The anionic polymerization is preferably initiated by a lithium containing base, for example dilithium diphenylsilanolate or dilithium tetramethyldisiloxanolate.
The compounds Ia, Ib and II can be polymerized in any order with respect to each other. They can also be mixed with each other before the initiation of the polymerization.
The invention will be described more in detail in The Experimental section in the following non-limiting examples.
Experimental
Spectroscopic Analysis
1
H,
13
C,
19
F and
29
Si NMR spectra were obtained on a Bruker AMX-500 MHz spectrometer. Forty percent w/v solutions in acetone-d
6
were used to obtain the spectra.
13
C and
19
F NMR spectra were obtained with broad band proton decoupling. An inverse gate decoupling pulse sequence with a 60 sec delay was used to acquire
29
Si NMR spectra. Tetramethylsilane (TMS) was used as an internal standard for
1
H,
13
C,
19
F and
29
Si NMR spectra, and CFCl
3
for
19
F spectra. IR spectra of neat films on NaCl plates were recorded on a Perkin Elmer Spectrum 2000 FT-IR spectrometer.


REFERENCES:
patent: 3070617 (1962-12-01), Holbrook
patent: 3364244 (1968-01-01), Selin
patent: 5350824 (1994-09-01), Kobayashi
Jyri K. Paulasaari and William P. Weber, “Preparation and polymerization of 1,3,3,5,5-pentamethyl-1-(2′-perfluorophenyl-1′,1′,2′,2′-tetrahydroethyl)cyclostrisiloxane (I). Comparison of anionic and cationic polymerization of I”, 39Polym. Prepr., 583-584 (1998) (Abstract).
Jyri K. Paulasaari and William P. Weber, “Preparation and Orthogonal Polymerizations of 1-Hydrido-1-vinyldimethylsiloxy-3,3,5,5-tetramethylcyclotrisiloxane”, 32Macromolecules5217-5221 (1999) (Abstract).
Jyri K. Paulasaari and William P. Weber, “Polymerization of 1-Hydrido-1-vinyldimethylsiloxy-3,3,5,5-tetramethylcyclotrisiloxane”, 40Polym. Prepr. 801-802 (1999) (Abstract).
Jyri K. Paulasaari and William P. Weber, “Preparation of Highly Regular Poly(1-Hydrido-1,3,3,5,5-pentamethyltrisiloxane) and Its Chemical Modification by Hydroxsilylation”, 32Macromolecules6574-6577 (1999) (Abstract).
Rozga-Wijas et al., “Controlled Synthesis of Siloxane Coploymers Having an Organosulfur Group by Polymerization of Cyclotrisiloxanes with Mixed Units”, 29Macromolecules, 2711-2720 (1996).
Vasilenko et al., “Hyperbranched H-functional polydimethylsiloxanes based on macromonomers”, STN International, File CAPLUS, Accession No. 1998: 142499, Book of Abstracts, 215th ACS National Meeting, Dallas, Mar. 29-Apr. 2(1998) POLY-254 Publisher: American

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