Functionalized silicone polymers and processes for making...

Details Functionalized silicone polymers and processes for making... Functionalized silicone polymers and processes for making...

1999-08-12

2001-08-07

Dawson, Robert (Department: 1712)

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

Synthetic resins

From silicon reactant having at least one...

C528S010000, C528S021000, C528S023000, C528S030000, C528S037000, C528S038000, C556S437000

Reexamination Certificate

active

06271330

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to novel protected functionalized silicone polymers, their optionally deprotected analogues, and to processes for preparing silicone polymers.
BACKGROUND OF THE INVENTION
Silicone polymers have many unique properties, such as wide service temperature range; low viscosity change versus temperature; low flammability; shear stability; chemical inertness; oxidative stability; UV stability; low toxicity; and the like. These properties have facilitated their adoption as dielectric, hydraulic, heat transfer, power transmission and damping fluids. Silicone polymers have also found application as additives incorporated into plastics and rubbers as process and release aids, into coatings for flow and level control and into process streams as antifoams. Other unique properties have led to their introduction in acoustical applications such as ultrasonic sensor and sonar buoys. This proliferation of applications has engendered many improvements and refinements of silicone polymers.
Anionic polymerization of cyclosiloxanes, particularly hexamethylcyclotrisiloxane (D
3
) and octamethyltetrasiloxane (D
4
), has been reported previously. It is known that D
3
polymerization does not occur in hydrocarbon solvents. C. L. Frye, R. M. Salinger, F. W. Fearon, J. M. Klosowski and T. deYoung,
J. Org. Chem.,
35, 1308 (1970). Although the anionic species was formed (Bu—Si(CH
3
)
2
)—O—Li
+
), it did not polymerize. Addition of a polar promoter, such as THF, diglyme, or DME then stimulated the polymerization. J. M. Yu, D. Teyssie, R. B. Khalife and S. Boileau, Polymer bulletin, 32, 35-40 (1994). The resultant polymer anion PDMS—O—Li
+
can then be protonated to afford PDMS—OH, capped with a silicon halide (R
3
R
4
R
5
—Si—X) to afford PDMS—O—SiR
3
R
4
R
5
, or coupled with suitable coupling agents (SiCl
4
, Me
2
SiCl
2
, HSi(OMe)
3
) to afford (PDMS)
n
, wherein n is the number of coupling agent functionalities. In spite of considerable synthetic efforts, however, there are few good ways to affix functionality to the termini of the silicone polymers.
SUMMARY OF THE INVENTION
The present invention provides novel protected functionalized silicone polymers. Exemplary protected functionalized silicone polymers of the invention include protected functionalized polymers of formula (I):
(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—(R
1
R
2
Si—O)
v
—H  (I);
protected functionalized polymers of formula (II):
(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—(R
1
R
2
Si—O)
v
—SiR
3
R
4
R
5
  (II);
protected functionalized macromonomers of formula (II′):
(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—(R
1
R
2
Si—O)
v
—SiR
3′
R
4′
R
5′
  (II′);
protected homotelechelic polymers of formula (III):
[(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—(R
1
R
2
Si—O)
v
]
2
—L  (III)
in which each —T—(A—R
7
R
8
R
9
)
m
as defined below is the same; protected heterotelechelic polymers of formula (III′):
[(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—(R
1
R
2
Si—O)
v
]
2
—L  (III′)
in which each —T—(A—R
7
R
8
R
9
)
m
as defined below differs; protected heterotelechelic polymers of formula (III″):
(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—(R
1
R
2
Si—O)
v
—FG  (III″)
in which —T—(A—R
7
R
8
R
9
)
m
and FG differ; and protected radial polymers of the formula (IV):
[(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—(R
1
R
2
Si—O)
v
]
z
—L′  (IV)
in which each —T—(A—R
7
R
8
R
9
)
m
may be the same or different.
In each of Formula (I), (II), (II′), (III), (III′), (III″), and (IV) above:
Q is an unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic compounds, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic compounds into the M-Z linkage;
n is an integer from 0 to 5;
Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl;
T is selected from the group consisting of oxygen, sulfur, and nitrogen groups, and mixtures thereof;
(A—R
7
R
8
R
9
)
m
is a protecting group in which A is an element selected from Group IVa of the Periodic Table of the Elements; R
7
, R
8
, and R
9
are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl; and m is l when T is oxygen or sulfur, and 2 when T is nitrogen;
v is an integer from 2 to 100,000;
R
1
and R
2
are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, and substituted aryl;
R
3
, R
4
, and R
5
are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, fluorinated alkyl, alkyl containing an acetal functionality, alkenyl, substituted alkenyl, aryl, and substituted aryl;
R
3′
, R
4′
, and R
5′
are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, fluorinated alkyl, alkyl containing an acetal functionality, alkenyl, substituted alkenyl, aryl, substituted aryl, and free radically polymerizable groups, with the proviso that at least one R
3′
, R
4′
, and R
5′
is a free radically polymerizable group;
FG is a protected or non-protected functional group;
L is a residue of a difunctional linking agent, such as a SiMe
2
residue derived from the difunctional linking agent SiMe
2
Cl
2
;
L′ is a residue of a multifunctional linking agent, such as a Si residue derived from the multifunctional linking agent SiCl
4
; and
z is an integer from 3 to 20.
The present invention also provides functionalized silicone polymers as described above in which at least one protecting group —(A—R
7
R
8
R
9
)
m
has been removed to liberate the protected functionality T (oxygen, nitrogen, or sulftir). The functional groups can then optionally participate in various copolymerization reactions by reaction of the functional groups on the ends of the polymer arms with selected difunctional or polyfunctional comonomers as described in more detail below to provide a silicone polymer having polymer segments.
The novel polymers of the invention can be optionally hydrogenated to afford other novel polymers. The protecting groups can be removed either prior to or following hydrogenation.
The polymers of the invention can be prepared by anionic polymerization of one or more suitable siloxane monomers of the formula (R
1
R
2
SiO)
y
, wherein R
1
and R
2
are as defined above and y is an integer from 3 to 10, in an inert solvent, optionally containing a polymerization promoter, at a temperature ranging from about −30C to about 250° C., for a period of at least one hour, with one or more protected functionalized initiators having the formula:
M—Q
n
—Z—T—(A—R
7
R
8
R
9
)
m
or
wherein each Q, Z, T, A, R
7
, R
8
, R
9
, m, and n are as defined above; M is an alkali metal; and 1 is an integer from 1 to 7, to produce protected functionalized living silicon polymer anions. The anions are then reacted with a protonating, capping, functionalzing, or coupling agent to provide protected functionalized silicone polymers as described above.
The present invention can provide several advantages over prior silicone polymers and processes. Typically silicone polymers are produced using equilibrium reaction approaches. Such processes, however, provide limited or no control of polymer molecular weight distribution and byproducts. In contrast, the polymers of the present invention are prepared using anionic polymerization techniques. This allows production of polymers having a relatively narrow molecular weight distribution (M
w
,M
n
), typically less than about 1.5, and fewer byproducts.
In addition, the molecular architecture of polymers of the present invention can be precisely controlled. For example, the monomer composition and the length and molecular weight of the arms of multi-branched polymers can be independen

Affiliated with

Also associated with

Rating

Functionalized silicone polymers and processes for making... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Functionalized silicone polymers and processes for making..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Functionalized silicone polymers and processes for making... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2490158