Protected functionalized diene and alkenyl substituted...

Details Protected functionalized diene and alkenyl substituted... Protected functionalized diene and alkenyl substituted...

2000-01-10

2002-02-05

Dawson, Robert (Department: 1712)

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

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

C525S100000, C525S101000, C525S103000, C525S106000, C525S474000, C525S477000, C525S479000, C525S326500, C525S342000, C525S941000

Reexamination Certificate

active

06344521

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to novel protected functionalized diene and alkenylsubstituted aromatic/silicone triblock copolymers, their optionally hydrogenated analogues, their optionally deprotected analogues, and processes for making the same.
BACKGROUND OF THE INVENTION
Silicone polymers have many unique properties, including wide service temperature range; low viscosity change vs. temperature; low flammability; shear stability; chemical inertness; oxidative stability; UV stability; low toxicity; and the like. These and other properties have facilitated the adoption of silicone polymers as dielectric, hydraulic, heat transfer, power transmission and damping fluids. Silicone polymers have also found applications 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.
Thermoplastic elastomers typically consist of a non-compliant, high modulus polymeric “hard segment” which is covalently bonded to a “soft” elastomeric segment comprised of polymer which is significantly above its glass transition temperature during use. These materials offer a useful combination of elastomeric properties without vulcanization.
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. See 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. See 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
, where n=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.
Conventional hydrocarbon-based polymers generally lack mechanisms for bringing about crosslinking via low-temperature or ambient temperature cure (e.g., moisture cure or addition-cure). Such cure pathways are known in the case of siloxane polymers, and the development of such facile cure mechanisms for organic systems is highly desirable.
Unfunctionalized hydrocarbon/silicone diblock copolymers have been prepared by anionic techniques, as described in U.S. Pat. No. 5,618,903,
Makromol. Chem.,
176, 1641 (1975),
Polym. Sci., Part B: Polym. Phys.,
30, 727 (1992),
Inorg. and Organomet. Polym.,
1, 397 (1991), and
Macromolecules,
29, 3397 (1996). Symmetrical, homotelechelic, functionalized hydrocarbon/silicone block copolymers were also prepared anionically, as detailed in U.S. Pat. No. 5,561,210. Symmetrical homotelechelic functionalized hydrocarbon/silicon block copolymers were also prepared anionically, as detailed in U.S. Pat. No. 5,561,210.
SUMMARY OF THE INVENTION
The present invention provides novel protected functionalized heterotelechelic silicone block copolymers having the formula (I) or (II):
(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—C′—(R
1
R
2
Si—O)
v
—H  (I);
(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—C′—(R
1
R
2
Si—O)
v
—SiR
3
R
4
R
5
  (II);
protected macromonomers of formula (II′):
(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—C′—(R
1
R
2
Si—O)
v
—SiR
3′
R
4′
R
5′
  (II′);
protected homotelechelic copolymers of formula (III):
[(R7R
8
R
9
—A)
m
—T—Z—Q
n
—C′—(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 copolymers of the formula (III′):
[(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—C′—(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 different and each C′ can be the same or different;
protected heterotelechelic copolymers of the formula (III″):
(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—C′—(R
1
R
2
Si—O)
v
—FG  (III″)
in which FG and T—(A—R
7
R
8
R
9
)
m
are different; and protected radial copolymers of the formula (IV) or (V):
[(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—C′—(R
1
R
2
Si—O)
v
]
z
—L′  (IV)
or
[(R
7
R
8
R
9
—A)
m
—T—Z—Q
n
—C′]
z
—DVB—[(R
1
R
2
Si—O)
v
—SiR
3
R
4
R
5
]
y
  (V)
in which each T—(A—R
7
R
8
R
9
)
m
and each C′ can be the same or different,
wherein:
Q is an unsaturated or hydrogenated 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;
C′ is a hydrogenated or unsaturated block derived by anionic polymerization of one or more conjugated dienes, for example 1,3-butadiene or isoprene, or one or more alkenylsubstituted aromatic compounds, such as styrene or alpha-methylstyrene, or mixtures of one or more conjugated dienes and one or more alkenylsubstituted aromatic compounds;
DVB is radial polymer core prepared by addition of protected functionalized polymer anions to an alkenylsubstituted aromatic compound which contains two or more independently polymerizable vinyl groups, such as meta-divinylbenzene or para-divinylbenzene;
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 or when T is nitrogen, R
9
is optionally a —(CR′R′)
l
-group linking two A wherein each R′ is each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, and substituted cycloalkyl, and 1 is an integer from 1 to 7; and m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen;
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;
v is an integer from 2 to 100,000;
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 of 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
y and z are each independently integers from 2 to 30.

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