Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1999-12-06
2002-01-15
Moore, Margaret G. (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...
C528S025000, C528S026000, C528S027000, C528S028000
Reexamination Certificate
active
06339131
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention is directed to poly(arylene ether) copolymers, and in particular to poly(phenylene ether)-poly(organosiloxane) copolymers and methods for the synthesis thereof.
Poly(arylene) ethers, and in particular poly(2,6-dimethyl-1,4-phenylene) oxide, are engineering thermoplastics characterized by excellent hydrolytic stability, dimensional stability, and dielectric properties. Poly(arylene) ethers also possess high glass transition temperatures, on the order of greater than 200° C., and high melt viscosity. Because of their high melt viscosity poly(arylene) ethers require high melt processing temperatures, which can lead to undesirable side-reactions such as degradation. Poly(arylene) ethers can also be brittle, and so are often blended with other polymers and copolymers.
Attempts to prepare blends, composites or copolymers of poly(arylene) ethers with poly(organosiloxane) polymers presents difficulties based on the extreme incompatibility of the poly(arylene) ether and poly(organosiloxane). Of these, methods for the preparation of copolymers of poly(arylene) ethers with poly(organosiloxane)s have been extensively investigated. A number of routes rely on activation of either the poly(arylene) ether or the poly(siloxane) moiety. For example, lithiation of a poly(arylene) ether followed by reaction with a chloro-terminated poly(organosiloxane) in solution leads to graft copolymers, as disclosed in JP 61,2525,214 to Matsui et al. This approach is prohibitively expensive for industrial production based on the costs of lithium reagents and the extremely pure conditions required for any solution lithiation process. Shea et al., in U.S. Pat. No. 4,814,392 report copolymer synthesis by reaction of anhydride-activated poly(arylene) ethers with an amino terminated poly(organosiloxane) in melt and in solution. The resulting copolymers are joined by either amide or imide linkages. Reaction of a hydroxy-terminated poly(arylene) ether with an amino-terminated poly(organosiloxane) is disclosed in U.S. Pat. No. 3,668,273 to Kranz et al. and U.S. Pat. No. 3,696,137 to Clark et al.
A reactive extrusion process has been used for preparation of poly(arylene) ether-poly(siloxane) copolymers from epoxy-, carboxy- or amino-functionalized poly(arylene) ethers with epoxy-, carboxy- or amino-functionalized poly(siloxane)s, in U.S. Pat. No. 5,385,984 to Blohm et al. Preparation of tri-block copolymers of poly(arylene ether)-poly(dimethylsiloxane)-poly(arylene ether) is disclosed by R. D. Allen and J. L. Hendrick, in Polym. Bull. Vol. 19, pp. 101-110 (1988). The copolymers were prepared based on phenolic hydroxyl-silylamine condensation via reaction of tertiary amino-stopped polydimethylsiloxane (PDMS) with the phenolic end groups of poly(arylene ether). These polymers are described as useful as additives for polystyrene-based materials.
Alternatively, U.S. Pat. No. 5,204,438 to Snow et al. and U.S. Pat. No. 5,281,686 to Blohm et al. disclose poly(arylene ether)-poly(organosiloxane) copolymers produced by incorporation of a silicon-containing phenol or bisphenol into a poly(arylene ether) chain by oxidative copolymerization with 2,6-xylenol. Graft co-polymers having up to about 20 mol % of poly(siloxane) may be prepared by this method. U.S. Pat. No. 5,357,022 to Banach et al. discloses formation of block copolymers by copolymerization of 2,6-xylenol with a phenol-stopped poly(siloxane) macromer. The macromer was prepared by hydrosilylation of an allylphenol derivative (e.g., eugenol, 2-methoxy-4-allyl-phenol) with dihydride-stopped polysiloxanes.
While suitable for their intended purposes, none of the preceding processes is cost-effective or suitable for industrial-scale preparation of poly(arylene ether)-poly(organosiloxane) copolymers. They use expensive reactants and/or preparation procedures, and the intermediates continue to exhibit thermal instability during processing. Accordingly, there remains a need in the art for methods for the industrially-feasible manufacture of poly(arylene ether)-poly(organosiloxane)copolymers having favorable processing characteristics, and which can be used as engineering thermoplastics, or which can be blended with poly(arylene) ethers or thermoset or rubber formulations to improve processing and other desirable properties such as flame retardancy and/or low smoke generation during burning.
SUMMARY OF THE INVENTION
The above-mentioned drawbacks and disadvantages are alleviated by a method for the synthesis of synthesis of poly(arylene ether)-poly(siloxane) copolymers, comprising
(a) synthesis of a poly(arylene ether) having the structure (1)
wherein each Q
1
is independently hydrogen, a primary or secondary alkyl group having from 1 to about 7 carbon atoms, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each Q
2
is independently hydrogen, halogen, a primary or secondary alkyl group having from 1 to about 7 carbon atoms, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; Q
3
is a hydrogen, a hydroxyl group, or a mixture thereof; and m is an integer having an average value in the range from about 3 to about 300;
(b) solution functionalization of polymer (1) to form functionalized poly(arylene ether) having the structure (2)
wherein Q
1
, Q
2,
and m are as defined above; X is a reactive functional group selected from the group consisting of anhydride, hydroxyl, epoxy, carboxyl, —R
1
OH, R
1
CO
2
R
2
, —R
1
CH
2
═CH
2
, or vinyl, wherein R
1
is a primary or secondary divalent alkyl or haloalkyl group having from 1 to 20 carbons, or an aryl group and R
2
is a primary or secondary alkyl group having from 1 to 10 carbons; and Q4 is hydrogen, X, or a mixture thereof;
(c) reaction of functionalized poly(arylene ether) (2) with a poly(organosiloxane) having structure (3):
wherein each R is independently a primary or secondary alkyl group having from one to 12 carbons, a primary or secondary haloalkyl group having from one to twelve carbons, an aryl group having from 6 to 12 carbons, an aralkyl group having from 7 to 18 carbons, or mixtures thereof; n is an integer having an average value from about 3 to about 500 inclusive; and A is a substituted or unsubstituted aromatic group having from 6 to about 18 carbon atoms, or a primary or secondary divalent saturated or unsaturated alkyl group having from 1 to about 30 carbon atoms; x is zero or one; and Y is a functional group reactive with X, selected from the group consisting of —OH, —CH
2
═CH
2
, epoxy, amino, carboxy, —C(O)CH
2
OH, or hydrogen, to form a poly(arylene ether)-poly(siloxane) copolymer; and
(d) isolation of the product poly(arylene ether)-poly(siloxane) copolymer, wherein the functionalization is in solution, and copolymer synthesis and isolation are effected by first solution and then melt copolymerization.
A further embodiment comprises a poly(arylene ether)-poly(siloxane) copolymer synthesized from a functionalized poly(arylene ether) wherein Q
1
, Q
2
, Q
4
, and X may be oriented in any of the available substitution positions on the aryl groups as generically indicated by structure (4):
wherein Q
1
, Q
2
, Q
4
X, and m are as defined above.
Another embodiment comprises a poly(arylene ether)-poly(siloxane) copolymer synthesized from a functionalized poly(arylene ether) (2) wherein Q
1
, Q
2
, and m are as defined above, and X is a reactive functional group selected from the group consisting of —R
1
OH, R
1
CO
2
R
2
, —R
1
CH
2
═CH
2
or vinyl, wherein R
1
is a primary or secondary divalent alkyl or haloalkyl group having from 1 to 20 carbons, an aryl group and R
2
is a primary or secondary alkyl group having from 1 to 10 carbons; and a poly(organosiloxane) having the structure (2) wherein each of R, A, and x is as defined above, and Y is —OH or —C(O)CH
2
OH when X is —R
1
OH or R
1
CO
2
R
2
; Y is vinyl or allyl when X is vinyl or allyl; or Y is H and x is 0 whe
Cella James A.
Guo Hua
Liska Juraj
Nye Susan Adams
Singh Navjot
General Electric Company
Moore Margaret G.
LandOfFree
Synthesis of poly (arylene ether)-poly(organosiloxane)... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Synthesis of poly (arylene ether)-poly(organosiloxane)..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Synthesis of poly (arylene ether)-poly(organosiloxane)... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2836108