Polymerizable halogenated vinyl ethers

Details Polymerizable halogenated vinyl ethers Polymerizable halogenated vinyl ethers

1999-03-18

2001-09-18

Killos, Paul J. (Department: 1623)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic acid esters

C568S607000, C568S615000, C560S105000, C560S125000, C560S184000

Reexamination Certificate

active

06291704

ABSTRACT:

FIELD OF INVENTION
The present invention relates to useful halogenated compounds. More specifically, this invention relates to a family of halogenated vinyl ether compounds, their uses, and the products resulting from their use.
BACKGROUND OF THE INVENTION
Vinyl ethers containing fluorine and also chlorine are of particular interest in coatings applications because they form polymers and copolymers that exhibit beneficial properties, including high chemical and thermal resistance, high electrical resistivity, low surface energy and low refractive index. These properties can be imparted to a coating surface and, consequently, halogenated vinyl ethers are particularly useful in making protective coatings, release coatings, as well as, surfactants, anticorrosion agents, antioxidizing agents and the like.
Some fluorinated chemical compounds are known in the art which contain oxyvinyl groups such as are described in U.S. Pat. No. 2,732,370 under the generic formula C
n
F
2n+1
CH
2
—O—CH═CH
2
. The fluorinated structures near the oxyvinyl group are believed either not to be radiation curable or not to have radiation curable reactivities to the extent desired.
JP 2,000,721 discloses aliphatic fluorinated vinyl ether compounds having the structure R′R″CH—O—CH
2
CH
2
—O—CH═CH
2
wherein R′ is a hydrogen, a lower alkyl group or a polyfluoroalkyl group and R″ is a polyfluoroalkyl group. U.S. Pat. No. 5,012,011 discloses the synthesis of fluorinated vinyl ethers such as CF
3
(CF
2
)
x
R
1
OCH
2
CH(OH)R
2
OCH═CH
2
(R
1
═C1-C20 alkylene, alkoxyethylene, arylene, aryloxyalkylene; R
2
═C1-C100 divalent organic radicals; and x=1-22). Fluorinated vinyl compounds containing a hydroxyl or alkoxy group are described by U.S. Pat. No. 4,559,179. The preparation of H(CF
2
CF
2
)
n
CH
2
OCH═CH
2
(n=2-4) is reported by Sukhinin et al.,
Zh. Vses. khim. O
-
va.,
26(3), 344-5 (1981). Because of the heavily fluorinated structure, adherence to substrates and compatibility with solvents and cosolutes may not be as good as desired.
Moreover, vinyl ether monomers or copolymers that can be cured via ultraviolet (UV) radiation offer even more advantages in coatings and other applications. Photocuring technology has grown rapidly within the last decade. The photocuring process involves the radiation induced polymerization or cross linking of monomers into a three dimensional network and has a number of advantages including the environmentally safe, solvent-free 100% conversion to a desired product, as well as short cycle times and limited space and capital equipment requirements.
In the telecommunications industry, for example, there is a need to develop photocurable compositions for optical wave guide and interconnect applications. In order to be useful in these applications, the photocurable compositions must polymerize to form polymers that are highly transparent at the working wavelength and possess low intrinsic absorption and scattering loss.
U.S. Pat. No. 5,274,174 discloses a new class of photocurable compositions comprised of certain fluorinated monomers, such as diacrylates with perfluoro or perfluoropolyether chains, which possess low intrinsic absorption loss. It is, therefore, possible to make low loss optical interconnects from a photocurable system including these materials.
Fluorine substitution in the polymer structure, however, also induces some other less desirable changes in the polymer's physical properties. One such change is the decrease in refractive index. For a highly fluorinated acrylate photopolymer, the refractive index decreases to the 1.32 region when the H/F mole ratio reaches 0.25. For optical interconnect applications, to avoid loss of light, it is important that the refractive index of the core of a planar waveguide approximate and preferably match that of the optical fiber (generally 1.45).
It is also important to be able to precisely control and fine tune the refractive index of the photopolymer at the working wavelength in optical waveguide and interconnect applications. A desired index of refraction can be produced by mixing photocurable monomers with different refractive indices. Most photopolymers made from conventional photocurable monomers have refractive indices in the region of 1.45-1.55. Depending on the application, it is often desirable to lower a photopolymer's refractive index. One way to do this is to mix low refractive index fluorinated monomers with conventional hydrocarbon-based monomers. Unfortunately, this is difficult to accomplish because of the incompatibility or insolubility of the different monomer systems. Thus, there is a need for photocurable compositions which: (i) possess low intrinsic absorption loss in the near-infrared region; (ii) possess a refractive index approaching traditional optical fibers; and (iii) are compatible with both conventional hydrocarbon-based and highly fluorinated monomers.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a family of halogenated vinyl ether compounds which are useful for making other compounds, including polymeric compounds, having a wide variety of uses. The vinyl ether compounds of the present invention exhibit the beneficial properties of fluorinated monomers and can be utilized to realize the benefits of photocuring processes.
These novel compounds are readily radiation curable and curable by other means. These compounds are soluble with other components (cosolutes) and in numerous recoverable and re-useable solvents, and can be formulated to be of low viscosity when applied.
The novel fluorine containing compounds provide enhanced surface properties, and are fast curing but have indefinite pot life before exposure to radiation or other curing processes. The compounds, when cured, have a low refractive index. The compounds have good substrate adhesion, and can be chemically bonded into other resins, eliminating migratory problems associated with materials which are not bonded into a formulation. In addition, the compounds can be made from commercially available materials by both known and novel processes. The compounds of the invention include oxyvinyl monoethers, oxyvinyl diethers, oxyvinyl monoesters and oxyvinyl diesters of fluorine containing structures.
In general the compounds of the invention have the general formula:
R—O—X—O—CH═CH
2
  (I)
wherein R is radical having a formula selected from: R
1
—C
n
H
m
—, R
1
—C
n
H
m
—C(═O)—, R
1
—C
n
H
m
CH[—O—X—O—CH═CH
2
]—, R
1
—C
n
H
m
CH[—O—X—O—CH═CH
2
]—C(═O)—, R
1
—C
n
H
m
CH[—C(═O)—O—X—O—CH═CH
2
]—, R
1
—C
n
H
m
CH[—C(═O)—O—X—O—CH═CH
2
]—C(═O)—, R
1
—[CFCl—CF
2-
]
p
CH
2
— and HCFCl—CF
2
—, wherein R
1
is hydrogen, an unsubstituted or substituted fluorinated aliphatic radical, an unsubstituted or substituted fluorinated cyclic aliphatic radical, an unsubstituted or substituted fluorinated aromatic radical, an unsubstituted or substituted fluorinated araliphatic radical, or an unsubstituted or substituted fluorinated heterocyclic radical; X is an unsubstituted or substituted aliphatic radical, an unsubstituted or substituted cyclic aliphatic radical, an un-substituted or substituted aromatic radical, an unsubstituted or substituted araliphatic radical, or a unsubstituted or substituted heterocyclic radical; n is between 1 and 6, inclusive; n≦m≦2n; and p is from 1 to 20, inclusive; provided that when R
1
of R
1
—C
n
H
m
— is a fluorinated aliphatic radical, X is not an ethylene or propylene radical.
Fluorinated oxyvinyl diethers of the invention may be represented by the formula:
R
1
C
n
H
m
[OXOCH═CH
2
]
2
Fluorinated oxyvinyl monoesters of the invention may be represented by the formula:
R
1
C
n
H
m
COOXOCH═CH
2
Fluorinated oxyvinyl diesters of the invention may be represented by the formula:
R
1
C
n
H
m
CH[COOXOCH═CH
2
]
2
Another aspect of the present invention provides curable compositions that

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