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
2000-01-13
2001-06-26
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S210000, C528S086000, C568S017000, C568S028000, C568S038000, C568S058000, C570S128000, C570S182000, C570S183000
Reexamination Certificate
active
06252001
ABSTRACT:
The present invention relates to ethynyl-substituted aromatic compounds, to polymers of ethynyl-substituted aromatic compounds, and to methods for the preparation and use of the ethynyl-substituted aromatic compounds and polymers thereof.
Polymeric materials which are relatively easy to process and are resistant to temperatures of 300° C. to 450° C. are of interest for preparing laminates, films, coatings, fibers, electronic components and composites. Depending on the specific end-use application, the polymers should exhibit one or more of the following properties: mechanical integrity, low moisture absorption, thermooxidative stability, thermal stability, solvent resistance, hydrolytic stability, resistance to highly acidic or basic solutions, a low coefficient of thermal expansion and a low dielectric constant. For example, in electronics, the material should exhibit a balance of low dielectric constant, good thermal stability and solvent resistance, and a low moisture uptake and coefficient of thermal expansion. In addition, processability can also be important to achieve uniform and defect-free films.
Polyimide resins are one class of materials which are commonly employed for preparing high strength films, fibers, composites, and coatings, including insulative or protective coatings in the electronics industry. However, polyimide resins tend to absorb water and hydrolyze, which can lead to corrosion and migration of metal ions. In addition, polyimides typically exhibit poor planarization and gap fill properties. Non-fluorinated polyimides exhibit undesirably high dielectric constants.
Polyarylenes are thermally stable polymers, but are often difficult to process due to low solubility in common organic solvents. A number of different routes for the preparation of high molecular weight polyphenylenes soluble in an organic solvent have been proposed. For example, U.S. Pat. No. 5,227,457, teaches introducing solubilizing groups such as phenyls onto the polymer chain. Unfortunately, these substituents may also make the resultant polymers sensitive to processing solvents. In another approach, cross-linkable polyphenylene compositions are prepared having a relatively low molecular weight initially, but which cross-link upon heating to form polymers exhibiting solvent resistance. (See, for example, U.S. Pat. Nos. 5,334,668; 5,236,686; 5,169,929; and 5,338,823). However, these compositions may not flow sufficiently to fill gaps, particularly submicron gaps, and planarize surfaces, a critical limitation in many applications, including electronics. Processable polyphenylenes have also been prepared by the reaction of a diacetylene with a biscyclopentadienone. However, the resulting polymers are thermoplastic materials and sensitive to organic solvents used in their processing.
Other polymers which are useful in electronic applications include poly(naphthalenevinylene) containing alternating naphthalene vinylene linkages; (see, for example, Antoun, S.; Gagnon, D. K.; Darasz, F. E.; Lenz, R. W.;
J. Polym. Sci
. Part C:
Polym. Lett.
1986, 24, 503); poly(perylene) or poly(perinaphthalene) or substituted poly(perylene) or poly(perinaphthalene) (see, for example, Lehmann, G.,
Synthetic Metals
1991, 41-43, 1615-1618; and monoaryl ortho-diacetylenes such as phenyl-1,2-bis(phenylacetylene) and their reaction to form linear polynaphthalene (see, for example, John, Jens A. and Tour, James M. in
J. Amer. Chem. Soc.,
1994, (116) 5011-5012. However, these polymers are soluble in organic solvents and thermoplastics material.
In view of the deficiencies in the prior art, it is desirable to provide a compound having the desirable balance of physical and processing properties.
Accordingly, in one aspect, the present invention is an ethynyl aromatic compound of the formula:
(R—C≡C&Parenclosest;
n
Ar—L&Brketopenst;Ar&Parenopenst;C≡C—R)
m
]
q
(I)
wherein each Ar is an aromatic group or inertly-substituted aromatic group; each R is independently hydrogen, an alkyl, aryl or inertly-substituted alkyl or aryl group; L is a covalent bond or a group which links one Ar to at least one other Ar; n and m are integers of at least 2; and q is an integer of at least 1. As such, the ethynyl aromatic compounds of the present invention have four or more ethynyl groups (for example, tetraethynyl aromatic compounds) and are useful as monomers in the preparation of polymers, including their oligomeric precursors.
In another aspect, the present invention is a polymer, including copolymers, which comprise units of:
wherein Ar′ is the residual of the reaction of product of (C≡C&Parenclosest;
n
Ar or Ar¦C≡C)
m
moieties and R and L are as defined above.
In a particularly preferred embodiment, the copolymers of the present invention comprise units of:
wherein Ar′ and R are as hereinbefore defined.
The ethynyl aromatic compounds of the present invention, prior to substantial curing, for example, oligomers or oligomeric precursors of the final polymers, exhibit good solution and melt processability. The resulting thermoset polymers are generally resistant to the high temperatures and solvents commonly used in their processing. In addition, when cross-linked, the polymers exhibit an exceptional balance of solvent resistance and mechanical strength, without loss of electrical properties such as low dielectric constant and dissipation factor. Coatings of the polymer on a variety of substrates can be prepared using conventional techniques such as applying an oligomer of the monomers from solution and thereafter forming the polymer. The polymers can resist high temperatures such as the temperatures required to anneal aluminum which may be as high as 450° C. for cumulative times reaching 2 hours or more. In addition, the polymers can be prepared without volatile materials being formed during polymerization, and at relatively low polymerization and cross-linking temperatures.
Because of their high dielectric strength, resistance to degradation by heat, oxygen and moisture and many chemicals, the polymers of the present invention are particularly useful as capacitor dielectric (films); in displays such as flat panel displays, especially liquid crystal (LC) displays; and as integrated circuit (IC) encapsulates.
As such, the polymers are useful for applications such as laminates, coatings or thin films in making integrated circuits such as microprocessors, memory and multichip-modules, as well as composite structures such as carbon matrices, as high performance matrix resins useful in aerospace and aircraft industries, high temperature adhesives and composite matrices, precursors for fibers or carbon glasses. In another aspect, the present invention is a substrate coated with the described polymer, for example, a computer chip having a coating of the described polymers such as a computer chip having the polymer as an interlayer dielectric insulation coating.
In yet another aspect, the present invention is a laminate having at least two layers at least one layer of which comprises a polymer of the present invention. Laminates of these polymers are particularly useful in electronics, building materials, matrix resins for aircraft and aerospace applications, and for applications requiring heat or weather resistance.
The invention is also a method for making the monomers of Formula (I). The method comprises:
(a) selectively halogenating a polyphenol to halogenate each phenolic ring with a halogen on one of the two available positions ortho to the phenolic —OH group;
(b) converting the phenolic —OH on the resulting poly(ortho-halophenol) to a leaving group which is reactive with terminal ethynyl groups, for example, sulfonate ester; and
(c) reacting the product of step (b) with an ethynyl-containing compound or an ethynyl synthon in the presence of an aryl ethynylation catalyst and an acid acceptor to replace the halogen and the leaving group (for example, trifluoromethylsulfonate) with an ethynyl-containing group.
Those ethynyl-containing groups which are substituted with protecti
Babb David A.
Godschalx James P.
Martin Steven J.
Smith, Jr. Dennis W.
The Dow Chemical Company
Truong Duc
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