Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phenol – phenol ether – or inorganic phenolate
Reexamination Certificate
2001-08-30
2002-09-24
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From phenol, phenol ether, or inorganic phenolate
C528S212000, C528S214000, C528S50200C, C528S503000
Reexamination Certificate
active
06455663
ABSTRACT:
FEDERALLY SPONSORED RESEARCH
Not Applicable
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a novel process for the manufacture of functionalized polyphenylene ether resins through redistribution with a functionalized phenolic compound in the polyphenylene ether resin polymerization reaction solution without the addition of an added redistribution catalyst or promoter.
The invention also relates to the functionalized polyphenylene ether resin made by the process as well as blends and articles containing the functionalized polyphenylene ether resin made by the process.
2. Brief Description of the Related Art
Polyphenylene ether resins (hereinafter “PPE”) are commercially attractive materials because of their unique combination of physical, chemical, and electrical properties. Furthermore, the combination of PPE with other resins provides blends, which result in additional overall properties such as chemical resistance, high strength, and high flow.
One obstacle to blending PPE with other resins is the lack of compatibility between the resins. This lack of compatibility often manifests itself as delamination and/or poor physical properties such as, for example, poor ductility. One useful method known in the art to improve the compatibility between resins is to generate reaction products between the polymers that will act as compatibilizers for the resins. The reaction products are often thought of as copolymers of the resins.
One challenge in preparing the aforementioned reaction products is the need for reactive sites on the resins that will lead to the formation of reaction products. Some polymers such as polyamides inherently possess both amine and carboxylic acid endgroups that can readily undergo reaction with another resin containing a wide variety of possible reactive moieties. Polymers like PPE contain primarily phenolic endgroups and are in general not sufficiently reactive to result in the aforementioned reaction products in commercially feasible processes.
It should be apparent that methods and processes to introduce functionality into PPE are highly sought after. Redistribution, also known as equilibration, of phenolic compounds containing at least one functional moiety has been shown to afford PPE having desirable functionality. In the redistribution reaction of PPE with phenolic compounds, the PPE are usually split into shorter units with the phenolic compound incorporated in the PPE.
In the redistribution reactions illustrated in the art, the PPE is dissolved in a solvent with the phenolic compound and a catalyst, optionally with a promoter, is add to the reaction mixture. After heating at elevated temperatures, generally between 60° C. and 80° C., the redistributed PPE is isolated.
In order to utilize the redistribution technology in a commercially feasible manner, a process was needed that would minimize the need for additional processes, reaction vessels, and handling of PPE. It should be apparent that a process that would take advantage of the PPE polymerization process and associated mechanical equipment would be extremely advantageous.
SUMMARY OF THE INVENTION
The needs discussed above have been generally satisfied by the discovery of a process for preparing a functionalized PPE through redistribution with a phenolic compound prior to isolation of the PPE from the oxidative coupling reaction mixture and without the addition of a catalyst or a promoter. The oxidative coupling reaction conditions can be adjusted to afford sufficient in situ catalyst for the redistribution reaction.
The description that follows provides further details regarding various embodiments of the invention.
DESCRIPTION OF THE DRAWINGS
Not applicable
DETAILED DESCRIPTION OF THE INVENTION
This invention provides for a process for the preparation of low molecular weight PPE, preferably about 0.05 dl/g and 0.5 dl/g, preferably about 0.08 dl/g and 0.4 dl/g, more preferably having an intrinsic viscosity between about 0.08 dl/g and 0.16 dl/g, by oxidative coupling at least one monovalent phenol species, preferably at least a portion of which have substitution in at least the two ortho positions and hydrogen or halogen in the para position, to produce a PPE having an intrinsic viscosity of greater than about 0.16 dl/g as measured in chloroform at 25° C. using an oxygen containing gas and a complex metal-amine catalyst, preferably a copper (I)-amine catalyst, as the oxidizing agent, redistributing at least one additional phenol species to produce a PPE having an intrinsic viscosity within the range of about 0.05 dl/g and 0.5 dl/g, preferably about 0.08 dl/g and 0.4 dl/g, more preferably about 0.08 dl/g to about 0.16 dl/g, and extracting at least a portion of the metal catalyst as a metal-organic acid salt with an aqueous containing solution, and isolating the PPE through devolatilization of the reaction solvent. In one embodiment, the additional phenol species comprises a functionalized phenol species. In another embodiment, the additional phenol species is equilibrated into the PPE without additional initiator.
The PPE employed in the present invention are known polymers comprising a plurality of structural units of the formula
wherein each structural unit may be the same or different, and in each structural unit, each Q
1
is independently halogen, primary or secondary lower alkyl (i.e., alkyl containing up to 7 carbon atoms), phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each Q
2
is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q
1
. Most often, each Q
1
is alkyl or phenyl, especially C
1-4
alkyl, and each Q
2
is hydrogen.
Both homopolymer and copolymer PPE are included. The preferred homopolymers are those containing 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include random copolymers containing such units in combination with (for example) 2,3,6-trimethyl-1,4-phenylene ether units. Also included are PPE containing moieties prepared by grafting vinyl monomers or polymers such as polystyrenes and elastomers, as well as coupled PPE in which coupling agents such as low molecular weight polycarbonates, quinones, heterocycles and formals undergo reaction in known manner with the hydroxy groups of two poly(phenylene ether) chains to produce a higher molecular weight polymer, provided a substantial proportion of free OH groups remains.
The PPE are typically prepared by the oxidative coupling of at least one monohydroxyaromatic compound such as 2,6-xylenol, 2,3,6-trimethylphenol, or mixtures of the foregoing. Catalyst systems are generally employed for such coupling and they typically contain at least one heavy metal compound such as a copper, manganese, or cobalt compound, usually in combination with various other materials.
It will be apparent to those skilled in the art from the foregoing that the PPE contemplated in the present invention include all those presently known, irrespective of variations in structural units or ancillary chemical features.
The polymerization of the phenolic monomer may be carried out by adding the phenolic monomer or monomers to a suitable reaction solvent and preferably, a copper-amine catalyst. It is preferred to carry out the polymerization in the presence of a cupric salt-secondary amine catalyst such as, for example, cupric chloride and di-n-butylamine. The polymerizations are advantageously carried out in the presence of an inorganic alkali metal bromide or an alkaline earth metal bromide. The inorganic bromides may be used at a level of from about 0.1 mole to about 150 moles per 100 moles of phenolic monomer. These catalyst materials are described in U.S. Pat. No. 3,733,299 (Cooper et al.). Tetraalkylammonium salts may also be employed as promoters if desired. These promoters are disclosed in U.S. Pat. No. 3,988,297 (Bennett et al.).
The primary, secondary or tertiary amine components of the catalyst complex generally co
Braat Adrianus J. F. M.
Engelbrecht Hugo G. E.
Liska Juraj
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