Stock material or miscellaneous articles – Hollow or container type article – Polymer or resin containing
Reexamination Certificate
1998-07-01
2003-07-08
Nolan, Sandra M. (Department: 1772)
Stock material or miscellaneous articles
Hollow or container type article
Polymer or resin containing
C428S035700, C528S101000, C528S406000
Reexamination Certificate
active
06589621
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to polyethers having pendant hydroxyl moieties. More particularly, this invention relates to hydroxy-functionalized polyetheramines or polyhydroxyaminoethers (PHAE).
Hydroxy-functionalized polyetheramines are known and are described, for example, in U.S. Pat. Nos. 5,275,853 and 5,464,924. These polyetheramines exhibit oxygen transmission rates of from 0.57 to 19 cm
3
-mil/100 in
2
-atm (O
2
)-day, and are useful in the fabrication of barrier containers and films and as molding, extrusion and casting resins.
Hydroxy-functionalized polyetheramines can sometimes undergo cross-linking when fabricated at elevated temperatures. Modified, melt-stable polyetheramines, along with a process for their preparation, would clearly be desirable.
SUMMARY OF THE INVENTION
The present invention is, in a first aspect, a composition comprising a blend of an inorganic base, an organic base, a monofunctional organic nucleophile or a multifunctional organic nucleophile and a thermoplastic hydroxy-functionalized polyetheramine having the formula:
wherein each A is independently an amine moiety and each B is independently a divalent aromatic moiety; R
1
is hydrogen or a hydrocarbyl moiety; each X is independently a monovalent moiety; and n is a whole number from about 5 to about 1000.
In a second aspect, the present invention is a process for preparing a blend which comprises contacting an inorganic base, an organic base, a monofunctional organic nucleophile or a multifunctional organic nucleophile with a polyetheramine.
In a third aspect, the present invention is a laminate structure comprising one or more layers of an organic polymer and one or more layers of the composition of the first aspect.
In a fourth aspect, the present invention is an article fabricated from the composition of the first aspect or laminate structure thereof, and can be in the form of a molded or coextruded container, or an impermeable monolayer or multilayer film. The article is suitable for packaging oxygen-sensitive materials such as foodstuffs and medicines.
In a fifth aspect, the present invention is a solvent or waterborne coating prepared from the composition of the first aspect.
These hydroxy-functionalized polyetheramine blends are melt-stable thermoplastics and exhibit oxygen transmission rates below 5.0 cc-mil/100 in
2
-atm-day.
In addition to their use as barrier containers, films, laminate structures and coatings, the compositions of this invention are also useful as molding, extrusion and casting resins.
DETAILED DESCRIPTION OF THE INVENTION
In preferred embodiments of the present invention, each A in the above formula is independently an amine moiety represented by any one of the formulas:
wherein R is independently a hydrocarbyl, heterohydrocarbyl, inertly-substituted hydrocarbyl or inertly-substituted heterohydrocarbyl moiety, wherein the substituent(s) is hydroxyl, cyano, halo, arlyloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl; R
3
and R
4
are independently a hydrocarbylene, heterohydrocarbylene, inertly-substituted hydrocarbylene or inertly-substituted heterohydrocarbylene moiety, wherein the substituent(s) is hydroxyl, cyano, halo, arlyloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl with ethylene and p-xylylene being most preferred; each X is independently hydrogen, a primary, secondary or tertiary amino moiety, a hydroxyl moiety, an alkyl, heteroalkyl, inertly-substituted alkyl or inertly-substituted heteroalkyl group, an aryl or inertly-substituted aryl group, an alkoxy or inertly-substituted alkoxy group; an aryloxy or inertly-substituted aryloxy group, an alkanethio or inertly-substituted alkanethio group; an arenethio or inertly-substituted arenethio group, wherein the substituent(s) is hydroxyl, cyano, halo, arlyloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl; or is represented by any one of the formulas:
wherein R
5
is independently an alkyl or heteroalkyl, inertly-substituted alkyl or heteroalkyl, aryl or inertly-substituted aryl group, wherein the substituent(s) is cyano, halo, arlyloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl; R
6
is independently hydrogen, an alkyl or heteroalkyl, inertly-substituted alkyl or heteroalkyl, aryl or inertly-substituted aryl group, wherein the substituent(s) is the same as that for R
5
; and R
7
is an alkylene or heteroalkylene, inertly-substituted alkylene or heteroalkylene, arylene or inertly-substituted arylene moiety, wherein the substituent(s) is the same as that for R
3
and R
4
.
In the more preferred embodiments of the present invention, X is 2-hydroxyethylamino, dimethylamino, diethylamino, piperadino, N-(2-hydroxyethyl)piperazino, methoxy, ethoxy, propoxy, 2-(methoxy)ethoxy, 2-(ethoxy)ethoxy, benzyloxy, phenyloxy, p-methylphenyloxy, p-methoxyphenoxy, 4-tert-butylphenyloxy, methylmercapto, ethylmercapto, propylmercapto, 2-(methoxy)ethylmercapto, 2-(ethoxy)ethylmercapto, benzylmercapto, 2,3-dihydroxypropylmercapto, phenylmercapto, p-methylphenylmercapto, acetate, benzoate, acetamido or benzenesulfonamido; R
1
is hydrogen or methyl; R
2
is methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, 2-(acetamido)ethyl, benzyl, phenyl, p-methoxyphenyl, p-methylphenyl; R
3
is ethylene, 1,2-propylene or 1,2-butylene and R
4
is ethylene, 1,2-propylene or 1,2-butylene, propylene, butylene, hexamethylene, 1,4-xylylene, 1,3-xylylene, 1,4-phenylene, 1,3-phenylene or 1,2-phenylene; and B is 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, methylenediphenylene, isopropylidenediphenylene, oxydiphenylene, thiodiphenylene, carbonyldiphenylene, diphenylflourene or a-methylstilbene or a combination thereof.
The hydroxy-functionalized polyetheramines employed in the present invention can be prepared by reacting a difunctional amine with a diglycidyl ether under conditions sufficient to cause the amine moieties to form a polymer backbone having amine linkages, ether linkages and pendant hydroxyl moieties. Residual epoxy end groups, should any remain, can optionally be reacted with a monofunctional nucleophile so that the isolated polyetheramine has no moieties capable of reacting with nucleophilic species.
As used herein, the term “diglycidyl ether” means the reaction product of an aromatic, aliphatic or poly(alkylene oxide) diol with epichlorohydrin.
The difunctional amines which can be employed in the practice of the present invention include the bis-secondary amines and primary amines. Suitable bis-secondary amines include piperazine and substituted piperazines, e.g., dimethylpiperazine and 2-methylamidopiperazine; bis(N-methylamino)benzene, 1,2-bis(N-methylamino)ethane, and N,N′-bis(2-hydroxyethyl)ethylenediamine. Preferred bis-secondary amines are piperazine, dimethylpiperazine, and 1,2-bis(N-methylamino)ethane. The most preferred bis-secondary amine is piperazine. Suitable primary amines include aniline and substituted anilines, e.g. 4-(methylamido)aniline, 4-methylaniline, 4-methoxyaniline, 4-tert-butylaniline, 3,4-dimethoxyaniline, 3,4-dimethyaniline; alkylamines, and substituted alkyl amines, e.g. butylamine and benzylamine; and alkanol amines; e.g. 2-aminoethanol and 1-aminopropan-2-ol. Preferred primary amines are aniline, 4-methoxyaniline, 4-tert-butylaniline, butylamine, and 2-aminoethanol. Most preferred primary amines are 4-methoxyaniline and 2-aminoethanol.
The diglycidyl ethers which can be employed in the practice of the present invention for preparing the polyetheramines include the diglycidyl ethers of the amide-containing bisphenols such as N,N′-bis(hydroxyphenyl)-alkylenedicarboxamides, N,N′-bis(hydroxyphenyl)arylene-dicarboxamides, bis(hydroxybenzamido)alkanes or bis(hydroxybenzamido)arenes, N-(hydroxyphenyl)hydroxybenzamides, 2,2-bis(hydroxyphenyl)acetamides, N,N′-bis(3-hydroxyphenyl)glutaramide, N,N′-bis(3-hydroxyphenyl)adipamide, 1,2-bis(4-hydroxybenzamido)ethane, 1,3-bis(4-hydroxybenzamide)benzene, N-(4-hydroxyphenyl)-4-hydroxybenzamide, and 2,2-bis(4-hydroxyphenyl)a
Beckerdite John M.
Glass Terry W.
Keillor, III Peter T.
Moseman Thomas E.
Sanford Joe F.
Damocles Nemia C.
Dow Global Technologies Inc.
Nolan Sandra M.
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