MXPA00013020A

MXPA00013020A - Thermally stable polyetheramines

Info

Publication number: MXPA00013020A
Application number: MXPA/A/2000/013020A
Authority: MX
Inventors: E White Jerry; Joe F Sanford; John M Beckerdite; Terry W Glass; David S Wang; Peter T Keillor Iii; Thomas E Moseman
Original assignee: Dow Global Technologies Inc
Priority date: 1998-07-01
Filing date: 2000-12-20
Publication date: 2002-02-26

Abstract

Compositions 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 can be formed into films and laminate structures by using conventional extrusion techniques. Containers and other molded parts can be fabricated from the films or laminate structures by using conventional fabricating techniques for thermoplastic polymers such as compression molding, injection molding, extrusion, thermoforming, blow molding and solvent casting.

Description

THERMALLY STABLE POLYETHERAMINES This invention relates to polyethers having pendant hydroxyl portions. More particularly, this invention relates to polyhydroxy-amino ethers or polyetheramines functionalized by hydroxy (PHAE). Hydroxy-functionalized polyetheramines are known and described, for example, in US Patents. 5,275,853 and 5,464,924. These polyetheramines exhibit oxygen transmission rates from 0.57 to 19 cm3-mil / 100 in2-atm (O2) -day, and are useful in the manufacture of barrier vessels and films and as molding, extrusion and casting resins. Hydroxy functionalized polyetheramines can sometimes be degraded when manufactured at elevated temperatures. The stable fusion polyetheramines, modified, together with a process for their preparation, could be clearly desirable. The present invention is, in a first aspect, a composition comprising a mixture of an inorganic base, an organic base, a monofunctional organic nucleophile or a multifunctional organic nucleophile and a polyetheramine functionalized by thermoplastic hydroxy having the formula: OH OH CH OH XCH2C «zOB« (- OCH2CCHzACHzCCHi03 -) - C: HzCCHií < R1 «f K1 wherein each A is independently a portion of amine and each B is independently a divalent aromatic moiety; R1 is hydrogen or a hydrocarbyl portion; each X is independently a monovalent portion; and n is an integer from 5 to 1000. In a second aspect, the present invention is a process for preparing a mixture comprising 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 laminated 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 made of the composition of the first aspect or laminated structure thereof, and may 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 food and medicine. In a fifth aspect, the present invention is a solvent or water coating prepared from the composition of the first aspect. These hydroxy functionalized polyetheramine blends are stable melt thermoplastics and exhibit oxygen transmission rates below 5.0 cc-mil / 100 in2-atm-day. In addition to their use as barrier vessels, films, laminated structures and coatings, the compositions of this invention are also useful as casting, extrusion, and molding resins. In preferred embodiments of the present invention, each A in the above formula is independently an amine moiety represented by any of the formulas: - N -NT ^ M-M- R ^ -N- wherein R 2 is independently a hydrocarbyl, heterohydrocarbyl, inertly substituted hydrocarbyl or inertly substituted heterohydrocarbyl portion, wherein the substituent (a) is hydroxyl, cyano, halo , aryloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl; R3 and R4 are independently a hydrocarbylene, heterohydrocarbylene, inertly substituted hydrocarbylene or inertly substituted heterohydrocarbylene portion, wherein the substituent (s) are hydroxyl, cyano, halo, aryloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl with ethylene and -xyxylene being more preferred; each X is independently hydrogen, a primary or secondary tertiary amino moiety, a glycidyloxy 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 an inertly substituted alkoxy group; an aryloxy or aryloxy group substituted inertly, an alknetium or alkanthi group substituted inertly; an arenetium or inertly substituted arenetium group, wherein the substituent (s and) are hydroxyl, cyano, halo, aryloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl; or it is represented by any of the formulas: wherein R5 is independently an alkyl or heteroalkyl, substituted alkyl inertly or heteroalkyl, aryl or inertly substituted aryl group, wherein the substituent (s) are cyano, halo, alkyl, aryl, alkoxy, aryloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl; R6 is independently hydrogen, an alkyl or heteroalkyl, substituted alkyl inertly or heteroalkyl, aryl or inertly substituted aryl group, wherein the substituent (s) is the same as for R5; and R7 is an alkylene or heteroalkylene, inert substituted alkylene or heteroalkylene, arylene or inertly substituted arylene portion, wherein the substituent (s) is the same as for R3 and R4. In the most 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-ferf-butylphenyloxy, methylmercapto, ethylmercapto, propylmercapto, 2- (methoxy) ethylmercapto, 2- (ethoxy) ethylmercapto, benzylmercapto, 2,3-dihydroxypropylmercapto, phenylmercapto, p -methylphenylmercapto, acetate, benzoate, acetamido or benzenesulfonamido; R1 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; R3 is ethylene, 1, 2-propylene or 1 -2-butylene and R4 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, methylene diphenylene, isopropylidenediphenylene, oxodiphenylene, thiodiphenylenecarbonyldiphenylene, diphenylfluorene or α-methylstyrene or a combination thereof. The hydroxy-functionalized polyetheramines employed in the present invention can be prepared by reacting a dysfunctional amine with a diglycidyl ether under conditions sufficient to cause the amine moieties to form a major polymer element having amine bonds, ether linkages and of suspended hydroxyl. Residual epoxy final groups, any remaining, can optionally be reacted with a monofunctional nucleophile in such a way that the isolated polyetheramine has no portions capable of reacting with nucleophilic species. As used herein, the term "diglycidyl ether" means the reaction product of an aliphatic diol or poly (alkylene oxide), aromatic with epichlorohydrin The dysfunctional amines which may be employed in the practice of the present invention, include bis-secondary amines and primary amines Suitable bis-secondary amines include piperazine and substituted piperazines, for example, dimethylpiperazine and 2-methylamidopiperazine; bis (N-methylamino) benzene, 1,2-bis (N-methylamino) ethane and N, N'-bis (2-hydroxyethyl) ethylenediamine The 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, for example, 4- (methylamido) anil ine, 4-methylaniline, 4-methoxyaniline, 4-tert-butylaniline, 3,4-dimethoxyanilinyl, 3,4-dimethylaniline, alkylamines, and substituted alkyl amines, for example, buti lamina and benzylamine; and alkanol amines; for example, 2-aminoethanol and 1 -aminopropan-2-ol. The preferred primary amines are aniline, 4-methoxyaniline, 4-tert-butylaniline, butylamine, and 2-aminoethanol. The most preferred primary amines are 4-methoxyaniline and 2-aminoethanol. The diglycidyl ethers which can be used in the practice of the present invention to prepare the polyetheramines include the diglycidyl ethers of the amide-containing bisphenols such as N, N'-bis (hydroxyphenyl) -alkylenedicarboxamides, N, N'-bis ( hydroxy enyl) arylene-dicarboxamides, bis (hydroxybenzamido) alkalins 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-idroxybenzamide) benzene, N- (4-hydroxyphenyl) -4-hydroxybenzamide, and 2.2 bis (4-hydroxyphenyl) ace1: amide, 9,9-bis (4-hydroxyphenyl) -fluorene, hydroquinone, resorcinol, 4,4'-sulfonyl-diphenol, 4,4'-thiodiphenol, 4,4'-oxydiphenol , 4,4'-dihydroxybenzophenone, tetrabromoisopropylidene-bisphenol, dihydroxy dinitrofluoreniliclenodiphenylene, 4,4-bis (4-hydroxyphenyl) -methane, a, a-bis (4-hydroxyphenyl) ethylbenzene, 2,6-dihydroxynaphthalene and 4,4 ' -isopropylidene bisphenol (bisphenol A). The most preferred diglycidyl ethers are the diglycidyl ethers of 9,9-bis- (4-hydroxyphenyl) fluorene, hydroquinone, resorcinol, 4,4'-sulfonyldiphenol, 4,4'-thiodiphenol, 4,4'-oxydiphenol, 4,4'-dihydroxybenzophenone, tetrabromoisopropylidenebisphenol, dihydroxy dinitrofluorenylidenediphenylene, 4,4'-biphenol, 4,4'-dihydroxybiphenylene oxide, bis (4-hydroxyphenyl) -methane, a, a-bis (4-hydroxyphenyl) ethylbenzene, 2, 6-dihydroxynaphthalene and 4,4'-isopropylidene bisphenol (bisphenol A). The most preferred diglycidyl ethers are the diglycidyl ethers of 4,4'isopropylidene bisphenol (bisphenol A), 4,4'-sulfonyldiphenol, 4,4'-oxydiphenol, 4,4'-dihydroxybenzophenone, and 9,9-bis (4-hydroxy-phenyl) fluorenp. Inorganic bases which can be employed in the practice of the present invention include potassium hydroxide, sodium hydroxide, ammonium hydroxide, calcium oxide, magnesium oxide and mixtures thereof. Organic bases that can be employed in the practice of the present invention include triethylene diamine and 1,5-diazabicyclo (54.0) undec-7- na. The monofunctional organic nucleophiles which may be employed in the practice of the present invention include a monofunctional amine, a hydroxyaryrene, an aryloxide salt, a carboxylic acid, a carboxylic acid salt, a thiol or a thiolate salt. Preferably, the monofunctional amine is dimethylamine, diethylamine, bis (2-hydroxyethyl) amine, dipoenylamine, piperazine, N- (2-hydroxyethylpiperazine) -2-methylimidazole; the hydroxyaryrene is phenol, cresol, methoxyphenol, or 4-ferf-butylphenol; the aryloxide salt is sodium or potassium phenate; the carboxylic acid is acetic acid or benzoic acid; the carboxylic acid salt is sodium acetate, potassium acetate, calcium acetate, copper (II) acetate, sodium propionate, potassium propionate, calcium propionate, sodium benzoate, potassium benzoate, sodium ethylhexanoate, ethylhexanoate of potassium, or calcium ethylhexanoate; the thiol is 3-mercapto-1,2-propanediol or benzenethiol; and the thiolate salt is potassium or sodium benzenethiolate. The multifunctional organic nucleophiles that can be employed in the practice of the present invention include a multifunctional amine, a multifunctional carboxylic acid, a multifunctional carboxylic acid salt, a multifunctional phenol, a multifunctional phenate salt, a multifunctional thiol, a multifunctional thiolate salt , an amino acid or an amino acid salt. Preferred multifunctional organic nucleophiles are ethylenediamine, propylene diamine, butylene diamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, polyethyleneamine, citric acid, potassium citrate or sodium glycine or potassium or sodium glycinate. The organic nucleophile can be the product of the reaction of a polyethylene polyamine with ethylene oxide or propylene oxide or a mixture of such products. In general, the inorganic base, organic base, monofunctional organic nucleophile or multifunctional organic nucleophile is mixed with the polyetheramines functionalized by thermoplastic hydroxy by conventional dry blending methods using conventional means such as, a cylinder mixer, or a counterbalancing mixer or by dry blending in an appropriate apparatus, such as an internal Banbury type mixer, rubber mill, extruder or single or twin screw mixer. The inorganic base, organic base, monofunctional organic nucleophile or multifunctional organic nucleophile can also be co-dissolved with the polyetheramines functionalized by thermoplastic hydroxy in a suitable solvent and the solvent is removed by evaporation. Examples of suitable solvents include 1-methyl-2-pyrrolidinone (NMP), and hydroxy ethers or ethers such as diglyme, triglyme, diethylene glycol etiol ether, diethylene glycol methyl ether, methyl glycol ether of dipropylene, propylene glycol phenyl ether, propylene glycol methyl ether and tripropylene glycol methyl ether. Another suitable method for preparing the mixtures of the present invention comprises reacting a dysfunctional amine, a diglycidyl ether and optionally a monofunctional nucleophile and thus mixing the reaction product in situ with an inorganic base, an organic base or a mono- or organic nucleophile. multifunctional in a solvent, in a molten state or in an extruder. The amount of the inorganic base, organic base, monofunctional organic nucleophile or multifunctional organic nucleophile more advantageously mixed with the hydroxy-functionalized polyether depends on a variety of factors including the specific polymers used in making the mixtures, as well as the desired properties of the polymers. the products that result from the mixtures. Typical amounts may vary from 0.1 to 15 weight percent of the mixture. Preferably, the inorganic base, organic base, monofunctional organic nucleophile or multifunctional organic nucleophile is used in an amount of from 0.5 to 10 weight percent, more preferably 0.5 to 3.0 weight percent and, more preferably, 0.1 to 2.0 percent by weight of the mixture. The composition of the present invention may be in the form of a conductive solvent coating, a water coating, a sheet, a foam, a film, a container or a molding article. Films prepared from the composition of the present invention generally have oxygen transmission rates (OTR) from 0.5 to 1.0 cc / mil / 100 in2 / atm / day, at 25 ° C and 60 percent relative humidity (ASTM D-3985) and carbon dioxide transmission rates (CO2TR) from 0.5 to 4.0 cc-mil / 100 in2-atm-day, at 23 ° C and 0 percent relative humidity. Laminated films and structures can be formed from the composition of the present invention by using conventional extrusion techniques such as regeneration extrusion, multiple nozzle coextrusion or combinations of the two, or by solvent spray or solution melt. Solution casting is a well-known process and is described, for example, in the Plastics Engineering Handbook of the Society of the Plastics Industry, Inc., 4th. Edition, page 448. Containers and other molded parts can be fabricated from the films or laminated structures comprising the composition of the present invention by using conventional manufacturing techniques for thermoplastic polymers such as compression molding, injection molding, extrusion, thermoforming, blow molding and solvent casting. In general, laminated structures can be formed from the composition of the present invention by co-extruding one or more layers of an organic polymer and one or more layers of the composition of the present invention, wherein the layer of the composition of the present invention is adheres to an adjacent organic polymer layer with or without an adhesive layer therebetween. Laminated structures can also be formed by co-injection of the composition of the present invention with an organic polymer; in some cases, the preforms produced by such co-injection can be blow molded into multilayer containers. The laminated structure can be a three layer sheet comprising a first outer layer of an organic polymer, a core layer of the composition of the present invention and a second outer layer of an organic polymer that is the same or different from the organic polymer of the first outer layer. The laminated structure may also be a sheet comprising a first outer layer of the composition of the present invention, a core layer of an organic polymer and a second outer layer of an organic polymer that is the same as or different from the organic polymer of the core layer. The laminated structure can also be a three layer sheet comprising a first outer layer of the composition of the present invention, a core layer of an organic polymer and a second outer layer of the composition of the present invention. The laminated structure can of course comprise more than three layers, including, for example, five-layer structures comprising outer layers and an inner layer of an organic polymer separated by two layers of the composition of the present invention. Organic polymers which can be used in the practice of the present invention to prepare the laminated structure include crystalline thermoplastic polyesters, such as polyethylene terephthalate (PET); polyamides, polyolefins, and polyolefins based on monovinyl aromatic monomers. Polyesters and methods for their preparation are well known in the art and are also referred to for the purposes of this invention. For purposes of illustration but not limitation, particular reference is made to pages 1-62 of Volume 12 of the Encyclopedia of Polymer Science and Engineering, Revision 1988, John Wiley & Sons. Polyesters that can be employed in the practice of the present invention include poly (ethylene terephthalate) and poly (ethylene-naphthalene (dicarboxylate).) Polyamides that can be employed in the practice of the present invention include various grades of nylon, such as nylon-6. , nylon-6,6 and nylon-12 Polyolefins based on monovalent aromatic monomers that can be used in the practice of the present invention include polystyrene, polymethylstyrene, styrene / methylstyrene or styrene / chlorostyrene copolymers. Polyester or polyamide can also be used in the practice of the present invention to prepare the laminated structure Such polymers include polyhexamethylene adipamide, polycaprolactone, polyhexamethylene sebacamide, polyethylene 2,6-naphthalate and polyethylene 1,5-naphthalate, polytetramethyl or 1, 2-dioxybenzoate and copolymers of ethylene terephthalate and ethylene isophthalate. The layer in the laminated structure depends on a number of factors, including the intended use, materials stored in the container, the length of storage before use and the specific composition employed in each layer of the sheet. In general, the laminated structure will have a total thickness of 0.5 to 500 mils, preferably from 1.0 to 250 mils; with the thickness of the polyetheramine layer (s) functionalized by hydroxy being from 0.05 to 100 thousand, preferably from 0.1 to 50 mils; and the thickness of the polyester layer (s) being from 0.45 to 400 mils, preferably from 0.9 to 200 mils. The composition of the present invention can also be prepared and manufactured in a profiled article by a reactive extrusion process wherein the reactants are fed and reacted in an extruder using the conditions described in the US Pat.

E.U. No. 4, 612, 156. The following working examples are given to illustrate the invention and should not be construed as limiting in scope. Unless otherwise indicated, all parts and percentages are by weight. Example 1 A. Polymer Preparation A polyhydroxy-amine ether polymer (PHAE) was prepared from the reaction of liquid epoxy resin (LER) DER ™ 332 (a liquid diglycidyl ether of bisphenol A) and ethanolamine (MEA) in a Werner &; Pfleiderer ZSK-30 that had two 30-mm double screws with a length-to-diameter ratio of 47: 1. The extruder consisted of 1 5 cylindrical sections with 9 heating zones. The temperature profile was zone 1 (cylindrical sections 1 and 2), 65 ° C; zone 2 (cylindrical sections 3 and 4), 1 10 ° C; zone 3 (cylindrical sections 5 and 6), 160 ° C; zone 4 (cylindrical sections 7 and 8), 1 80 ° C; zone 5 (cylindrical section 9), 190 ° C; zone 6 (cylindrical sections 10 and 11), 190 ° C; zones 7 and 8 (cylindrical sections 12 to 15), 200 ° C; and zone 9 (head of the extruder), 200 ° C. The speed of rotation of the propeller was 130 to 150 rpm. The LER and MEA were fed in cylindrical section 1 using Zenith HPB-5704 variable speed gear pumps with positive displacement flow meters Model Max 213-300. The temperatures of the feed streams were measured with platinum RTD thermometers and density corrections applied to the reference points of the gear pump to provide exactly mass flow rates. The flow rate of the total reagent was controlled at 20 pounds / hour with a molar ratio of LER to MEA of 0.971: 1. Diethanolamine (DEA), a degrading suppressant additive, was fed into the cylindrical section 14 to 2 weight percent of the mixture using two 0.5 liter syringe pumps Model Isco LC-5000 so that one was injected while the other Was filling.

The resulting extrusion was processed through a gear pump, filter pack, fixed cooling channel filled with water, and a twisted push button (pelletizer). B. Thermal Stability Test The thermal stability of the PHAE polymer containing a degrading suppressant was measured using a Haake Reocord 9000 power measurement drive equipment with a Haake Reomix 600 mixing chamber. The Reocord 9000 drive equipment provides a power measurement of the polymer mixture in controlled temperature and rotation speed. The mixing chamber was preheated to 140 ° C metal temperature, and the power reading was set to zero with the rotation speed at 50 rpm. Sixty grams of the polymer was poured into the chamber's feed port for a period of 3 to 4 minutes as the material was drawn into the chamber by the rotors. When all the polymer was charged, a piston was reduced in the feed port, closing the chamber. A slow nitrogen purge was injected across the top of the closed feed port to minimize exposure to oxygen. Within 10 minutes of the start of the polymer addition, the power reading had reached a permanent state, and the metal temperature control setpoint was increased to 220 ° C. The start of the isothermal power readings (time equal to zero minutes) was established at the time when the metal temperature reached the 220 ° C reference point. The melting temperature and the power readings were recorded for 83 minutes. In 10 minutes of time zero, the power had decreased 10 percent, and in 30 minutes the power had decreased 17 percent. The relative changes in power readings in 10 minutes and 30 minutes of time zero are recorded in Table I. Examples 2 and 3 Two PHAE polymers were prepared and evaluated as in Example 1, except that the additives charged to the extruder are those described in Table I. Relative changes in the power readings in 10 minutes and 30 minutes of time zero were recorded in Table I. Comparative Example A A. Polymer Preparation A PHAE polymer was produced from the LER reaction Y MEA as described in Example 1 except that the molar ratio of LER to MEA was 0.99: 1 and did not mix DEA in the polymer. The Haake mixing chamber described in Example 1 was preheated to 140 ° C metal temperature, and the power reading was set to zero with the rotation speed at 50 rpm. Sixty grams of the polymer was poured into the chamber's feed port for a period of 3 to 4 minutes as the material was drawn into the chamber by the rotors. When all the polymer was charged, a piston was reduced in the feed port, closing the chamber. A slow nitrogen purge was injected across the top of the closed feed port to minimize exposure to oxygen. Within 10 minutes of the start of the polymer addition, the power reading had reached a permanent state, and the metal temperature control set point was increased to 220 ° C. The start of the isothermal power readings (time equal to zero minutes) was established at the time when the metal temperature reached the reference point of 220 ° C. The melting temperature and the power readings were recorded for 10 minutes. In 10 minutes of time zero, the potency had increased 552 percent and the material had gelled. The relative change in the power reading in 10 minutes of time zero is recorded in Table IB Barrier Testing A suitable film for oxygen transmission rate determination (O2TR) was prepared by pressing approximately 1.2 grams of polymer to 10,000 pounds of pressure in a Tetrahedron Associates, Inc. press, MTP at 195 ° C for 5 minutes. The resulting film was 3.96 mils in average thickness and 4 to 6 inches in diameter. The O2TR of the film was tested following the method ASTM D3985-81 in an Ox Tran 10/50 at 24 ° C, a relative humidity of 63 percent on the oxygen side of the film and 63 percent on the nitrogen side . The result of O2TR was 0.87 (c x thousand) / (100 in2 x day x atm O2), and is listed in Table IV. Example 4 The Haake mixing chamber described in Example 1 was preheated to 140 ° C metal temperature, and the power reading was set to zero with the rotation speed at 50 rpm. The polymer produced in Comparative Example A, 58.93 grams, was poured into the feed port of the chamber for a period of 3 to 4 minutes as the material was drawn into the chamber by the rotors. As the last of the polymers was loaded into the chamber, 1066 grams of 2- (2-aminoethylamino) ethanol (AEEA) were also loaded. When all the polymer and amine were charged, the piston was reduced in the feed port, closing the chamber. A slow nitrogen purge was injected through the top of the closed feed port to minimize exposure to oxygen. Within 20 minutes of the start of the polymer addition, the materials were mixed homogeneously, and the metal temperature control setpoint was increased to 220 ° C. The start of the isothermal power readings (time equal to zero minutes) was established at the time when the metal temperature reached the set point at 220 ° C. Metal temperature and power readings were recorded for 100 minutes. In 10 minutes of time zero, the power had decreased 1 1 percent, and in 30 minutes the power had decreased 34 percent. The relative changes in power readings in 10 minutes and 30 minutes of time zero are recorded in Table II. Examples 5-25 Various PHAE polymers were prepared following the procedure described in Example 4, except that the additives charged in the Haake mixing chamber are those described in Table II. The relative changes in power readings in 10 minutes and 30 minutes of time zero are recorded in Table II. Example 26 The Haake mixing chamber described in Example 1 was preheated to 150 ° C metal temperature, and the power reading was set to zero with the rotation speed at 50 rpm. Fifty grams of polymer that were prepared in a manner similar to Example 1 and which was the polymerization product of LER and MEA, and in which 0.5 weight percent diethanolamine was mixed, were poured into the chamber feeding port for a period of 3 to 4 minutes as the material was removed in the chamber by the rotors. The time equal to zero minutes was established at the end of the polymer addition. In 5 minutes of time zero, 0.7615 grams of calcium ethylhexanoate was charged. In 10 minutes of zero time, the power reading had reached a permanent state, and the metal temperature control set point was manually increased to 5 ° C in 2 minute intervals at 230 ° C. The melting temperature and the power readings were recorded for 50 minutes. As the polymer heated up, the power reading is eliminated with decreasing viscosity until degradation results in a minimum power at 47 minutes, after the power values increase with increasing gelation. The time in the minimum power is recorded in Table III. Examples 27-30 Various PHAE polymers were prepared and evaluated following the procedure described in Example 26, except that in 5 minutes of time zero, the additives described in Table III were loaded into the Haake mixing chamber. The time in the minimum power is recorded in Table III. Example 31 A. Preparation of PHAE Polymer The mixing chamber described in Example 1 was preheated to 140 ° C metal temperature, and the power reading was set to zero with the rotation speed at 50 rpm. The polymer produced in Comparative Example A, 58.8 grams, was poured into the feed port of the chamber for a period of 3 to 4 minutes as the material was drawn into the chamber by the rotors. As the last of the polymers was loaded into the chamber, 1,221 grams of AEEA were also loaded. When all the polymer and amine were charged, the piston was reduced in the feed port, closing the chamber. At 20 minutes from the start of the polymer addition, the materials were mixed homogeneously, and the mixture was coated from the mixing chamber. B. Barrier Test A suitable film for determining oxygen transmission rate (O2TR) was prepared by pressing about 1.2 grams of polymer at 10,000 pounds of pressure using the press described in Comparative Example A. The resulting film was 3.10 mils in thickness and 4 to 6 inches in diameter. The O2TR of the film was tested using the same equipment and procedure as described in Comparative Example A at 24 ° C, a relative humidity of 63 percent on the oxygen side of the film and 63 percent on the nitrogen side . The result of O2TR was 0.73 (ce x thousand) / (100 in2 x day x atm O2), and is listed in Table IV. Examples 32-36 Various PHAE polymers were prepared and evaluated following the procedure described in Example 31, except that the additives charged in the Haake mixing chamber are those described in Table IV. The results of O2TR are listed in Table IV.

Table I Table II NJ Table II (continued) 01 Table III N > OR) Table IV FO ~ 4

Claims

CLAIMS 1. A composition comprising a mixture of an inorganic base, an organic base, a monofunctional organic nucleophile or a multifunctional organic nucleophile and a polyetheramine functionalized by thermoplastic hydroxy having the formula: wherein each A is independently an amine moiety and each B is independently a heterohydrocarbylene or divalent hydrocarbylene moiety; R1 is hydrogen or a hydrocarbyl portion; each X is independently a monovalent portion; and n is an integer from 5 to 1000.
2. The composition according to claim 1, characterized in that A in the polyetheramine formula is represented by any of the formulas: -K- -KG * N-; 3 ^ N "_R __- N_ K7 R2 wherein R 2 is independently a hydrocarbyl, heterohydrocarbyl, inertly substituted hydrocarbyl or inertly substituted heterohydrocarbyl portion, wherein the substituent (s) is hydroxyl, cyano, halo, aryloxy, alkylamido , arylamido, alkylcarbonyl, or arylcarbonyl; R3 and R4 are independently a hydrocarbylene, heterohydrocarbylene, inertly substituted hydrocarbylene or inertly substituted heterohydrocarbylene portion, wherein the substituent (s) are alkylamido hydroxy, alkoxy, halo, cyano, aryloxy, alkylcarbonyl, or arylcarbonium
3. The composition according to Claim 2, characterized in that each X in the formula of the polyetheramine is independently hydrogen, a primary or secondary tertiary amino portion, a glycidyloxy portion, a hydroxyl portion, an alkyl, heteroalkyl, inert substituted alkyl or heteroalkyl group inertly substituted, an aryl or aryl group substituted inertly, an alkoxy or substituted alkoxy group; an aryloxy or aryloxy group substituted inertly, an alknetium or alkanthi group substituted inertly; an arenetium or inertly substituted arenetium group, wherein the substituent (s) are hydroxyl, cyano, halo, aryloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl.
4. The composition according to claim 2, characterized in that X in the formula of polyetheramine is independently represented by any of the formulas: wherein R5 is independently an alkyl or heteroalkyl, substituted alkyl inertly or heteroalkyl, aryl or inertly substituted aryl group, wherein the substituent (s) are cyano, halo, alkyl, aryl, alkoxy, aryloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl; Fl6 is independently hydrogen, an alkyl or heteroalkyl, substituted alkyl inertly or heteroalkyl, aryl or inertly substituted aryl group, wherein the substituent (s) is the same as for R5; and R7 is an alkylene or heteroalkylene, inert substituted alkylene or heteroalkylene, arylene or inertly substituted arylene portion, wherein the substituent (s) is the same as for R3 and R4.
The composition according to claim 3, characterized in that X in the formula of polyetheramine is 2-hydroxyethylamino, dimethylamino, diethylamino, piperadino, N- (2-hydroxyethyl) piperazino, methoxy, ethoxy, propoxy, 2- (methoxy) ethoxy , 2- (ethoxy) ethoxy, be ncyloxy, phenyloxy, p-methylphenyloxy, p-methoxyphenoxy, 4-tert-butylphenyloxy, methylmercapto, ethylmercapto, propylmercapto, 2- (methoxy) ethylmercapto, 2- (ethoxy) ethylmercapto, benzylmercapto, 2 , 3-dihydroxypropyl ercapto, phenylmercapto, p-methylphenylmercapto, acetate, benzoate, acetmido or benzenesulfonamido.
6. The composition according to claim 2, characterized in that in the formula of the polyetheramine, R1 is hydrogen or methyl; R 2 is methyl, ethyl, propyl, isopropyl, 2-hydroxyethylol, 3-l-hydroxypropyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, 2- (acetamido) ethyl, benzyl, phenyl, p-methoxyphenyl, p-methylphenyl; R3 is ethylene, 1, 2-propylene or 1 -2-butylene and R4 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.
The composition according to claim 2, characterized in that B in the formula of polyetheramine is 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, methylene diphenylene, isopropylidene phenylene, oxodiphenylene, thiodiphenylene, carbonyldiphenylene, diphenylfluorene or α-methylstyrene or a combination thereof.
The composition according to claim 1, characterized in that the polyetheramine is the reaction product of a diglycidyl ether, a dysfunctional amine and optionally a monofunctional nucleophile
9. The composition according to claim 1, characterized in that the organic nucleophile is a monofunctional nucleophile. .
10. The composition according to claim 9, characterized in that the monofunctional nucleophile is an amine, a hydroxyrene, an aryloxide salt, a carboxylic acid, a carboxylic acid salt, a thiol or a thiolate salt.
The composition according to claim 10, characterized in that the amine is dimethylamine, diethylamine, bis (2-hydroxyethyl) amine, diphenylamine, piperadine, N- (2-hydroxyethylpiperazine) -2-methylimidazole; the hydroxyaryrene is phenol, cresol, methoxyphenol, or 4-ferf-butylphenol; the aryloxide salt is sodium or potassium phenate; the carboxylic acid is acetic acid or benzoic acid; the carboxylic acid salt is sodium acetate, potassium acetate, calcium acetate, copper (II) acetate, sodium propionate, potassium propionate, calcium propionate, sodium benzoate, potassium benzoate, sodium ethylhexanoate, ethylhexanoate of potassium, or calcium ethylhexanoate; the thiol is 3-mercapto-1,2-propanediol or benzenethiol; and the thiolate salt is potassium or sodium benzenethiolate.
12. The composition according to claim 1, characterized in that the organic nucleophile is a multifunctional nucleophile.
The composition according to claim 12, characterized in that the multifunctional nucleophile is a multifunctional amine, a multifunctional carboxylic acid, a multifunctional carboxylic acid salt, a multifunctional phenol, a multifunctional phenate salt, a multifunctional thiol, a multifunctional thiolate salt , an amino acid or an amino acid salt.
The composition according to claim 13, characterized in that the multifunctional amine is ethylenediamine, propylene diamine, butylene diamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, polyethyleneamine, the mullifunctional carboxylic acid is citric acid; the multifunctional carboxylic acid salt is potassium or sodium citrate; the amino acid is glycine; and the amino acid salt is potassium or sodium glycinate.
15. The composition according to claim 1, characterized in that the organic nucleophile is the product of the reaction of polyethylenepolyamine with ethylene oxide or propylene oxide or a mixture of such products.
16. The composition according to claim 1, characterized in that the inorganic base is potassium hydroxide, sodium hydroxide, ammonium hydroxide, calcium oxide, magnesium oxide.
17. The composition according to claim 1, characterized in that the organic base is triethylene diamine or 1,5-diazabicyclo (5.4.0) undec-7-ene.
The composition according to claim 1, characterized in that the inorganic base, organic base or organic nucleophile is presented in an amount of 0.1 to 15.0 weight percent based on the weight of the composition.
19. A process for preparing the composition according to claim 1, comprising contacting an inorganic base, an organic base or a mono- or multifunctional organic nucleophile with a polyetheramine.
The process according to claim 19, characterized in that the inorganic base, organic base, monofunctional organic nucleophile or multifunctional organic nucleophile is added to the polyetheramine in a melting state.
The process according to claim 19, characterized in that the inorganic base, organic base, monofunctional organic nucleophile or multifunctional organic nucleophile is mixed with the polyetheramine in an extruder.
22. The process according to claim 19, characterized in that the inorganic base, organic base, monofunctional organic nucleophile or multifunctional organic nucleophile is co-dissolved with the polyetheramine in a solvent and the solvent is removed by evaporation.
23. A process for preparing the composition according to claim 1, comprising first reacting a dysfunctional amine, a diglycidyl ether and optionally a monofunctional nucleophile, and mixing the reaction product in situ with an inorganic base, an organic base, a nucleophile monofunctional organic or a multifunctional organic nucleophile in a solvent or in a state of fusion.
24. The process according to claim 23, characterized in that the dysfunctional amine, diglycidyl ether and the optional monofunctional nucleophile are first reacted, and are thus mixed in situ with the inorganic base, organic base, monofunctional organic nucleophile or multifunctional organic nucleophile in an extruder
25. The composition according to claim 1, in the form of a conductive solvent coating, a water coating, a sheet, a foam, a container or molding article.
26. A multilayer structure comprising alternating layers of a polyester, polyamide, polyolefins or polymers based on monovinyl aromatic monomers and the composition of claim 1.
27. The structure according to claim 26, characterized in that the polyester is poly. (ethylene terephthalate) or poly (ethylene naphthalenedicarboxylate).
28. The structure according to claim 26 in the form of an extruded film, an extrusion blown film, an extruded sheet, a thermoformed container or a blow molded container or bottle by extrusion or injection.