CZ20001072A3 - Thermoplastic polyether amine, process of its preparation, laminate structure, polyether amine in the form of a protective film - Google Patents

Abstract

The laminate structures comprise one or more layers organic polymer and one or more layers a polyetheramine containing hydroxyl functional groups; wherein the polyetheramine is adhered directly to the adjacent layer an organic polymer without an adhesive layer between the two layers. Hydroxyl-containing polyetheramine functional group is prepared by reaction of (1) difunctional amine with (2) diglycidyl ether or diepoxyfunctionalized poly (alkylene oxide) under conditions sufficient to render it the amine moieties could react with the epoxy moieties so that they would react with the epoxy moieties the polymer backbone has formed amine bonds, ether bonds and hindered hydroxyl moieties a followed by treatment of the product, reaction monofunctional nucleophile, which is not a primary or secondary amine.

Description

Thermoplastic polyetheramine, process for its preparation, laminate structure, polyetheramine in the form of a protective film

Technical field

The present invention relates to polyethers having pendant hydroxyl moieties and methods of using them as barrier products to protect oxygen-sensitive materials. More specifically, the present invention relates to hydroxyl-functional polyetheramines.

BACKGROUND OF THE INVENTION

Polypeptides containing hydroxyl functional groups are known and are described, for example, in US Patents 5,275,853 and 5,464,924. These polyetheramines have an oxygen transfer rate of from 0.57 to 19 cm ³ -mil / 100 in ² -atm (O ₂ ) -den and are useful in the manufacture of protective coatings and films and as resins used in molding, extrusion and casting.

Residual epoxy end groups in hydroxyl-functional polyetheramines may sometimes limit their applicability by promoting cross-linking and gelling during the melting process. Melt-resistant polyetheramines containing hydroxyl functionalities during the preparation process are desired.

SUMMARY OF THE INVENTION

The present invention is, in a first aspect, a hydroxyl-functional polyetheramine represented by the formula:

OH OH OH OH

I II I

XCH ₂ eCH ₂ OB - (- OCH ₂ CCH ₂ ACH ₂ OCH ₂ OB-) _n -OCH ₂ CCH ₂ X i

Wherein each A is independently an amino moiety and each B is independently a divalent aromatic moiety; R ¹ is a hydrogen or hydrocarbyl moiety; X is (a) a monovalent moiety that is not a secondary or tertiary amine and that does not contain a substituent capable of crosslinking polyetheramine at normal operating temperature, or (b) a combination of (i) a monovalent moiety that is not a secondary or tertiary amine and and (ii) a monovalent moiety that is a secondary or tertiary amine and n is an integer from 5 to 1000.

In a second aspect, the present invention is a process for preparing hydroxyl functional polyetheramine comprising reacting (1) a difunctional amine with (2) a diglycidyl ether or a diepoxyfunctionalized poly (alkylene oxide) under conditions sufficient to react the amine moieties with the apoxy moieties. to form a backbone of a polymer having amine bonds, ether bonds, and pendant hydroxyl moieties, and then treating the reaction product with a monofunctional nucleophile that is not a primary or secondary amine, optionally in the presence of a catalyst.

In a third aspect, the present invention is a laminate structure consisting of one or more layers of an organic polymer and one or more layers of a hydroxyl-functional polyetheramine according to the first aspect, wherein the polyetheramine layer is attached directly to the organic polymer interface layer without adhesive layer therebetween.

In a fourth aspect, the invention is an article made of a hydroxyl-functional polyetheramine or a laminate structure thereof may be in the form of shaped or co-extruded containers or a monolayer or multilayer impermeable film. This article is suitable for packaging oxygen-sensitive materials such as food raw materials and pharmaceuticals.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

J 9 4 ·········· · · 4 ········ · · 44 4 9 4 9.9 9 9 99

In a fifth aspect, the invention is a solvent or water-borne coating prepared from a hydroxyl-functional polyetheramine.

These polyetheramines are melt-resistant thermoplastics and exhibit oxygen transfer rates below 20cc-mil / 100 in ² -at-day.

In addition to being used as protective vessels, films, laminate structures and coatings, the polymers of this invention are also useful as molding, extrusion and casting resins.

In a preferred embodiment of the invention, each A in the above formula is independently an amine moiety represented by any of the formulas:

—N— I

R ²

—N — R ⁴ —N — II

R ² R ² wherein R is hydrocarbyl, heterocarbyl, an inertly substituted hydrocarbyl or an inertly substituted heterohydrocarbyl moiety wherein the substituent (s) is hydroxyl, cyano, halo, aryloxy, alkylamido, arylamido, alkylcarbonyl or arylcarbonyl; R ³ and R ⁴ are independently hydrocarbylene, heterocarbylene, an inertly substituted hydrocarbylene or an inertly substituted heterocarbylene moiety wherein substituent (s) is hydroxyl, cyano, halo, aryloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl with ethylene and p-xylene, which are most preferred; each X is independently a hydrogen primary amino moiety, a hydroxyl moiety, an alkyl, heteroalkyl, an inertly substituted alkyl or an inertly substituted heteroalkyl group, an aryl or an inertly substituted aryl group, an alkoxy or an inertly substituted alkoxy group; aryloxy or inertly substituted aryloxy, alkanthio or inertly substituted alkanthio; arenthio or an inertly substituted arenthio group wherein substituent (s) is hydroxyl, cyano, halo,

Aryloxy, alkylamido, arylamido, alkylcarbonyl or arylcarbonyl or is represented by any of the formulas:

OOSOR ⁶ OR ⁶

R — C — O R — C — S — R — C — S — R — C — N — R - S — N—

RC ^; -ď

CHR ⁷ CHII

Wherein R ⁵ is independently an alkyl or heterolaalkyl inert-substituted alkyl or heteroalkyl aryl or inert substituted aryl group wherein substituent (s) is cyano, halo, aryloxy, alkylamido, arylamido, alkylcarbonyl, or arylcarbonyl; R ⁶ is independently hydrogen, alkyl or heteroalkyl, inert substituted alkyl or heteroalkyl, aryl or inert substituted aryl, wherein substituent (s) is the same as that for R ⁵ ; and R ⁷ is an alkylene or heteroalkylene, an inertly substituted alkylene or a heteroalkylene arylene or an inertly substituted arylene moiety in which 1 µM is a (a) moiety.

In a preferred embodiment of the present invention, X is methoxy, ethoxy, propoxy, 2- (methoxy) ethoxy, 2- (ethoxy) ethoxy, benzyloxy, phenyloxy, p-methylphenyloxy, p-methoxyphenoxy, 4-tert-butylphenyloxy, methylmercapto, benzylmercapto, 2,3-dyhydroxypropylmercapto, 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-dyhydroxypropyl, 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, propylene, butylene, hexamethylene, 1,4 • s · a · · · · · that it ·· '· · ·' · · · ^Γ '• a personal identification · ··· · «· ·

-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, diphenylfluorene or methylstilbene or combinations thereof.

The hydroxyl-functional polyetheramine of the invention can be prepared by reacting a difunctional amine with an excess of diglycidyl ether under conditions sufficient to form amine moieties containing amino linkages, ether linkages and pendant hydroxyl moieties, followed by treatment of the reaction product with a monofunctional nucleophile , which is not a primary or secondary amine, optionally in the presence of a catalyst. Alternatively, hydroxyl-containing polyetheramines may be prepared by reacting a difunctional amine and an equimolar amount of diglycidyl ether and then treating the reaction product with a monofunctional nucleophile that is not a primary or secondary amine, optionally in the presence of a catalyst.

The term "diglycidyl ether" is used herein to mean the reaction product of an aromatic, aliphatic or poly (alkylene oxide) diol with epichlorohydrin.

Diaminating amines that may be used in the practice of this invention include bis-secondary amines and primary amines. Suitable bis-secondary amines include piperazine and substituted piperazines such as 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 desirable bis-secondary amine is piperazine. Suitable primary amines include aniline and substituted anilines such as 4- (methylamido) aniline, 4-methylaniline, 4-methoxyaniline, 4-tert-butylaniline, 3,4-dimethoxyaniline, 3,4-dimethylaniline; alkylamines and substituted alkylamines such as bytlamine and benzylamine; and alkanolamines such as 2-aminoethanol and 1-aminopropan-2-ol. Preferred primary amines are aniline, 4-methoxyaniline, 4-tert-butyl-6-aniline, butylamine and 2-aminoethanol. The most preferred primary amines are 4-methoxyaniline and 2-aminoethanol.

Diglycidyl ethers that can be used in the practice of the present invention for preparing polyetheramines include diglycidyl ethers amide-containing bisphenols such as N, N'-bis (hydroxyphenyl) alkylenedicarboxamides, N, N'-bis (hydroxyphenyl) arylendicarboxamides, bis (hydroxybenzamido) alkanes or bis (hydroxybenzamidojarenes, 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) acetamide, 9,9-bis (4-hydroxyphenyl) fluorene , hydroquinone, resorcinol, 4,4'-sulfonyl-diphenol, 4,4'-thiodiphenol, 4,4'-oxydiphenol, 4,4-dihydroxybenzophenone, tetrabromoisopropylidene-bisphenol, dihydroxydinitrofluorenylidenediphenylene, 4,4-bis (4-hydroxyphenyl) methane, α, α-bis (4-hydroxyphenyl) ethylbenzene, 2,6-dihydroxynaphthalene and 4,4'-isopropylidenebisphenol (bisphenol A). ycidyl ethers of 9,9-bis (4-hydroxyphenyl) -fluorene, hydroquinone, resorcinol, 4,4'-sulfenyldifenol, 4,4'-thiodifenol, 4,4'-oxydiphenol, 4,4'-dihydroxybenzophenone, tetrabromoisopropylidenebisphenol, dihydroxydinitroflenoriphenyl fluoride 4,4'-biphenol, 4,4'-dihydroxybiphenylene oxide, bis (4-hydroxyphenyl) methane, α, α-bis (4-hydroxyphenyl) ethylbenzene, 2,6-dihydroxynaphthalene and 4,4'-isopropylidenebisphenol (bisphenols A) . The most preferred diglycidyl ethers are the diglycidyl ethers of 4,4 ' -isopropylidenebisphenol (bisphenols A), 4,4 ' -sulfenyldiphenol, 4,4 ' -oxydifenol,

4,4 ' -dihydroxybenzophenone and 9,9-bis (4-hydroxyphenyl) fluorene.

Monofunctional nuclei which may be used in the practice of this invention include water, hydrogen sulfide, ammonia, ammonium hydroxide, hydroxylarene, aryloxide salt, carboxylic acid, carboxylic acid salt, mercaptan or thiolate salt. Preferably, the hydroxyarene is phenol, cresol, methoxyphenol or 4-tert. butylphenol; the aryloxydate is sodium or potassium phenoate;

The carboxylic acid is acetic acid or benzoic acid; the carboxylic acid salt is sodium acetate, sodium benzoate, sodium ethylhexanoate, potassium acetate, potassium benzoate, potassium ethylhexanoate or calcium ethylhexanoate; the mercaptan is 3-mercapto-1,2-propanediol or benzethiol and the thiolate salt is sodium or potassium benzethiolate.

Preferred catalysts include metal hydroxides, quaternary ammonium salts, or quaternary phosphonium salts. Particularly preferred catalysts are sodium hydroxide, potassium hydroxide, ammonium hydroxide, ethyltriphenylphosphonium acetate, tetrabutylammonium bromide and bis (triphenylphosphoranylidenammonium chloride).

The conditions under which the reaction is carried out most preferably depend on various factors including the specific reactants, the solvent and the catalyst used, but generally the reaction is conducted under non-oxidizing atmosphere conditions such as a nitrogen blanket preferably at a temperature of 100 ° C to 190 ° C. The reaction may be conducted as pure (without solvent or diluents). However, in order to ensure homogeneous reaction mixtures at such temperatures, it is often desirable to use inert organic solvents for the reactants. Examples of suitable solvents include 1-methyl-2-pyrrolidinone (NMP) and ethers or hydroxyethers such as diglyme, triglyme, diethylene glycol ethyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol phenyl ether, propylene glycol methyl ether, and tripropylene glycol methyl ether.

After treatment of the reaction product with a monofunctional nucleophile that is not a primary or secondary amine, the polyetheramine can be recovered from the reaction mixture by conventional methods. For example, the polymer-containing reaction mixture can be diluted with a suitable solvent such as dimethylformamide, cooled to room temperature, and the polymer isolated by precipitation from a non-solvent such as a 50/50 mixture of methanol and water. The precipitated polymer can then be purified by washing as in the first wash with fresh 50/50 methanol / water and then fresh water. The polymer is collected by filtration, washed with a suitable solvent such as water, and dried.

Films prepared from the polyetheramine of the present invention containing hydroxyl functional groups typically have oxygen transfer rates (OTRs) of 0.1 to 4 cc / mil / 100 in ² / atm / day at 25 ° C and 60 percent relative humidity (ASTM D-3985); carbon dioxide transmission rates (CO2TR) from 1.5 to 35 cc-mil / 100 in ² -atm-day at 23 ° C and 0 percent relative humidity and water vapor transmission rates (WVTR) ) from 0.7 to 3.5 cc-mil / 100 in ² -at-day at 38 ° C and 90 percent relative humidity (ASTM F-372).

Film and laminate structures may be formed from a hydroxyl functional polyetheramine of the present invention using conventional extrusion techniques such as feedblock extrusion, multiple damped coextrusion, or a combination of both, or by spraying or solution casting. Solution casting is a known process and is described, for example, in the Plastics Engineering Handbook of the Society of Plastics Industry, Inc. 4th Edition, page 448.

The containers and other molded parts can be made from film or laminate structures comprising the polyetheramines of the invention using conventional manufacturing techniques for thermoplastic polymers such as compression molding, injection molding, extrusion, heat molding, blow molding and casting.

Generally, laminate structures may be formed from hydroxyl functional polyetheramines of the invention by co-extrusion of one or more layers of organic polymer and one or more layers of hydroxyl functional polyetheramine wherein the polyetheramine adheres directly to the organic polymer interface layer without using an adhesive layer therebetween.

The laminate structure may be a three-layer laminate consisting of a first outer layer of an organic polymer, an inner layer of a polyetheramine containing hydroxyl functional groups, and a second outer layer of an organic polymer that is the same or different from the organic polymer of the first outer layer.

--: »Τ '* ·%

The laminate structures may also be three-layer laminates, consisting of a first outer layer of a hydroxyl-functional polyetheramine, an inner layer of an organic polymer, and a second outer layer of an organic polymer that is the same or different from the organic polymer of the inner layer.

The laminate structure may also be a three-layer laminate consisting of a first outer layer of a hydroxyl-functional polyetheramine, an inner layer of an organic polymer, and a second outer layer of a polyetheramine that is the same or different from the polyetheramine of the first outer layer.

Organic polymers that can be used in the practice of this invention to prepare laminate structures include crystalline thermoplastic polyesters such as polyethylene terephthalate (PET), polyamides, polyolefins, and monovinyl aromatic monomer polyolefins.

Polyesters and methods for their preparation are well known in the art, and references have been made for the purpose of this invention. For purposes of illustration and not limitation, the references refer specifically to pages 1 - 62 of the Encyclopedia of Polymer Science and Engineering, 1988 revision, John Wiley & Sons.

Polyamides that can be used in the practice of the present invention include various types of nylon such as nylon 6, nylon 66 and nylon 12.

Polyolefins that can be used in the practice of the present invention include, for example, low density polyethylene, linear low density polyethylene, very low density polyethylene, polypropylene, polybutene, ethylene / vinyl acetate copolymers, ethylene / propylene copolymers, and ethylene / butene- copolymers. 1.

Polyolefins based on monovinyl aromatic monomers that can be used in the practice of this invention include polystyrene, polymethylstyrene and styrene / methylstyrene or styrene / chlorstyrene copolymers.

Other organic polymers of polyesters or types of polyamides can also be used in the practice of the present invention to prepare laminate structures. Such polymers include polyhexamethylene adipamide, polycaprolactone, " 4 ".

4 polyhexamethylenesebacamide, polyethylene 2,6-naphthalate and polyethylene 1,5-naphthalate, polytetramethylene 1,2-dioxybenzoate, and ethylene terephthalate ethylene isophthalate copolymers.

The reinforcement of each layer in the laminate structure depends on many factors including the intended use, the materials stored in the containers, the length of storage before use and the specific composition used in each layer of the laminate.

Generally, the laminate structures should have a total thickness of from 0.5 to 500 mils, preferably from 1.0 to 250 mils, with a layer thickness (e) of the hydroxyfunctionalized polyetheramine from 0.5 to 100 mils, preferably from 0.1 to 50 mils, and at a polyester layer (ev) thickness of from 0.45 to 400 mils, preferably from 0.9 to 200 mils.

The hydroxyl-functional polyetheramine can also be prepared and made into a shaped article by a reactive extrusion process in which the reactans are fed into the extruder and reacted therein under the conditions described in U.S. Patent No. 4,612,156.

The following working examples are given to illustrate the invention and should not be construed as limiting the scope thereof. Unless otherwise indicated, all parts and percentages are by weight.

DETAILED DESCRIPTION OF THE INVENTION

Comparative example A:

A stirred solution of bisphenol A diglyciether A (epoxy equilibrium weight = 172.3; 212.56 g, 0.617 mol), ethanolamine (37.44 g, 0.614 mol) and dipropylene glycol methyl ether (170 mL) was slowly heated to 152 ° C and then kept at 152 ° C. temperature to 140 ° C to 143 ° C for 1.5 hours, during which time 90 ° C.

* · · ♦. · <£ β is added in 20 to 50 ml aliquots of additional solvent (330 ml) to ensure adequate mixing as soon as the viscosity of the solution increases. The solution was cooled to room temperature and then poured into a vigorously stirred solution of methanol (300 mL) and ice water (2.2 L) to precipitate the polyetheramine as a fibrous powder which was separated by decantation, stirred with methanol, water and collected by filtration . The product was then mechanically stirred with 4: 1 methanol / water for 24 hours, collected by filtration, dried under vacuum at 35 ° C for 4 hours, redissolved in tetrahydrofuran (2 ml / gram of product), reprecipitated from the mixture methanol / water and dried under vacuum at 82 ° C for 16 hours after which the polymer was no longer soluble in tetrahydrofuran or dimethylformamide (DMF). These results show that the polymer crosslinks at elevated temperature and is not thermoplastic.

Example 1:

A total amount of 85.7 g of a solution of polyetheramine (29.5 g) in dipropylene glycol methyl ether prepared as described in Comparative Example A prior to precipitation and isolation of the product was heated to 52 ° C with stirring, 0.91 g of ammonium hydroxide solution ( 28-30% aqueous ammonia solution) and then held at 71 ° C for 18 hours. Additional aqueous ammonia solution (0.65 g) was then added and stirring was continued at 143 ° C

1.5 hours. The product was then isolated in the same manner as described in Comparative Example A. After drying under vacuum at 76 ° C for 16 hours, the product remained soluble in DMF, having an intrinsic viscosity of 0.64 dl / g (0.5 g / dl; DMF; 25 ° C) and did not exhibit substantially a change in initial melt viscosity of about 1000 Pa.s after 30 minutes at 200 ° C as measured by the rheometer in an oscillating manner at 5% voltage and 10 rad / s over a gap distance of 0.5 mm. These results showed that ammonia did not consume any residual epoxy groups of the product and a heat-treatable thermoplastic was obtained.

· Fe · · * * * * * * * fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe · «· · · · · · · fefefe fe '

Example 2:

To 98.7 g of a stirred solution of polyetheramine (34.0 g) in dipropylene glycol methyl ester prepared as described in Comparative Example A prior to precipitation and isolation was added benzoic acid (2.0 g) and then maintained at 134 ° C to 143 ° C for for 2 hours. The product was then isolated as described in Comparative Experiment A. After drying under vacuum at 82 ° C for 16 hours, the product remained soluble in DMF, having an intrinsic viscosity of 0.68 dl / g (0.5 g / dl; DMF; 25). Essentially did not show a change in the initial melt viscosity of about 1000 Pa.s after 30 minutes at 200 ° C as measured by a rheometer in an oscillating manner at 5% voltage and 10 rad / s at a gap distance of 0.5 mm. These results showed that ammonia did not consume any residual expoxy groups of the product and a heat-treatable thermoplastic was obtained.

Example 3:

To 98.1 g of a stirred solution of polyetheramine (33.8 g) in dipropylene glycol methyl ester, prepared as described in Comparative Example A before precipitation and isolation of the product, phenol (1.52 g) was added and heated to 80 ° C, then 0 was added. 11 g of tetrabutylphosphonium acetate (50 percent in methanol) and the resulting solution was maintained at 150 ° C for 2.5 hours. The product was then isolated as described in Comparative Example A. After drying under vacuum at 82 ° C for 16 hours, the product remained soluble in DMF, having an intrinsic viscosity of 0.55 dl / g (0.5 g / dl; DMF;

And showed no change in the initial melt viscosity of about 1000 Pa.s after 30 minutes at 200 ° C as measured by a rheometer in an oscillating manner at 5% voltage and 10 rad / s at a gap distance of 0.5 mm. These results show that ammonia did not consume any residual epoxy groups of the product and that a heat-treatable thermoplastic was obtained.

· · Χ ι ι f c c!!!!!!!!!!!!!!! β • f c c c c c <<<<c;;;;;;;;;;;; φ · fcfc

Example 4:

Κ 98.8 g of a stirred solution of polyetheramine (34.0 g) in dipropylene glycol methyl ether, prepared as described in Comparative Experiment A before precipitation and isolation of the product, 3-mercapto-1,2-propanediol (2.0 g) was added and then kept at 81 ° C for 12 hours and then at 149 ° C for 3 hours. The product was then isolated as described in Comparative Experiment A. After drying under vacuum at 82 ° C for 16 hours, the product remained soluble in DMF, having an intrinsic viscosity of 0.46 dl / g (0.5 g / dl; DMF;

° C) and did not exhibit essentially a change in the initial melt viscosity of about 1000 Pa.s after 30 minutes at 200 ° C as measured by a rheometer in an oscillating manner at 5 percent voltage and 10 rad / s at gap spacing (holes)

0.5 mm. These results showed that ammonia did not consume any residual epoxy groups in the product and a heat-treatable thermoplastic was obtained.

Example 5:

Κ 111.5 g of a stirred solution of polyetheramine (38.4 g) in dipropylene glycol methyl ether, prepared as described in Comparative Example A before precipitation and isolation of the product, 4-tert-butylphenol (2.76 g) was added and heated to 80 ° C. Tetrabutylphosphonium acetate (50 percent in methanol; 0.086 g) was then added and the solution was stirred at 149 ° C for 3 hours. The product was then isolated as described in Comparative Experiment A. After drying under vacuum at 82 ° C for 16 hours, the product remained soluble in DMF, having an intrinsic viscosity of 0.46 dl / g (0.5 g / dl; DMF; 25 °). C) and did not exhibit substantially a change in the initial melt viscosity of about 1000 Pa.s after 30 minutes at 200 ° C as measured by the rheometer in an oscillating manner at 5 percent voltage and 10 rad / s at a gap distance of 0.5 mm. These results showed that ammonia did not consume any residual epoxy groups in the product and a heat-treatable thermoplastic was obtained.

· «·» ·. ·· ·· · «·. áh® ^- • · 0 · * 0 '· 0 0j 0' · • 0 '0 00 0 · 0 0 0 0'><0 0 »• 0 * 0 0 <0 · 00 00 · · 0 0 0 · · · 0 ·

000 00 00J 0 0 00

Claims (25)

PATENT CLAIMS 1. A hydroxyl-containing thermoplastic polyetheramine having the formula: OH OH OH OH I XCH ₂ CH ₂ OB - (- OCH ₂ CH ₂ ACH ₂ CH ₂ OB-) _n -OCH ₂ CH ₂ XR ¹ R ¹ R ¹ Ai \ N-Ni wherein each A in the above formula is represented by any of the following formulas: —N — R ⁴ —N— ii R ² R ² wherein each R ² is independently alkyl, an inertly substituted alkyl, aryl or an inertly substituted aryl moiety wherein substituent (s) is hydroxyl, halo, aryloxy, alkylamido, arylamido, alkylcarbonyl or arylcarbonyl, wherein each R is independently alkylene inert a substituted alkylene, arylene or inertly substituted arylene moiety wherein the substituent (s) is alkylamido, hydroxy, alkoxy, halo, cyano, aryloxy, alkylcarbonyl or arylcarbonyl; wherein each B is 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, methylenediphenylene, isopropylidenediphenylene, oxydiphenylene, thiodiphenylene, carbonyldiphenylene, diphenylfluorene or a combination thereof, wherein each R 1 is a hydrogen or hydrocarbyl moiety wherein each X is independently hydrogen a primary amino moiety, a hydroxyl moiety, an alkyl, heteroalkyl, an inertly substituted alkyl or an inertly substituted heteroalkyl group, an aryloxy or an inertly substituted aryloxy group, an alkanthi or an inertly substituted alkanthio group, an arenthio or an inertly substituted arenthio group wherein the substituent is hydroxyl, cyano, halo, aryloxy, alkylamido, arylamido, alkylcarbonyl or arylcarbonyl or independently represented by one of the formulas: ♦ toto · · to to to to to to to to to. · To · «to 'toi to to * tototo ¹ to ^; to · to · to · to · to · to · to · to this to this * to this OR ⁽ OR ⁶ R ⁵ —C — OR ⁵ —C — S — R ⁵ —C — S — R ⁵ —C — N — R ⁵ —S — N— R-C / -c c CH— CH wherein each R ⁵ is independently an alkyl or heteroalkyl inertly substituted alkyl or heteroalkyl, aryl or inertly substituted aryl group wherein substituent (s) is cyano, halo, aryloxy, alkylamido, arylamido, alkylcarbonyl or arylcarbonyl; R ⁶ is independently hydrogen, alkyl or heteroalkyl, inert substituted alkyl or heteroalkyl, aryl or inert substituted aryl, wherein substituent (s) is the same as for R ³ and R ⁷ is alkylene or heteroalkylene inert substituted alkylene or heteroalkylene, arylene or inert a substituted arylene moiety wherein substituent (s) is alkylamido, hydroxy, alkoxy, halo, cyano, aryloxy, alkylcarbonyl or arylcarbonyl or combinations thereof with a monovalent moiety that is a secondary or tertiary amine and n is an integer from 5 to 1000. Polyetheramine according to claim 1, wherein X is methoxy, ethoxy, propoxy, 2- (methoxy) ethoxy, 2- (ethoxy) ethoxy, benzyloxy, phenyloxy, p-methylphenyloxy, p-methoxyphenoxy, 4-tert-butylphenoxy, methylmercapto, ethylmercapto, propylmercapto, 2- (methoxy) ethylmercapto, 2- (ethoxy) ethylmercapto, benzylmercapto, 2,3-dihydroxypropylmercapto, phenylmercapto, p-methylphenylmercapto, acetate, benzoate, acetamido or benzenesulfenamido. ·· * · * · «► ♦ ♦ ·» · it · · · * It '· a · <·' • · it · ·· ···> «γ · ¹ · * * · it · · To to to 'to to to to> «« «« «« «« «« Polyetheramine according to claim 2, wherein R ¹ is hydrogen or methyl, R ² is methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2,3-dihydroxpropyl, 2- (acetamido) ethyl , benzyl, phenyl, p-methoxyphenyl, p-methylhenyl, 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. The polyetheramine of claim 1, which is the reaction product of a diglycidyl ether, a difunctional amine and a monofunctional nucleophile that is not a primary or secondary amine. 5. A process for preparing a hydroxyl-containing thermoplastic polyetheramine comprising reacting a difunctional amine with an excess or an equimolar amount of dyglycidyl ether and treating the reaction product with a monofunctional nucleophile that is not a primary or secondary amine, optionally in the presence of a catalyst. The method of claim 9, wherein the monofunctional nucleophile is water, hydrogen sulfide, ammonia, ammonium hydroxide, hydroxyarene, aryloxide salt, carboxylic acid, carboxylic acid salt, mercaptan or thiolate salt. 7. The process of claim 10 wherein the hydroxyarene is phenol, cresol, methoxyphenol or 4-tert-butylphenol. 8. The process of claim 10 wherein the alloxide salt is sodium or potassium phenate. 0 0 '♦ ·· »00 00.-00 09' ♦ 9 9 0 '0 ·» ·. 9 9 9 '9' 9 0 0 0 99 99 9 9 β 9 9 9 '' 0 0 0 0 9 9 0 0 0 9 • ·· «0 9 9’ 9 0 0 0 0 0 9 '9 9 9 9 9 9 9 0 9' 0 0 9. The process of claim 10 wherein the carboxylic acid is acetic acid or benzoic acid. The method of claim 10, wherein the carboxylic acid salt is sodium acetate, sodium benzoate, sodium ethylhexanoate, potassium acetate, potassium benzoate, potassium ethylhexanoate or calcium ethylhexanoate. The method of claim 10, wherein the mercaptan is 3-mercapto-1,2-propanediol or benzethiol. The method of claim 10, wherein the thiolate salt is sodium or potassium benzoethiolate. 13. The process of claim 9 wherein the catalyst is a quaternary ammonium salt, a quaternary phosphonium salt, or a metal hydroxide. 14. The process of claim 9 wherein the catalyst is ammonium hydroxide, ethyltriphenylphosphonium acetate, tetrabutylammonium bromide, bis (triphenylphosphoranilidine) ammonium chloride, sodium hydroxide or potassium hydroxide. 15. A laminate structure comprising one or more layers of a hydroxyl-functional polyetheramine, wherein said hydroxyl-functional polyetheramine layer is attached directly to an adjacent organic polymer layer without the use of an adhesive layer therebetween, a hydroxyl-functional polyetheramine layer. has the formula: 0 000 0 0 · 0 »0 000 0 0. 0 0 0 0 0 0 0 0 0 0 0 '0 β i · S 0' 0 '· 0 00 0 0 0 0 0 '0 * 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0. 0 0 0 0 0 0 OH OH OH AND OH XCH ₂ eCH ₂ OB - (- OCH ₂ CCH ₂ ACH ₂ CCH ₂ OB-) _n -OCH ₂ CCH ₂ XR ¹ RR ¹ R ¹ wherein each A in the above formula is represented by any of the following formulas: / ^R \ —Ν NN— I τλ2 —N — R ⁴ —N— I l R ² R ² wherein each R is independently an alkyl inertly substituted alkyl aryl or an inertly substituted aryl moiety wherein substituent (s) is hydroxyl, cyano, halo, aryloxy, alkylamido, arylamido, alkylcarbonyl or arylcarbonyl, wherein each R is independently alkylene, inert substituted alkylene and wherein R ⁴ is independently alkylene inertly substituted alkylene, arylene or inertly substituted arylene moiety wherein substituent (s) is alkylamido, hydroxy, halo, cyano, ayloxy, alkylcarbonyl or arylcarbonyl, wherein each B is 1,4-phenylene 1,3-phenylene, 1,2-phenylene, methylenediphenylene, isopropylidenediphenylene, oxydiphenylene, thiodiphenylene, carbonyldiphenylene, diphenylfluorene or a combination thereof, wherein each R ¹ is a hydrogen or hydrocarbyl moiety; wherein each X is independently a hydrogen, primary amino, hydroxyl, alkyl heteroalkyl, inertly substituted alkyl or inertly substituted heteroalkyl group, aryl or inertly substituted aryl group, alkoxy or inertly substituted alkoxy group, aryloxy or inertly substituted aryloxy group, alkanthio or inert a substituted alkanthio, arenthio or inertly substituted arenthio group wherein substituent (s) is hydroxyl, cyano, halo, aryloxy, alkylamido, arylamido, alkylcarbonyl or arylcarbonyl or is independently represented by any of the formulas: R ⁵ —C — OR ⁵ —C — SS R ⁵ —C — S— OR ⁶ . II I R ³ —C — N— AB ⁶ ₅ II I R ⁵ —S — N— II o R ⁵ - R ⁵ - ^C x CH - wherein R ⁵ is independently alkyl or heteroalkyl, an inertly substituted alkyl or heteroalkyl, aryl or inertly substituted aryl group wherein substituent (s) is cyano, halo, aryloxy, 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 for R and R is an alkylene or heteroalkylene inertly substituted alkylene or heteroalkylene, arylene or inertly substituted arylene moiety wherein the substituent (s) is alkyl amide, hydroxy, alkoxy, halo, cyano, aryloxy, alkylcarbonyl or arylcarbonyl, or a combination thereof in a monovalent moiety that is a secondary or thermal amine and is an integer from 5 to 1000. A laminate structure according to claim 19, characterized in that it comprises an outer layer of an organic polymer and an inner layer of a polyetheramine containing hydroxyl functional groups. A laminate structure according to claim 19, characterized in that it comprises a first outer layer of a hydroxyl-functional polyetheramine, an inner layer of an organic polymer, and a second outer layer: fefefe fefe f ef ef ef f • f f z z z z z z z z z z z z z z z z z z z z z z z z z z z z z z z z z z z z z of the polymer inner layer. A laminate structure according to claim 19, characterized in that it comprises a first outer layer of a polyetheramine containing hydroxyl functional groups, an inner layer of an organic polymer and a second outer layer of a polyetheramine containing hydroxyl functional groups which is the same or different from a polyetheramine containing hydroxyl functional groups. the first outer layer. 19. The laminate of claim 19 wherein the organic polymer is a crystalline thermoplastic polyester, polyamide, polyolefin or polyolefin based on monovinyl aromatic monomers. 20. The laminate structure of claim 23 wherein the crystalline polyester is polyethylene terephthalate. 21. The laminate of claim 23 wherein the polyamide is nylon 6, nylon 66 or nylon 12. 22. The laminate of claim 23 wherein the polyolefin is polyethylene and the monovinyl aromatic monomer polyolefin is polystyrene, polymethylstyrene, styrene / methylstyrene copolymer or styrene / chlorostyrene copolymer. Laminate structure according to claim 23, characterized in that the organic polymer is polyhexamethylene adipamide, polycaprolactone, polyhexamethylenesebacamide, polyethylene 2,6-naphthalate, polyethylene 1,5 9 · * · -naphthalate, polytetramethylene 1,2-dioxybenzoate or ethylene terephthalate / ethylene isophthalic copolymer. 24. Polyetheramine according to claim 1, characterized in that it is in the form of a protective film, a protective coating, a protective coating, a foamed or shaped article. 25. A water-borne or solvent-borne coating composition which is prepared from a hydroxyl-functional polyetheramine according to claim 1.