WO2002059177A2

WO2002059177A2 - Poly (hydroxyaminoethers) having a low chloride content

Info

Publication number: WO2002059177A2
Application number: PCT/US2001/048717
Authority: WO
Inventors: Terry W. Glass; Michael B. Cavitt; Jerry E. White
Original assignee: Dow Global Technologies Inc.
Priority date: 2000-12-22
Filing date: 2001-12-14
Publication date: 2002-08-01
Also published as: AU2002248191A1; WO2002059177A3

Abstract

A poly(hydroxyaminoether) having a chloride content of not greater than 1900 ppm and prepared by (1) epoxidizing a diphenol or a blend of diphenols to produce the diglycidyl ethers having the desired purity and (2) reacting the diglycidyl ether or blend of diglycidyl ethers with one or more amine dinucleophiles, such as monoethanolamine to produce a poly (hydroxyaminoether) having reduced chloride content.

Description

LOW CHLORIDE COMPOSITION FOR THE MANUFACTURE OF POLY (HYDROXYAMINOETHERS) (PHAE)

This invention relates to a process for the manufacture of poly (hydroxyaminoethers) . Poly (hydroxyaminoethers) are prepared by reacting diglycidyl ethers or blends of diglycidyl ethers with dinucleophiles, such as monoethanolamine (MEA) . One particular blend of commercial interest consists of a blend of resorcinol diglycidyl ether (RDGE) and bisphenol A diglycidyl ether (BADGE) . This blend has been prepared by mixing together commercially available sources of RDGE and BADGE. Currently, PHAE manufacturers' options on raw materials, purity of raw materials and economics are limited, due to small volume sources of diglycidyl ethers, such as RDGE, and product performance has been adversely affected.

Commercially available glycidyl ethers have chloride contents that negatively affect the performance of poly (hydroxyaminoethers) . This effect is notable in the torque changes with time at a given processing temperature as described below. It would be desirable to provide a composition of matter for preparing PHAE having reduced chloride contents using raw materials that are commercially available in large quantities .

In a first aspect, the present invention^' is a poly (hydroxyaminoether) having a chloride content of not greater than 1900 ppm.

In a second aspect, the present invention is a process for preparing PHAE which comprises (1) providing a diglycidyl ether or a blend of diglycidyl ethers formed from a mixture of two or more diphenols, (2) epoxidizing the diglycidyl ether or blend of diglycidyl ethers to produce an intermediate product containing the desired mixture of diglycidyl ethers having the desired purity and (3) reacting the diglycidyl ether or blend of diglycidyl ethers with one or more dinucleophiles, such as monoethanolamine to produce a poly (hydroxyaminoether) having reduced chloride content.

In a third aspect, the present invention is a composition of matter comprising from 40 weight percent to 90 weight percent of a first diglycidyl ether and from 10 weight percent to 60 weight percent of a second diglycidyl ether.

, The process for preparing the poly (hydroxyaminoether) in accordance with the present invention comprises (1) providing a diglycidyl ether or a blend of diglycidyl ethers formed from a mixture of two or more diphenols, (2) epoxidizing the diglycidyl ether or blend of diglycidyl ethers to produce an intermediate product containing the desired mixture of diglycidyl ethers having the desired purity, and (3) reacting the mixture of . diglycidyl ethers with one or more dinucleophiles to produce a poly (hydroxyaminoether) having reduced chloride contents .

The reaction conditions involved in the epoxidation of the diglycidyl ethers blend depends on a variety of factors, including temperature, pressure and phase transfer catalyst. In general, the epoxidation is conducted in the presence of a phase transfer catalyst at a temperature of from 45°C to 0°C, more preferably from 50°C to 90°C and most preferably from 60°C to 80°C; for a reaction time that gives conversion of the phenolic groups to epoxy groups, usually for 1.5 hours to 12 hours, preferably from 2 hours to 6 hours and most preferably 4 hours. The pressure can vary but, in general, the pressure should be at a pressure to allow an azeotropic removal of water to balance with the feed rate of the caustic solution and the water being generated during the reaction, usually from 100 mbar to 600 mbar, preferably from 160 mbar to 300 mbar, and most preferably from 180 mbar to 270 mbar.

The diphenols which can be employed in the practice of the present invention for preparing the poly (hydroxyaminoether) include resorcinol, hydroquinone, 4, 4 ' -isopropylidene bisphenol (bisphenol A),

4,4' -dihydroxydiphenylethylmethane, 3,3' -dihydroxy- diphenyldiethyI ethane, 3,4' -dihydroxydiphenyl- methylpropylmethane, 4,4' -dihydroxydiphenyloxide, 4,4' -dihydroxydiphenylmethane , 4,4' -dihydroxydiphenyl- cyanomethane, 4 , 4 ' -dihydroxybiphenyl ,

4,4' -dihydroxybenzophenone (bisphenol-K) , 4,4' -dihydroxydiphenyl sulfide, 4,4' -dihydroxydiphenyl sulfone, 2 , 6-dihydroxynaphthalene, 1, 4-dihydroxy- naphthalene, catechol, 2 , 2-bis (4-hydroxyphenyl) -acetamide, 5-methylresorcinol, methoxyhydroquinone , 2, 2-bis (4- hydroxyphenyl) ethanol , 2,2-bis (4-hydroxyphenyl ) -N- methylacetamide, 2, 2-bis (4-hydroxy-phenyl) -N,N- dimethylacetamide, 3 , 5-dihydroxyphenyl-acetamide, 2 , 4-dihydroxyphenyl-N- (hydroxyethyl) -acetamide, 4, 4' - (ethylenedioxy) iphenol, 3 , 3 ' - (ethylenedioxy) diphenol, 4, 4 ' - (1, 3-adamantanediyl) diphenol, 4 , 4 ' -biphenol , diethylstilbestrol, meso-hexestrol, and other dihydric phenols listed in U.S. Patents 3,395,118, 4,438,254 and 4,480,082, as well as mixtures of one or more of such diglycidyl ethers. More preferred diphenols are bisphenol-A, hydroquinone, and resorcinol with bisphenol-A being most preferred. The dinucleophiles which can be employed in the practice of the present invention for preparing the poly (hydroxyaminoether) include monoethanolamine, 3-amino- 1-propanol, 2-amino-l-propanol, isopropanolamine, 2-amino- 2-ethyl-l, 3-propanediol, 2-amino-2-methyl-l-propanol,

4-amino-l-butanol, 4-aminocyclohexanol, 2-amino-2-methyl- 1-propanol, tris (hydroxymethyl) aminomethane, serinol 4-amino-l-butanol, methylamine, ethanylamine, propylamine, isopropylamine, butylamine, tert-butylamine, hexylamine, 1- (3-aminopropyl) imidazole, 4- (3-aminopropyl) morpholine, 1- (3-aminopropyl) -2-pipecoline, 1- (3-aminopropyl) -2- pyrrolidinone, isoamylamine, propylamine, isopropylamine, piperazine, 2-methylpiperazine, benzyla ine, methylbenzylamine, cyclopentylamine, cyclohexane- methylamine, 2- (1-cyclohexenyl) ethylamine,

4-methylcyclohexylamine, 2-amino-l-methoxypropane, 3-methoxypropylamine, cyclohexylamine . More preferred dinucleophiles are monoethanolamine, isopropanolamine, benzylamine, propylamine, cyclohexylamine and isopropylamine, with monoethanolamine, cyclohexylamine and benzylamine being the most preferred.

The first diglycidyl ether can be the diglycidyl ether of 4, 4 ' -isopropylidene bisphenol and the second diglycidyl ether can be the diglycidyl ether of resorcinol, hydroquinone, 4, 4 ' -dihydroxydiphenyl- ethyImethane, 3,3' -dihydroxydiphenyldiethylmethane, 3,4' -dihydroxydiphenylmethylpropylmethane, 4,4' -dihydroxydiphenyloxide, 4,4' -dihydroxydiphenyl- methane, 4,4' -dihydroxydiphenylcyanomethane, 4, 4'-dihydroxybiphenyl, 4, 4 ' -dihydroxybenzophenone

(bisphenol K) , 4 , 4 ' -dihydroxydiphenyl sulfide, 4,4' -dihydroxydiphenyl sulfone, 2 , 6-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, catechol, 2, 2-bis (4- hydroxyphenyl) -acetamide, 5-methylresorcinol, methoxyhydroquinone, 2 , 2-bis (4-hydroxyphenyl) ethanol, 2 , 2-bis (4-hydroxyphenyl) -N-methylacetamide, 2 , 2-bis (4- hydroxyphenyl) -N, N-dimethylacetamide, 3 , 5-dihydroxyphenyl , 2 , 4-dihydroxyphenyl-N- (hydroxyethyl) -acetamide, 4, 4 '- (ethylenedioxy) diphenol, 3 , 3 '- (ethylenedioxy) dipheno1, 4 , ' - ( 1 , 3-ada antanediy1) dipheno1 , 4,4'- biphenol, diethylstilbestrol, meso-hexestrol, or the diglycidyl ethers of dihydric phenols disclosed in U.S. Patents 3,395,118, 4,438,254 and 4,480,082, as well as mixtures of one or more of such diglycidyl ethers .

The phase transfer catalysts which can be employed in the practice of the present invention for preparing the poly (hydroxyaminoether) include quaternary amines such as benzyltrimethylammonium chloride, diallyldimethylammonium chloride and tetramethylammonium chloride; inorganic compounds such as lithium hydroxide, lithium chloride, sodium hydroxide and potassium hydroxide; primary and secondary alcohol's such as propanol, 2-propanol, butanol and 2-butanol; alcohols with ether linkages such as 2- (2-butoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2-butoxyethanol , 2-ethoxyethanol, 2-methoxyethanol and l-methoxy-2- propanol .

The following examples are for illustrative purposes only and are not intended to limit the scope of this invention. Unless otherwise indicated, all parts and percentages are by weight.

Example 1

Step 1 Preparation Of The Blend Of Diglycidyl Ethers

Bisphenol A (52.86 g) and resorcinol (37.16 g) were mixed. To this mixture was added epichlorohydrin (729 g) and DOWANOL™ PM propylene glycol methyl ether (1-methoxy-2-propanol) , a product of The Dow Chemical Company (81 g) . To compensate for the water azeotrope, a side arm funnel was used that was filled with 10 percent DOWANOL PM and 90 percent epichlorohydrin . The mixture was heated to 65°C and the pressure reduced to 267 mbar. At 49.26 percent NaOH solution (92.51 g) was added in 4 hours at 0.385 g/min. The mixture was cooled to ambient temperature whereupon the mixture was filtered to remove salt. The resulting solution was water-washed three times using a 10:1 organic to water ratio. After the third water wash the organic material was coalesced via 2-ply Whatman 2^'-V fluted filter paper. The organic material was vacuum- distilled at < 20 mmHG at 180°C with a final 1 hour helium purge resulting in 130 g of product. This composition had an epoxide equivalent weight of 138.

Step 2

The product of Step 1 was reacted with monoethanolamine in a 150 mL reaction vessel fitted with a stirrer, temperature control and nitrogen purge. To the reaction vessel was added Step 1 epoxy (23 g) , DOWANOL PM

(18.7 g) and monoethanolamine (5.09 g) . This reaction mixture was heated to 145°C and maintained at that temperature for 13 minutes whereupon diethanolamine (2 g) in DOWANOL DPM (5 g) was added. The reaction temperature was held at 150°C for 3 hours and 35 minutes then cooled to 130°C. This polymer solution was slowly poured into an ice water slurry using a high shear mixer to obtain a solid polymer. The polymer was washed with water then dried in a vacuum oven over night at 40°C. The resulting polymer had a molecular weight of 64,618 and a Tg of 63°C. This polymer contained 859 ppm chloride. Example 2

The product of Step 1 was reacted with cyclohexylamine in a 150 mL reaction vessel fitted with a stirrer, temperature control and nitrogen purge. To the reaction vessel was added Step 1 epoxy (22 g) , DOWANOL PM (19.9 g) and cyclohexylamine (7.91 g) . This reaction mixture was heated to 80°C for 7 hours then cooled to ambient temperature and allowed to set overnight. The next morning, the reaction mixture was heated to 135°C and held for 2 hours and 35 minutes whereupon diethanolamine (2 g) in DOWANOL DPM (5 g) was added. The reaction temperature was held at 120°C for 4 hours and 20 minutes then cooled to 100°C. This polymer solution was slowly poured into an ice water slurry using a high shear mixer to obtain a solid polymer . The polymer was washed with water then dried in a vacuum oven over night at 40°C. The resulting polymer had a molecular weight of 51,726 and a Tg of 68°C. This polymer contained 1004 ppm chloride.

Example 3

The product of Step 1 was reacted with monoethanolamine and cyclohexyamine in a 150 mL reaction vessel fitted with a stirrer, temperature control and nitrogen purge. To the reaction vessel was added Step 1 epoxy (22 g) , DOWANOL DPM (18.9 g) , monoethanolamine (2.4 g) and cyclohexylamine (3.94 g) . This reaction mixture was heated to 80°C and held for 2 hours and 24 minutes then cooled to ambient temperature and allowed to set overnight. The next morning, the reaction mixture was heated to 135°C and held for 1 hour and 30 minutes whereupon diethanolamine (2 g) in DOWANOL DPM (5 g) was added. The reaction temperature was held at 120°C for 1 hour and 34 minutes then cooled to 90°C. This polymer solution was slowly poured into an ice water slurry using a high shear mixer to obtain a solid polymer. The polymer was washed with water then dried in a vacuum oven over night at 40°C. The resulting polymer had a molecular weight of 75,977 and a Tg of 67°C. This polymer contained 996 ppm chloride.

Example 4

The product of Step 1 was reacted with monoethanolamine, cyclohexylamine, and propylamine in a 150 mL reaction vessel fitted with a means of stirring, temperature control and nitrogen purge. To the reaction vessel was added 20 g of Step 1 epoxy, 16.7 g of DOWANOL DPM, 2.2 g of monoethanolamine, 1.80 g of cyclohexylamine and 1.07 g of propylamine. This reaction mixture is maintained at 25°C for 2 hours and 13 minutes. The temperature was increased to 50°C and allowed to slowly increase to 80°C over a time period of 3 hours and 32 minutes then cooled to ambient temperature and allowed to set overnight . The next morning the reaction mixture was heated to 145°C and held for 1 hour whereupon 2 g of diethanolamine in 5 g of DOWANOL DPM was added. The reaction temperature was held at 120°C for 1 hour and 30 minutes then cooled to 90°C. This polymer solution was slowly poured into an ice water slurry using a high shear mixer to obtain a solid polymer. The polymer was washed with water then dried in a vacuum oven over night at 40°C. The resulting polymer has a molecular weight of 64,173 and a Tg of 60°C. This polymer contained 966 ppm chloride.

Example 5

A PHAE sample having a chloride content of 2074 ppm is placed in the bowl of a HAA E FISONS RHEOCORD 9000 coupled with a Haake Rheomix 600 bowl which is equipped with roller rotors, giving a free volume of 69 ccm and incorporating a 3:2 (left: right) rotor angular velocity. The bowl is maintained at a temperature of 180°C. After 10.7 minutes, a 50 percent torque increase is noted.

Example 6

The same procedure as described above was followed except that the PHAE had a chloride content of 1469 ppm. A 50 percent torque increase is noted after 19.6 minutes. This increase in time to a 50 percent torque increase gives those using poly (hydroxyaminoethers) more working time to make successful articles.

Example 7

Step 1 - Recrystallize Diglycidyl Ether of Bisphenol A Bisphenol A (DGEBA) (212.56 g) was washed several times with methanol, recrystallized in a refrigerator, let stand for several days in methanol on shelf at room temperature and then dried in a vacuum oven at 30 °C for 2 days. Step 2

To the product of Step 1 was added monoethanolamine (MEA) (37.44 g) and DOWANOL™ PM propylene glycol methyl ether (l-methoxy-2-propanol) , a product of The Dow Chemical Company (170 ml) . The mixture was precipitated in ice water (2.5 L) with MeOH (300ml) whereupon the mixture was filtered to remove salt. The resulting solution was water-washed three times using a 4:1 water to MeOH ratio. After the third water wash the organic material was dried in a vacuum oven at 35 to 40 C for 36 to 48 hours, dissolved in THF (3 mL THF/g polymer) and shaken overnight. This polymer contained 966 ppm chloride .

Claims

WHAT IS CLAIMED IS:

1. A poly (hydroxyaminoether) having a chloride content of not greater than 1900 ppm.

2. The poly (hydroxyaminoether) of Claim 1 formed from a single diglycidyl ether.

3. The poly (hydroxyaminoether) of Claim 1 formed from a blend of 40 weight percent to 90 weight percent of a first diglycidyl ether, and from 10 weight percent to 60 weight percent of a second diglycidyl ether.

4. The poly (hydroxyaminoether) of Claim 3 wherein the first diglycidyl ether is 4, 4 ' -isopropylidene bisphenol and the second diglycidyl ether is resorcinol, hydroquinone, 4,4' -dihydroxydiphenylethylmethane, 3,3'- dihydroxy-diphenyldiethylmethane, 3,4' -dihydroxydiphenyl- methylpropylmethane, 4,4' -dihydroxydiphenyloxide, 4,4' -dihydroxydiphenylmethane, 4,4' -dihydroxydiphenyl- cyanomethane, 4,4' -dihydroxybiphenyl , 4,4' -dihydroxy- benzophenone (bisphenol K) , 4 , 4 ' -dihydroxydiphenyl sulfide, 4, 4 ' -dihydroxydiphenyl sulfone,

2,6 -dihydroxynaphthalene, 1, 4-dihydroxy-naphthalene, catechol, 2, 2-bis (4-hydroxyphenyl) -acetamide, 5-methylresorcinol, methoxyhydroquinone , 2, 2-bis (4- hydroxyphenyl) ethanol , 2 , 2-bis (4-hydroxyphenyl ) -N- methylacetamide, 2 , 2-bis (4-hydroxyphenyl) -N,N- dimethylacetamide, 3 , 5-dihydroxyphenyl , 2 , 4-dihydroxyphenyl-N- (hydroxyethyl) -acetamide, 4 , 4 ' - (ethylenedioxy) diphenol , 3 , 3 ' - (ethylenedioxy) diphenol , 4 , 4 ' - (1 , 3-adamantanediyl) diphenol , 4, 4' -biphenol, diethylstilbestrol, or meso-hexestrol .

5. A process for preparing a poly (hydroxyaminoether) which comprises (1) providing a diglycidyl ether or a blend of diglycidyl ethers formed from a mixture of two or more diphenols, (2) epoxidizing the diglycidyl ether or blend of diglycidyl ethers to produce an intermediate product containing the desired mixture of diglycidyl ethers and (3) reacting the diglycidyl ether or blend of diglycidyl ethers with a dinucleophile to produce a poly (hydroxyaminoether) having a reduced chloride content.

6. The process of Claim 5 wherein the dinucleophile is selected from the group consisting of monoethanolamine, 3-amino-1-propanol, 2-amino-1-propanol, isopropanolamine, 2-amino-2-ethyl-l, 3-propanediol, 2- amino-2-methyl-l-propanol, 4-amino-l-butanol, 4- aminocyclohexanol, 2-amino-2-methyl-l-propanol, tris (hydroxymethyl) aminomethane, serinol

4-amino-l-butanol, methylamine, ethanylamine, propylamine, isopropylamine, butylamine, tert-butylamine, hexylamine, 1- (3-aminopropyl) imidazole, 4- (3-aminopropyl )morpholine, 1- (3-aminopropyl) -2-pipecoline, 1- (3-aminopropyl) -2- pyrrolidinone, isoamylamine, propylamine, isopropylamine, piperazine, 2-methylpiperazine, benzylamine, methylbenzylamine, cyclopentylamine, cyclohexanemethylamine, 2- (1-cyclohexenyl) ethylamine, 4-methylcyclohexylamine, 2-amino-l-methoxypropane, 3-methoxypropylamine, cyclohexylamine and mixture thereof.

7. The process of Claim 5 wherein the diphenol is selected from the group consisting of resorcinol, hydroquinone, 4, 4 ' -isopropylidene bisphenol (bisphenol A), 4,4' -dihydroxydiphenylethylmethane, 3,3' -dihydroxydiphenyl-diethylmethane, 3,4' -dihydroxydiphenyl- methylpropylmethane, 4,4' -dihydroxydiphenyloxide, 4,4' -dihydroxydiphenyl-methane, 4,4' -dihydroxydiphenyl- cyanomethane, 4,4' -dihydroxybiphenyl , 4,4' -dihydroxy- benzophenone (bisphenol-K) , 4, 4 ' -dihydroxydiphenyl sulfide, 4 , 4 ' -dihydroxydiphenyl sulfone, 2 , 6-dihydroxynaphthalene, 1,4' -dihydroxy-naphthalene, catechol, 2 , 2-bis (4-hydroxyphenyl) -acetamide, 2, 2-bis (4- hydroxyphenyl ) ethanol , 2,2-bis (4-hydroxyphenyl) -N- methylacetamide, 2 , 2-bis (4-hydroxy-phenyl) -N,N- dimethylacetamide, 3 , 5-dihydroxyphenyl-acetamide, and 2 , 4-dihydroxyphenyl-N- (hydroxyethyl ) -acetamide .

8. The process of Claim 7 wherein the diphenol is selected from the group consisting of bisphenol A, resorcinol, hydroquinone, bisphenol F, bisphenol K and bisphenol S.

9. The process of Claim 5 wherein the epoxidation is conducted in the presence of a phase transfer catalyst at a temperature of from 45°C to 90°C, for a reaction time of from 1.5 hours to 12 hours .

10. The process of Claim 5 wherein the epoxidation is conducted at a pressure of from 100 mbar to 600 mbar.