Title of Invention	A PROCESS FOR THE PREPARATION OF A NOVEL POLYMER ALLOY USEFUL FOR MAKING PROTECTIVE COATINGS
Abstract	A process for the preparation of a novel polymer alloy useful for making protective coatings by refluxing an oligomeric resin containing terminal oxirane oxygen and having molecular weight <4000 in an organic solvent/solvent mixture optionally with the addition of an amide of Mannich's base type along with esters of different types having molecular formula H2C=C(R1)COO(R2) where R1 may be preferably of C1-6 type and R2 of C2-8 an acrylic crosslinking agent selected from ethylene glycol dimethyl acrylate, a free radical polymeric initiator and a catalyst such as herein described for a period of at least two hours under inert atmosphere to obtain the novel polymer alloy.

Title of Invention

A PROCESS FOR THE PREPARATION OF A NOVEL POLYMER ALLOY USEFUL FOR MAKING PROTECTIVE COATINGS

Abstract

A process for the preparation of a novel polymer alloy useful for making protective coatings by refluxing an oligomeric resin containing terminal oxirane oxygen and having molecular weight <4000 in an organic solvent/solvent mixture optionally with the addition of an amide of Mannich's base type along with esters of different types having molecular formula H2C=C(R1)COO(R2) where R1 may be preferably of C1-6 type and R2 of C2-8 an acrylic crosslinking agent selected from ethylene glycol dimethyl acrylate, a free radical polymeric initiator and a catalyst such as herein described for a period of at least two hours under inert atmosphere to obtain the novel polymer alloy.

Full Text	The present invention particularly relates to a process for the preparation of a novel polymer alloy useful for making protective coatings. This novel polymer alloy is a high performance alloy of epoxy, urethane and polyacrylate polymers formed by interpenetrating polymer network (IPN) technique and is a base material which when cured with an appropriate curing agents is capable of forming films under ambient conditions. These polymer alloy films obtained by curing with an appropriate curing agent possess highly improved corrosion, chemical and weather resistance and mechanical properties over that of the individual component polymers and using this novel polymer alloy as the base binder material, henceforth a large variety of new organic coatings suitable to a number of applications requiring improved corrosion resistance and mechanical properties, can be formulated. Hitherto a number of individual polymeric systems such as alkyds, acrylics, phenolics, chlorinated rubber, epoxy-polyamide, polyurethane etc., have been used as binder materials for formulating various types of coatings, the last two systems being more effective and versatile, are commonly used for corrosion protection. These individual ambient curing crosslinked polymer systems (epoxy-polyamide and polyurethane) provide coatings with good corrosion resistance and good mechanical properties. Hitherto for some specialised applications wherein improved properties are required, two individual monomers are sometimes chemically blended (co-polymerisation, the product is co-polymer) in which the individual monomers are linked by means of covalent bonds. This type of co-polymerisation to result in co-polymers is possible for selected polymer classes. For polymers which do not have possibilities for co-polymerisation, the other way of improving film properties has been hitherto mere physical blending of two or more such incompatible polymers after the process of polymerisation of the individual polymers is completed, to result in some improvements in the final film properties obtained thereafter. In these cases of polymer blends, the molecules of individual polymers are only physically blended leading to some enhancement in properties which is very limited in scope and superficial in character. The individual polymeric molecules of the final blend are susceptible to micro-separation on ageing under service conditions resulting in the loss of integrity of the film due to the inherent incompatibility of the polymers and thereby meeting premature failures. In the present technique of alloying different incompatible polymers, instead of mere physical blending, the individual polymers (either linear or crosslinked) are synthesised in such a way that during the polymerisation process the polymeric molecules are entangled/interlocked physically and permanently like a woven fabric to form a network of the polymers. The films obtained from these polymer alloys show better resistance to corrosion and chemicals. Because of a network formation in this kind of polymer alloy, besides better corrosion resistance, mechanical properties are also enhanced over that of the individual component polymers from which the polymer alloy is made. Because of these improved properties, new varieties of coatings possessing improved corrosion resistance and mechanical properties over the conventional epoxy-polyamide and polyurethane systems can be formulated for application in a variety of aggressive environments. The technique of alloying polymers is based on taking two or more incompatible polymers and making them compatibilised using a special kind of synthetic procedures in such a way that the component polymers get alloyed through permanent physical entanglements (without forming any covalent bonds between them). This type of alloying of polymers for getting improved properties is a novel process in the field of surface coatings. The main object of the present invention is to provide a process for the preparation of a novel polymer alloy useful for making protective coatings which possess improved corrosion resistance, chemical resistance, UV resistance, mechanical properties and ability to provide protective coatings with suitable pigmentation. Accordingly the present invention provides a process for the preparation of a novel polymer alloy useful for making protective coatings whkh comprises refluxing an oligomeric resin comai«ing termmal oxirane oxygen and having molecular weight Accordingly, the present invention provides a process for the preparation of a novel polymer alloy useful for making protective coatings which comprises refluxing an oligomeric resin containing terminal oxirane oxygen and having molecular weight In an embodiment of the present invention, the oligomeric resin containing terminal oxirane oxygen used may be such as diglycidyl ether bisphenol A based epoxy resin, cylcoaliphatic epoxy resin (of epoxy index 0.30-0.50 Aeq/Kg) In an embodiment of the present invention, the organic solvent used may be such as methyl isobutyl ketone, methyl ethyl ketone, xylene, toluene, n-butyl acetate ethylene glycol mono ethyl ether and mixtures thereof. In yet another embodiment of the present invention, the amide of a Mannich's base type used is a reaction product of phenol, formaldehyde and an aliphatic/aromatic amine having molecular formula of (C6H5)OH CH2.(R1)N(R2)3 where R1 may be C4-6 may be C4-6 type and R2 may be C2-8 type. In yet another embodiment of the present invention, the esters of different types having molecular formula H2C=C(R1)COO(R2) where R1 is preferably of C1-6 type and R2 of C2-8 used is such as methyl methacrylate, butyl methacrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, 2-ethyl hexyl acrylate, hydroxyl ethyl acrylate, hydroxyl ethyl methacrylate wherein the polymer alloy material prepared using hydroxyl functional acrylic monomers will yield a full-IPN and without such monomers will yield a grafted-IPN in the final cured films. In yet another embodiment of the present invention, a crosslinking agent which is an ester prepared from H2C=CR,COOH (where R, may be C0-4) and dihydroxy alcohol containing ethylenic bond to yield a compound C10H14O4 used may be such as ethylene glycol dimethacrylate. In yet another embodiment of the present invention, the free radical polymerization initiators used may be such as benzoyl peroxide, tertiary butyl perbenzoate, 2,2'-azobis(isobutyronitrile) etc. In yet another embodiment of the present invention, a catalyst promoting the formation of -NHC(=O)-O- bonds used may be such as dibutyl tin dilaurate, zirconium oxychloride, diazobicyclooctane etc. In yet another embodiment of the present invention, the inert atmosphere used may be created by passing nitrogen, argon or helium gas into the reaction chamber. Steps for the preparation of the polymer alloy binder material include the preparation of a 42-53 wt. % solids solution of an oligomric resin containing terminal oxirane oxygen in a solvent mixture of 0.6-1.4 : 0.4-1.8 of aliphatic ketone and aromatic hydrocarbon with an Isocyanate Index >3000 and optionally followed by the addition of an amide of Mannich base type which may be a reaction product of phenol, formaldehyde and an aliphatic/aromatic amine having molecular formula of (C6H5)OHCH2-(R1)N(R2)3 where R1 may be C4-6 type and R2 may be C2-8 with an amine/epoxy equivalent ratio 0.58-1.34 for over a period of 20-50 minutes under constant stirring while maintaining the temperature between 20-25°C for 60 minutes and subsequently stirring the contents at 30°C followed by the addition of above said solvent mixture till the solution reaches homogeneous state and followed by addition of a mixture of different acrylic ester monomers (free from any stable-pack inhibitor impurities such as amines/quinones through vacuum distillation) having molecular formula H2C=C(R1)COO(R2) where R1 may be preferably of C1-6 type and R2 of C2-8 in the molar ratio of 0.45-1.68 : 0.08-0.51 : 0.02-0.95 along with a free radical polymerisation initiator recrystallized in acetone and preferably having an half-life period 28-36 minutes at temperature 90-95°C and optionally an acrylic crosslinking agent of an ester prepared from H2C=CRCOOH and dihydroxy alcohol containing ethylenic bond to yield a compound C10H14O4 and solvent mixture over a period of 2-3 hours under inert atmosphere with constant stirring while maintaining the temperature between 85-90°C for 3 hours and raising the temperature to 120-130°C for another 30-50 minutes followed by the addition of 0.01-0.04 wt. % of an ester of lauric acid containing heavy metals like zirconium / tin based urethane catalyst solution in vacuum distilled methyl ethyl ketone and moisture & acid free butyl acetate, cooled to get a turbid free, clear, homogeneous resinous solution of polymer alloy whose properties are shown in table 1. Table-1 Properties of Polymer Alloy Solution (Table Removed) This polymer alloy is capable of being used as a useful base material for making protective coatings when mixed with appropriate curing agents such as isocyanate terminated urethane prepolymer crosslinking agent. The following examples are given by way of illustration of the present invention and should not be construed to limit the scope of the present invention. Example-1 328 gms of diglycidyl ether bisphenol A based epoxy resin (of Epoxy Index 0.30 - 0.50 Aeq/Kg) is dissolved in 145 gms. of methyl isobutyl ketone and 180 gms xylene and 60 gms of butyl acetate under refluxing temperature for a period of 55 minutes to a clear homogenous solution and by adding an amide of type having molecular formula HO-Ph-CH2NH (CH2)2-NH2 with an amine/epoxy equivalent ratio 0.62 - 1.29 for over a period of 50 minutes under constant stirring while maintaining the temperature at 35°C for 45 minutes till a clear homogenous solution is obtained followed by the addition of a mixture containing approximately about 40 gms. of solvent methyl isobutyl ketone to the contents and followed by the addition of 273 gms of butyl methacrylate, 64 gms. of ethyl acrylate, 8.8 gms of ethylene glycol dimethacrylate, 18.5 gms. of benzoyl peroxide in 55 gms. of xylene and the contents are heated for a period of 3 hours while maintaining the temperature at 90°C for 3 hours and raising the temperature to 130°C for another 50 minutes followed by the addition of 12.8 gms of diazobicyclo octane as 8-12% wt. / vol. solution in methyl isobutyl ketone and xylene solvent mixture and cooled to get a turbid free, clear, homogeneous resin solution whose properties are shown in Table 2. Table-2 Properties of Polymer Alloy Solution (Table Removed) Example - 2 280 gms of diglycidyl ether bisphenol A based epoxy resin (of Epoxy Index 0.30-0.50 Aeq/Kg) is dissolved in 95 gms of methyl isobutyl ketone and 115 gms of xylene under refluxing temperature for a period of 40 minutes to a clear homogenous solution and by adding an amide of type having molecular formula HO-Ph-CH2 NH (CH2)2 NH2 with an amine/epoxy equivalent ratio 0.62 - 1.29 for over a period of 30 minutes till a clear homogenous solution is obtained followed by the addition of a mixture containing approximately 37 gms of solvent methyl isobutyl ketone to the contents and followed by the addition of 210 gms of butyl methacrylate, 25 gms of 2-ethyl hexyl acrylate, 3.0 gms of ethylene glycol dimethacrylate, 10 gms of benzoyl peroxide in 50 gms of xylene and the contents are heated for a period of 2 hours while maintaining the temperature at 80°C for 2 hours and raising the temperature to 120°C for 30 minutes followed by the addition of 2 gms of dibutyl tin dilaurate as 8-10% wt/vol. solution in methyl isobutyl ketone and xylene solvent mixture and cooled to get a turbid free, clear, homogenous resin solution whose properties are shown in Table 3. Table-3 Properties of Polymer Alloy Solution (Table Removed) Example-3 320 gms of diglycidyl ether bisphenol A based epoxy resins (of Epoxy Index 0.30-0.50 Aeq./kg) is dissolved in 145 gms of methyl isobutyl ketone and 180 gms xylene and optionally 60 gms of butyl acetate under refluxing temperature for a period of 55 minutes to a clear homogenous solution followed by the addition of a mixture containing 38 gms of a solvent mixture of methyl isobutyl ketone and xylene to the contents and followed by the addition of 250 gms of butyl methacrylate 58 gms of 2-ethyl hexyl acrylate, 69 gms of hydroxy ethyl methacrylate, 8.8 gms of ethylene glycol dimethacrylate, 18.5 gms of benzoyl peroxide in 55 gms of xylene and the contents are heated for a period of 3 hours while maintaining the temperature at 90°C for 3 hours and raising the temperature to 130°C for another 50 minutes followed by the addition of 12.8 gms of diazobicyclo octane as 9.4% wt. / vol. solution in methyl isobutyl ketone and xylene solvent mixture and cooled to get a turbid free, clear homogenous resin solution whose properties are shown in Table 4. Table-4 Properties of Polymer Alloy Solution (Table Removed) Example 4 240 gms of diglycidyl ether bisphenol A based epoxy resin (of Epoxy Index 0.30-0.50 Aeq./Kg) is dissolved in 105 gms of methyl isobutyl ketone and 130 gms xylene and 45 gms of butyl acetate under refluxing temperature for a period of 40 minutes to a clear homogenous solution and by adding an amide of type having molecular formula HO-Ph-CH2 NH(CH2)2 NH2 with an amine-epoxy equivalent ratio 0.8 to 1.1 for over a period of 35 minutes while maintaining the temperature at 40°C for 40 minutes till a clear homogenous solution is obtained followed by the addition of a mixture containing approximately about 30 gms of solvent methyl isobutyl ketone to the contents and followed by the addition of 180 gms of butyl methacrylate 40 gms of butyl acrylate, 45 gms of hydroxy ethyl acrylate, 6.0 gms of ethylene glycol dimethacrylate, 15 gms on benzoyl peroxide in 40 gms of xylene and the contents are heated for a period of 2 hours while maintaining the temperature at 70°C for 2 hours and raising the temperature to 110°C for another 40 minutes followed by the addition of 9 gm of dibutyl tin dilaurate as 8% wt. / vol. solution in methyl isobutyl ketone and xylene solvent mixture and cooled to get a turbid free, clear, homogenous resin solution whose properties are shown in table 5. Table-5 Properties of Polymer Alloy Solution (Table Removed) The novelty of the present invention lies in its ability to achieve interpenetration by segmental interlocking within the polymer molecules so as to avoid the susceptibility to micro-separation of macro-molecules on aging under aggressive conditions which is quite common with polymer blends systems in which the blending of the individual polymers is done through simple physical mixing. The advantages of the present invention are 1. In this process, incompatible polymers (i.e. polyurethane, epoxies and acrylics) have been compatibilised using special kind of synthetic procedures to form a polymer alloy. 2. Physical and permanent entanglements have been made in the polymer alloy where they may be absent in mere physical blending of polymers. 3. Micro-phase separation of the component polymers is almost restricted in polymer alloys wherein it is predominant in the polymer blends. 4. To produce polymer alloys which possess improved corrosion resistance, chemical resistance, UV resistance, mechanical properties than the component polymers when applied as a coating. We claim: 1. A process for the preparation of a novel polymer alloy useful for making protective coatings which comprises refluxing an oligomeric resin containing terminal oxirane oxygen and having molecular weight 2. A process as claimed in claim 1 wherein the oligomeric resin containing terminal oxirane oxygen used is diglycidyl ether bisphenol A based epoxy resin, cycloaliphatic epoxy resin (of epoxy index 0.30-0.50 Aeq/Kg). 3. A process as claimed in claim 1-2 wherein the organic solvent used is methyl isobutyl ketone, methyl ethyl ketone, xylene, toluene, n-butyl acetate ethylene glycol mono ethyl ether and mixtures thereof. 4. A process as claimed in claims 1-3 wherein the amide of a Mannich's base type having molecular formula of (C6H5)OH CH2.(R1)N(R2) 3 where R1 may be C4-6 may be C4-6 type and R2 may be C2-8 type. 5. A process as claimed in claims 1-4 wherein the esters of different types having molecular formula H2C=C(R1)COO(R2) where R1 is preferably of C1-6 type and R2 of C2-8 used is methyl methacrylate, butyl methacrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, 2-ethyl hexyl acrylate, hydroxyl ethyl acrylate, hydroxyl ethyl methacrylate. 6. A process as claimed in claims 1-5 wherein the free radical polymerization initiators used is benzoyl peroxide, tertiary butyl perbenzoate, 2,2'- azobis(isobutyronitrile). 7. A process as claimed in claims 1-6 the catalyst used is dibutyl tin dilaurate, zirconium oxychloride, diazobicyclooctane. 8. A process as claimed in claims 1-8 wherein the inert atmosphere used may be created by passing nitrogen, argon or helium gas into the reaction chamber. 9. A process for the preparation of a novel polymer alloy useful for making protective coatings substantially as herein desribed with respect to the examples.

Full Text

The present invention particularly relates to a process for the preparation of a novel polymer alloy useful for making protective coatings.
This novel polymer alloy is a high performance alloy of epoxy, urethane and polyacrylate polymers formed by interpenetrating polymer network (IPN) technique and is a base material which when cured with an appropriate curing agents is capable of forming films under ambient conditions. These polymer alloy films obtained by curing with an appropriate curing agent possess highly improved corrosion, chemical and weather resistance and mechanical properties over that of the individual component polymers and using this novel polymer alloy as the base binder material, henceforth a large variety of new organic coatings suitable to a number of applications requiring improved corrosion resistance and mechanical properties, can be formulated.
Hitherto a number of individual polymeric systems such as alkyds, acrylics, phenolics, chlorinated rubber, epoxy-polyamide, polyurethane etc., have been used as binder materials for formulating various types of coatings, the last two systems being more effective and versatile, are commonly used for corrosion protection. These individual ambient curing crosslinked polymer systems (epoxy-polyamide and polyurethane) provide coatings with good corrosion resistance and good mechanical properties. Hitherto for some specialised applications wherein improved properties are required, two individual monomers are sometimes chemically blended (co-polymerisation, the product is co-polymer) in which the individual monomers are linked by means of covalent bonds. This type of co-polymerisation to result in co-polymers is possible for selected polymer classes. For polymers which do not have possibilities for co-polymerisation, the other way of improving film properties has been hitherto mere physical blending of two or more such incompatible polymers after the process of polymerisation of the individual polymers is completed, to result in some improvements in the final film properties obtained thereafter. In these cases of polymer blends, the molecules of individual polymers are only physically blended leading to some enhancement in properties which is very limited in scope and superficial
in character. The individual polymeric molecules of the final blend are susceptible to micro-separation on ageing under service conditions resulting in the loss of integrity of the film due to the inherent incompatibility of the polymers and thereby meeting premature failures. In the present technique of alloying different incompatible polymers, instead of mere physical blending, the individual polymers (either linear or crosslinked) are synthesised in such a way that during the polymerisation process the polymeric molecules are entangled/interlocked physically and permanently like a woven fabric to form a network of the polymers. The films obtained from these polymer alloys show better resistance to corrosion and chemicals. Because of a network formation in this kind of polymer alloy, besides better corrosion resistance, mechanical properties are also enhanced over that of the individual component polymers from which the polymer alloy is made. Because of these improved properties, new varieties of coatings possessing improved corrosion resistance and mechanical properties over the conventional epoxy-polyamide and polyurethane systems can be formulated for application in a variety of aggressive environments.
The technique of alloying polymers is based on taking two or more incompatible polymers and making them compatibilised using a special kind of synthetic procedures in such a way that the component polymers get alloyed through permanent physical entanglements (without forming any covalent bonds between them). This type of alloying of polymers for getting improved properties is a novel process in the field of surface coatings.
The main object of the present invention is to provide a process for the preparation of a novel polymer alloy useful for making protective coatings which possess improved corrosion resistance, chemical resistance, UV resistance, mechanical properties and ability to provide protective coatings with suitable pigmentation.
Accordingly the present invention provides a process for the preparation of a novel polymer alloy useful for making protective coatings whkh comprises refluxing an oligomeric resin comai«ing termmal oxirane oxygen and having molecular weight Accordingly, the present invention provides a process for the preparation of a novel polymer alloy useful for making protective coatings which comprises refluxing an oligomeric resin containing terminal oxirane oxygen and having molecular weight In an embodiment of the present invention, the oligomeric resin containing terminal oxirane oxygen used may be such as diglycidyl ether bisphenol A based epoxy resin, cylcoaliphatic epoxy resin (of epoxy index 0.30-0.50 Aeq/Kg)
In an embodiment of the present invention, the organic solvent used may be such as methyl isobutyl ketone, methyl ethyl ketone, xylene, toluene, n-butyl acetate ethylene glycol mono ethyl ether and mixtures thereof.
In yet another embodiment of the present invention, the amide of a Mannich's base type used is a reaction product of phenol, formaldehyde and an aliphatic/aromatic amine having molecular formula of (C6H5)OH CH2.(R1)N(R2)3 where R1 may be C4-6 may be C4-6 type and R2 may be C2-8 type.
In yet another embodiment of the present invention, the esters of different types having molecular formula H2C=C(R1)COO(R2) where R1 is preferably of C1-6 type and R2 of C2-8 used is such as methyl methacrylate, butyl methacrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, 2-ethyl hexyl acrylate, hydroxyl ethyl acrylate, hydroxyl ethyl methacrylate wherein the polymer alloy material prepared using hydroxyl functional acrylic monomers will yield a full-IPN and without such monomers will yield a grafted-IPN in the final cured films.
In yet another embodiment of the present invention, a crosslinking agent which is an
ester prepared from H2C=CR,COOH (where R, may be C0-4) and dihydroxy alcohol containing ethylenic bond to yield a compound C10H14O4 used may be such as ethylene glycol dimethacrylate.
In yet another embodiment of the present invention, the free radical polymerization initiators used may be such as benzoyl peroxide, tertiary butyl perbenzoate, 2,2'-azobis(isobutyronitrile) etc.
In yet another embodiment of the present invention, a catalyst promoting the formation of -NHC(=O)-O- bonds used may be such as dibutyl tin dilaurate, zirconium oxychloride, diazobicyclooctane etc.
In yet another embodiment of the present invention, the inert atmosphere used may be created by passing nitrogen, argon or helium gas into the reaction chamber.
Steps for the preparation of the polymer alloy binder material include the preparation of a 42-53 wt. % solids solution of an oligomric resin containing terminal oxirane oxygen in a solvent mixture of 0.6-1.4 : 0.4-1.8 of aliphatic ketone and aromatic hydrocarbon with an Isocyanate Index >3000 and optionally followed by the addition of an amide of Mannich base type which may be a reaction product of phenol, formaldehyde and an aliphatic/aromatic amine having molecular formula of (C6H5)OHCH2-(R1)N(R2)3 where R1 may be C4-6 type and R2 may be C2-8 with an amine/epoxy equivalent ratio 0.58-1.34 for over a period of 20-50 minutes under constant stirring while maintaining the temperature between 20-25°C for 60 minutes and subsequently stirring the contents at 30°C followed by the addition of above said solvent mixture till the solution reaches homogeneous state and followed by addition of a mixture of different acrylic ester monomers (free from any stable-pack inhibitor impurities such as amines/quinones through vacuum distillation) having molecular formula H2C=C(R1)COO(R2) where R1 may be preferably of C1-6 type and R2 of C2-8 in the molar ratio of 0.45-1.68 : 0.08-0.51 : 0.02-0.95 along with a free radical polymerisation initiator recrystallized in acetone and preferably having an half-life period 28-36 minutes at
temperature 90-95°C and optionally an acrylic crosslinking agent of an ester prepared from H2C=CRCOOH and dihydroxy alcohol containing ethylenic bond to yield a compound C10H14O4 and solvent mixture over a period of 2-3 hours under inert atmosphere with constant stirring while maintaining the temperature between 85-90°C for 3 hours and raising the temperature to 120-130°C for another 30-50 minutes followed by the addition of 0.01-0.04 wt. % of an ester of lauric acid containing heavy metals like zirconium / tin based urethane catalyst solution in vacuum distilled methyl ethyl ketone and moisture & acid free butyl acetate, cooled to get a turbid free, clear, homogeneous resinous solution of polymer alloy whose properties are shown in table 1.
Table-1 Properties of Polymer Alloy Solution

(Table Removed)
This polymer alloy is capable of being used as a useful base material for making protective coatings when mixed with appropriate curing agents such as isocyanate terminated urethane prepolymer crosslinking agent.
The following examples are given by way of illustration of the present invention and should not be construed to limit the scope of the present invention.
Example-1
328 gms of diglycidyl ether bisphenol A based epoxy resin (of Epoxy Index 0.30 - 0.50 Aeq/Kg) is dissolved in 145 gms. of methyl isobutyl ketone and 180 gms xylene and 60 gms of butyl acetate under refluxing temperature for a period of 55 minutes to a clear
homogenous solution and by adding an amide of type having molecular formula HO-Ph-CH2NH (CH2)2-NH2 with an amine/epoxy equivalent ratio 0.62 - 1.29 for over a period of 50 minutes under constant stirring while maintaining the temperature at 35°C for 45 minutes till a clear homogenous solution is obtained followed by the addition of a mixture containing approximately about 40 gms. of solvent methyl isobutyl ketone to the contents and followed by the addition of 273 gms of butyl methacrylate, 64 gms. of ethyl acrylate, 8.8 gms of ethylene glycol dimethacrylate, 18.5 gms. of benzoyl peroxide in 55 gms. of xylene and the contents are heated for a period of 3 hours while maintaining the temperature at 90°C for 3 hours and raising the temperature to 130°C for another 50 minutes followed by the addition of 12.8 gms of diazobicyclo octane as 8-12% wt. / vol. solution in methyl isobutyl ketone and xylene solvent mixture and cooled to get a turbid free, clear, homogeneous resin solution whose properties are shown in Table 2.
Table-2 Properties of Polymer Alloy Solution

(Table Removed)
Example - 2
280 gms of diglycidyl ether bisphenol A based epoxy resin (of Epoxy Index 0.30-0.50 Aeq/Kg) is dissolved in 95 gms of methyl isobutyl ketone and 115 gms of xylene under refluxing temperature for a period of 40 minutes to a clear homogenous solution and by adding an amide of type having molecular formula HO-Ph-CH2 NH (CH2)2 NH2 with an amine/epoxy equivalent ratio 0.62 - 1.29 for over a period of 30 minutes till a clear homogenous solution is obtained followed by the addition of a mixture containing
approximately 37 gms of solvent methyl isobutyl ketone to the contents and followed by the addition of 210 gms of butyl methacrylate, 25 gms of 2-ethyl hexyl acrylate, 3.0 gms of ethylene glycol dimethacrylate, 10 gms of benzoyl peroxide in 50 gms of xylene and the contents are heated for a period of 2 hours while maintaining the temperature at 80°C for 2 hours and raising the temperature to 120°C for 30 minutes followed by the addition of 2 gms of dibutyl tin dilaurate as 8-10% wt/vol. solution in methyl isobutyl ketone and xylene solvent mixture and cooled to get a turbid free, clear, homogenous resin solution whose properties are shown in Table 3.
Table-3 Properties of Polymer Alloy Solution

(Table Removed)
Example-3
320 gms of diglycidyl ether bisphenol A based epoxy resins (of Epoxy Index 0.30-0.50 Aeq./kg) is dissolved in 145 gms of methyl isobutyl ketone and 180 gms xylene and optionally 60 gms of butyl acetate under refluxing temperature for a period of 55 minutes to a clear homogenous solution followed by the addition of a mixture containing 38 gms of a solvent mixture of methyl isobutyl ketone and xylene to the contents and followed by the addition of 250 gms of butyl methacrylate 58 gms of 2-ethyl hexyl acrylate, 69 gms of hydroxy ethyl methacrylate, 8.8 gms of ethylene glycol dimethacrylate, 18.5 gms of benzoyl peroxide in 55 gms of xylene and the contents are heated for a period of 3 hours while maintaining the temperature at 90°C for 3 hours and raising the temperature to 130°C for another 50 minutes followed by the addition of 12.8 gms of
diazobicyclo octane as 9.4% wt. / vol. solution in methyl isobutyl ketone and xylene solvent mixture and cooled to get a turbid free, clear homogenous resin solution whose properties are shown in Table 4.
Table-4 Properties of Polymer Alloy Solution

(Table Removed)
Example 4
240 gms of diglycidyl ether bisphenol A based epoxy resin (of Epoxy Index 0.30-0.50 Aeq./Kg) is dissolved in 105 gms of methyl isobutyl ketone and 130 gms xylene and 45 gms of butyl acetate under refluxing temperature for a period of 40 minutes to a clear homogenous solution and by adding an amide of type having molecular formula HO-Ph-CH2 NH(CH2)2 NH2 with an amine-epoxy equivalent ratio 0.8 to 1.1 for over a period of 35 minutes while maintaining the temperature at 40°C for 40 minutes till a clear homogenous solution is obtained followed by the addition of a mixture containing approximately about 30 gms of solvent methyl isobutyl ketone to the contents and followed by the addition of 180 gms of butyl methacrylate 40 gms of butyl acrylate, 45 gms of hydroxy ethyl acrylate, 6.0 gms of ethylene glycol dimethacrylate, 15 gms on benzoyl peroxide in 40 gms of xylene and the contents are heated for a period of 2 hours while maintaining the temperature at 70°C for 2 hours and raising the temperature to 110°C for another 40 minutes followed by the addition of 9 gm of dibutyl tin dilaurate as 8% wt. / vol. solution in methyl isobutyl ketone and xylene solvent mixture and cooled to get a turbid free, clear, homogenous resin solution whose properties are shown in table 5.
Table-5 Properties of Polymer Alloy Solution
(Table Removed)
The novelty of the present invention lies in its ability to achieve interpenetration by segmental interlocking within the polymer molecules so as to avoid the susceptibility to micro-separation of macro-molecules on aging under aggressive conditions which is quite common with polymer blends systems in which the blending of the individual polymers is done through simple physical mixing.
The advantages of the present invention are
1. In this process, incompatible polymers (i.e. polyurethane, epoxies and acrylics) have been
compatibilised using special kind of synthetic procedures to form a polymer alloy.
2. Physical and permanent entanglements have been made in the polymer alloy where they
may be absent in mere physical blending of polymers.
3. Micro-phase separation of the component polymers is almost restricted in polymer alloys
wherein it is predominant in the polymer blends.
4. To produce polymer alloys which possess improved corrosion resistance, chemical
resistance, UV resistance, mechanical properties than the component polymers when
applied as a coating.

We claim:
1. A process for the preparation of a novel polymer alloy useful for making protective coatings which comprises refluxing an oligomeric resin containing terminal oxirane oxygen and having molecular weight 2. A process as claimed in claim 1 wherein the oligomeric resin containing terminal oxirane oxygen used is diglycidyl ether bisphenol A based epoxy resin, cycloaliphatic epoxy resin (of epoxy index 0.30-0.50 Aeq/Kg).
3. A process as claimed in claim 1-2 wherein the organic solvent used is methyl isobutyl ketone, methyl ethyl ketone, xylene, toluene, n-butyl acetate ethylene glycol mono ethyl ether and mixtures thereof.
4. A process as claimed in claims 1-3 wherein the amide of a Mannich's base type having molecular formula of (C6H5)OH CH2.(R1)N(R2) 3 where R1 may be C4-6 may be C4-6 type and R2 may be C2-8 type.
5. A process as claimed in claims 1-4 wherein the esters of different types having molecular formula H2C=C(R1)COO(R2) where R1 is preferably of C1-6 type and R2 of C2-8 used is methyl methacrylate, butyl methacrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate, 2-ethyl hexyl acrylate, hydroxyl ethyl acrylate, hydroxyl ethyl methacrylate.
6. A process as claimed in claims 1-5 wherein the free radical polymerization
initiators used is benzoyl peroxide, tertiary butyl perbenzoate, 2,2'-
azobis(isobutyronitrile).
7. A process as claimed in claims 1-6 the catalyst used is dibutyl tin dilaurate, zirconium oxychloride, diazobicyclooctane.
8. A process as claimed in claims 1-8 wherein the inert atmosphere used may be
created by passing nitrogen, argon or helium gas into the reaction chamber.
9. A process for the preparation of a novel polymer alloy useful for making protective
coatings substantially as herein desribed with respect to the examples.

Documents:

699-del-2000-abstract.pdf

699-del-2000-claims.pdf

699-del-2000-correspondence-others.pdf

699-del-2000-correspondence-po.pdf

699-del-2000-description (complete).pdf

699-del-2000-form-1.pdf

699-del-2000-form-19.pdf

699-del-2000-form-2.pdf

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Patent Number

218364

Indian Patent Application Number

699/DEL/2000

PG Journal Number

21/2008

Publication Date

23-May-2008

Grant Date

31-Mar-2008

Date of Filing

31-Jul-2000

Name of Patentee

COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH

Applicant Address

RAFI MARG, NEW DELHI- 110 001, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	SWAMINATHAN KRISHNAN	CENTRAL ELECTROCHEMICAL RESEARCH INSTITUTE (CSIR) KARAIKUDI 630 006. INDIA
2	PORAIYAR SARANGAPANI MOHAN	CENTRAL ELECTROCHEMICAL RESEARCH INSTITUTE (CSIR) KARAIKUDI 630 006. INDIA
3	THANGAVEL ANANDARAJ	CSIR SENIOR RESEARCH FELLOW, ALAGAPPA UNIVERSITY, KARAIKUDI 630 003, INDIA.
4	KRISHNASWAMY BALAKRISHNA	CSIR EMERITUS SCIENTIST ALAGAPPA UNIVERSITY, KARAIKUDI 630 003, INDIA

PCT International Classification Number

C23C14/20

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA