Title of Invention	"A PROCESS FOR PREPARATION OF BIS(3-AMINO PHENYL) METHYL PHOSPHINE OXIDE BASED HEXACLHORO NADICIMIDES"
Abstract	This invention relates to a process for preparation of Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide and its chain extended derivatives wherein prepration of Bis (3-amino phenyl) methyl phosphine oxide based monohexachloronadicimide, involves, reacting hexachlornadic anhydride recrystallised from acetic anhydride with Bis (3-amino phenyl) methyl phosphine oxide in glacial acetic acid; refluxing solution of Bis (3-amino phenyl) methyl phosphine oxide dissolved in acetic acid and then adding hexachloronadic anhydride; precipitating the resultant nadicimide resin in 100 ml ice water; preparation of 3.3', 4.4'-benzophenone letracarboxylic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide involves, dissolving mononadicimide in dried acetone; addition of 3.3', 4.4'-benzop>henone tetracarboxylic acid di-anhydride; refluxing the solution; chemical cyclisation of amic acid to imide using preferably fused sodium acetate and acetic acid as cyclo-dehydrating agent; precipilating the resultant resin on crushed ice and water; prepration of pyromellitic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide involving, dissolving mono hexachloronadicimide in dry acetone; adding pyromellitic dianhydride; refluxing the solution; chemical cyclisation of amic acid to imide using fused sodium acetate and acetic acid as cyclodehydrating agent; precipating the resin on crushed ice and water;

Title of Invention

"A PROCESS FOR PREPARATION OF BIS(3-AMINO PHENYL) METHYL PHOSPHINE OXIDE BASED HEXACLHORO NADICIMIDES"

Abstract

This invention relates to a process for preparation of Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide and its chain extended derivatives wherein prepration of Bis (3-amino phenyl) methyl phosphine oxide based monohexachloronadicimide, involves, reacting hexachlornadic anhydride recrystallised from acetic anhydride with Bis (3-amino phenyl) methyl phosphine oxide in glacial acetic acid; refluxing solution of Bis (3-amino phenyl) methyl phosphine oxide dissolved in acetic acid and then adding hexachloronadic anhydride; precipitating the resultant nadicimide resin in 100 ml ice water; preparation of 3.3', 4.4'-benzophenone letracarboxylic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide involves, dissolving mononadicimide in dried acetone; addition of 3.3', 4.4'-benzop>henone tetracarboxylic acid di-anhydride; refluxing the solution; chemical cyclisation of amic acid to imide using preferably fused sodium acetate and acetic acid as cyclo-dehydrating agent; precipilating the resultant resin on crushed ice and water; prepration of pyromellitic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide involving, dissolving mono hexachloronadicimide in dry acetone; adding pyromellitic dianhydride; refluxing the solution; chemical cyclisation of amic acid to imide using fused sodium acetate and acetic acid as cyclodehydrating agent; precipating the resin on crushed ice and water;

Full Text	FIELD OF INVENTION The invention relates to a process for preparation of Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins used in preparation of composite materials for aerospace applications.. PRIOR ART Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimides are basically a new type of nadicimide resins. These resins find their most important application in preparation of composite materials which are utilised in Aerospace applications. These composite materials are light weight and have right combination of mechanical and thermal properties. These are basically made from carbon or glass fibers which is further reinforced either by epoxy or by bis maleimides or by nadicimides resins. However, composite materials which are reinforced through epoxy resins can withstand temperature upto 120°C only. Similarly, composite materials which are reinforced utilising Bis maleimides can withstand temperature upto 250°C only. However, composite materials reinforced through Nadicimide resins can withstand temperature upto 400°C. Nadicimide resins are generally prepared by polymerisation of monomeric reactants (PMR) i.e. by the reaction of monomethyl ester of 5 -norbornene 2,3 -dicarboxylic acid and 4, 4' - diamino dipheylmethane in a suitable solvent which could be alcohol, acetone or tetrahydrofuran (THF). However, these nadicimides suffer from following disadvantages. The main disadvantage of these known resins is that both the resin solution and prepreg have to be stored at very low temperature around -15°C Yet another disadvantage of these known resins is that shelf life of these resins is around six months only. Still another disadvantage of these known resins is that one of the reactant, involved in the preparation of aromatic diamine, is highly carcinogenic causing cancer. Further disadvantage of these known resins is that during reinforcement of composite material, solvents evaporate causing voids in the composite material which adversely affect the mechanical properties of composite material. OBJECTS OF THE /PRESENT INVENTION Primary object of the present invention is to provide a process for preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins. Another object of the invention is to provide a process of preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins which adopts preformed oligomeric approach . Yet another object of the invention is to provide a process of preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins having phosphorus , nitrogen and chlorine atom in the backbone thus having better flame resistance property. Still another object of the invention is to provide a process of preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins which can give high char yield and which can be used as an ablative material. Yet another object of the invention is to provide a process of preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins which can be stored at room temperature. Still another object of the invention is to provide a process of preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins which have higher shelf life. Still further object of the invention is to provide Bis (3-amino phenyl ) methyl phosphine oxide based hexachloronadicimide resins which dissolve in solvent with low boiling temperature like acetone thereby not causing voids in the composite during its fabrication at higher temperature as the solvent goes off completely while drying in oven. Yet further object of the invention is to provide a process for preparing chain extended Bis (3—amino phenyl) methyl phosphine oxide based hexachloronadicimide resins with modified mechanical and thermal properties. Still another object of the invention is to provide a process for preparing chain extended Bis (3—amino phenyl) methyl phosphine oxide based hexachloronadicimide resins which have higher impact strength. Still further object of the invention is to provide a process for preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resin which can be utilised as planarising coating material for electronic components. Yet further object of the invention is to provide a process for preparing Bis (3—amino phenyl) methyl phosphine oxide based hexachloronadicimide resin which is transparent to electromagnetic radiation pertaining to radar wavelength (2-18 GHz). DESCRIPTION OFTHE DRAWINGS Fig. (1) shows reaction scheme for the synthesis of Bis (3-amino phenyl) methyl phosphine oxide based mono hexachloronadicimide resin Fig. (2) shows reaction scheme for the synthesis of 3,3', 4,4'-benzophenone tetra carboxylic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide Fig. (3) shows reaction scheme for the synthesis of Pyromellitic chain extended Bis (3-amino Phenyl) methyl hexachloronadicimide. SUMMARY OF THE INVENTION According to this present invention there is provided a process for preparation of Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide comprising of: (i) reacting hexachlornadic anhydride recrystallised from acetic anhydride with Bis (3-amino phenyl) methyl phosphine oxide in glacial acetic acid; (ii) refluxing solution of Bis (3-amino phenyl) methyl phosphine oxide dissolved in acetic acid and then adding hexachloronadic anhydride; (iii) precipitating the resultant nadicimide resin in 100 ml ice water; (b) preparation of 3.3', 4.4'-benzophenone tetracarboxylic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide involves: (i) dissolving mononadicimide in dried acetone; (ii) addition of 3.3', 4.4'-benzophenorie tetracarboxylic acid di-anhydride; (iii) re fluxing the solution; (iv) chemical cyclisation of amic acid to imide using preferably fused sodium acetate and acetic acid as cyclo-dehydrating agent; (v) precipilating the resultant resin on crushed ice and water; (c ) prepration of pyromellitic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide involving: (i) dissolving mono hexachloronadicimide in dry acetone; (ii) adding pyromellitic dianhydride; fiii) refluxing the solution; iiv) chemical cyclisation of amic acid to imide using fused sodium acetate and acetic acid as cyclodehydrating agent; (v) precipating the resin on crushed ice and water; In accordance with this invention there is provided a process for preparing a new type of Nadicimide i.e. mono Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resin and Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resin with extended chains which are prepared using performed oligomeric approach. Composite materials reinforced through such nadicimide resins, show better combination of mechanical and thermal properties. These nadicimide resins are basically prepared by polymerisation of monomeric reactants like monomethyl ester of nadic dicarboxylic acid and diamine in a solvent viz. alcohol, acetone, THF etc. In accordance with this invention, Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide is prepared by condensation of Bis (3-amino phenyl) methyl phosphine oxide with hexachloronadic anhydride in glacial acetic acid. This resin could be chain extended by molecular engineering using 3,3', 4,4' — benzophenone tetracarboxylic acid dianhydride and pyromellitic dianhydride. These chain extended Bis (3-aminophenyl) methyl phosphine oxide based hexachloronadicimides have modified mechanical and thermal properties. The impact strength of chain extended Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimides is more than that of Bis (3—aminophenyl) methyl phosphine oxide based monohexachloro nadicimide. The prepared hexachloronadicimides can be kept at room temperature and has longer shelf life. The composite materials resulting from reinforcement with these hexachloronadicimide resins have better combination of mechanical and thermal resistant properties. DESCRIPTION OF THE INVENTION According to present invention, Bis (3—aminophenyl) methyl phosphine oxide based mono hexachloronadicimide and chain extended Bis (3—aminophenyl) methyl phosphine oxide based hexachloronadicimides are prepared by following steps s (A) Preparationof Bis (3-amino phenyl) methyl phosphine oxide based mono hexachloronadicitnide 1 mole hexachloronadic anhydride recrystallised from acetic anhydride is reacted with 1 mole Bis (3-amino phenyl) methyl o phosphine oxide in 20 ml glacial acetic acid and refluxed at 120 C and atmospheric pressure for approximate 8 hours. The resultant mono hexachloronadicimide is precipitated on crushed ice & cold water. The precipitated mono hexachloronadicimide resin is washed several times with water and aqueous sodium bicarbonate and dried under vacuum at 60 mm of mercury. The mono hexachloronadicimide resin thus obtained is purified by dissolving it in chloroform and precipitating in methanol. (B) Preparation of chain extended Bis (3-amino phenyl ) methyl phosphine oxide based hexachloronadicimides The mono hexachloronadicimide, prepared in above manner, can be chain extended by allowing it to react with different anhydrides. (i) 3,3'. 4,4'-benzophenone tetra carboxvlic chain extended Bis (3-amino phenyl) Methyl Hexachloronadicimide The mono hexachloronadicimide is dissolved in dried acetone (20 ml) at 60°C and then 0.005 mole of 3,3', 4,4'-benzophenone tera carboxvlic acid dianhydride is added to this portion. The solution is refluxed at 60 °C for four hours. This is again followed by chemical cyclisation of the amic acid to imide using fused sodium acetate (0.1 gm) and acetic anhydride (2 ml) as the cyclodehydrating agent and refluxed for 1 more hour. Again the resultant resin is precipitated on crushed ice and 100 ml water. The precipitated resin is washed several times with water and aqueous sodium bicarbonate. (ii) Pvromellitic chain extended Bis (3-amino phenyl) Methyl Hexachloronadicimide .01 mole of mono hexachloronadicimide is dissolved in 20 ml dry acetone at 60°C and .005 mole of pyromellitic dianhydride was added in portion. The solution was refluxed at 60°C for 4 hours followed by chemical cyclisation of amic acid to imide using 0.1 gm fused sodium acetate and 2 ml acetic acid as the cyclodehydrating agent. Again the resultant resin is precipitated on crushed ice and 100 ml water. Finally, this precipitated chain extended Bis (3-amino phenyl) methyl hexachloronadicimide is washed several times with water and aqueous sodium bicarbonate and dried under vacuum. After completion of chemical process, structural characteristics of these hexachloronadicimides are determined with the help of Infrared Spectroscopy and Nuclear Magnetic Resonance Spectroscopy whereas thennal characteristics of these hexachloronadicimides are determined with the help of Differential Scanning Calorometery and Thermo Gravimetric Analysis technique. The process of the present invention will now be illustrated with working examples which are intended to be typical examples to illustrate the working of the invention and are not intended to be taken restrictively to imply any limitation on the scope of the present invention. WORKING EXAMPLES: (a) Preparation of Bis (3-amino phenyl) methyl phosphine oxide based mono hexachloronadicimide resin 24.8 gm of bis (3-aminophenyl) methyl phosphine oxide was dissolved in 100 ml glacial acetic acid taken in a three necked flask equipped with a reflux condenser having calcium chloride guard tube and a solid transfer tube. Next, 37.0 gm of hexachloronadic anhydride was added with constant stirring in 2-3 portions. The solution was refluxed for 12 hours at 120°C. The resultant nadicimide resin was precipitated in 1000 ml ice water. The precipitated mono hexachloronadicimide was washed several times and dried under vacuum. Finally, the prepared mono hexachloronadicimide resin was purified by dissolving in chloroform and precipitating in methanol. (b) Preparation of 3,3, 4.4'-benzophenone tera carboxylic chain extended Bis (3-amino phenvl) Methyl Hexachloronadicimide 12 gm mono hexachloronadicimide prepared by above process is dissolved in 20 ml dried acetone and the solution is taken in three necked flask equipped with a reflux condenser having calcium chloride guard tube and a solid transfer tube. Next, 3.22 gm of 3,3', 4,4'-benzophenone tera carboxylic acid dianhydride is added to this portion. The solution is refluxed at 60 °C for four hours. This is followed by chemical cyclisation of the amic acid to imide using fused sodium acetate (0.1 gm) and acetic anhydride (2 ml) as the cyclodehydrating agent. Again the resultant resin is precipitated on crushed ice and 100 ml water. The precipitated resin is washed several times with water and aqueous sodium bicarbonate. (c) Preparation of pvromelh'tic chain extended Bis (3-amino phenvl) Methyl Hexachloronadicimi de 12 gm mono hexachloronadicimide resin is dissolved in 20 ml dried acetone and the solution is taken in three necked flask equipped with a reflux condenser having calcium chloride guard tube and a solid transfer tube. Next 2.18 gm of pyromellitic dianhydride is added in portion. The solution is refluxed at 60 °C for four hours. This is followed by chemical cyclisation of the amic acid to imide using fused sodium acetate (0.5 gm) and acetic anhydride (2 ml) as the cyclodehydrating agent. Again, the resultant chain extended hexachloro nadicimide resin is precipitated on crushed ice and 100 ml water. Finally, precipitated resin is washed several times with water and aqueous sodium bicarbonate The structural characteristics of these hexachloronadicimides. prepared by above mentioned processes are determined with the help of Infrared Spectroscopy and Nuclear Magnetic Resonance Spectroscopy whereas thermal characterisation of these hexachloronadicimides are determined with the help of Differential Scanning Calorimetry and Thermo Gravimetric Analysis technique. It is to be understood that the process of the present invention is susceptible to adaptations, changes, modifications by those skilled in the art. Such adaptations, changes, modifications are intended to be within the scope of the present invention which is further set forth by following claims. WE CLAIM: 1. A process for preparation of Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide comprising of : (i) reacting hexachlornadic anhydride recrystallised from acetic anhydride with Bis (3-amino phenyl) methyl phosphine oxide in glacial acetic acid; (ii) refluxing solution of Bis (3-amino phenyl) methyl phosphine oxide dissolved in acetic acid and then adding hexachlororiadic anhydride; (iii) precipitating the resultant nadicimide resin in 100 ml ice water; (b) preparation of 3,3', 4.4'-benzophenone tetracarboxylic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide involves: (i) dissolving mononadicimide in dried acetone; (ii) addition of 3.3', 4-4'-benzophenone tetracarboxylic acid di- anhydride; (iii) refluxing the solution; (iv) chemical cyclisation of amic acid to imide using preferably fused sodium acetate and acetic acid as cyclo-dehydrating agent; (v) precipilating the resultant resin on crushed ice and water; (c ) prepration of pyromellitic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide involving: (i) dissolving mono hexachloronadicimide in dry acetone; i (ii) adding pyromellitic dianhydride; (iii) refluxing the solution; liv) chemical cyclisation of amic acid to imide using fused sodium acetate and acetic acid as cyclodehydrating agent; (v) precipating the resin; on crushed ice and water; 2. A process for preparation of Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide as substantially described and illustrated herein.

Full Text

FIELD OF INVENTION
The invention relates to a process for preparation of Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins used in preparation of composite materials for aerospace applications..
PRIOR ART
Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimides are basically a new type of nadicimide resins. These resins find their most important application in preparation of composite materials which are utilised in Aerospace applications. These composite materials are light weight and have right combination of mechanical and thermal properties. These are basically made from carbon or glass fibers which is further reinforced either by epoxy or by bis maleimides or by nadicimides resins. However, composite materials which are reinforced through epoxy resins can withstand temperature upto 120°C only. Similarly, composite materials which are reinforced utilising Bis maleimides can withstand temperature upto 250°C only. However, composite materials reinforced through Nadicimide resins can withstand temperature upto 400°C.
Nadicimide resins are generally prepared by polymerisation of monomeric reactants (PMR) i.e. by the reaction of monomethyl ester of 5 -norbornene 2,3 -dicarboxylic acid and 4, 4' - diamino dipheylmethane in a suitable solvent which could be alcohol, acetone or tetrahydrofuran (THF). However, these nadicimides suffer from following disadvantages.
The main disadvantage of these known resins is that both the resin solution and prepreg have to be stored at very low temperature around -15°C
Yet another disadvantage of these known resins is that shelf life of these resins is around six months only.
Still another disadvantage of these known resins is that one of the reactant, involved in the preparation of aromatic diamine, is highly carcinogenic causing cancer.
Further disadvantage of these known resins is that during reinforcement of composite material, solvents evaporate causing voids in the composite material which adversely affect the mechanical properties of composite material.
OBJECTS OF THE /PRESENT INVENTION
Primary object of the present invention is to provide a process for preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins.
Another object of the invention is to provide a process of preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins which adopts preformed oligomeric approach .
Yet another object of the invention is to provide a process of preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins having phosphorus , nitrogen and chlorine atom in the backbone thus having better flame resistance property.
Still another object of the invention is to provide a process of preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins which can give high char yield and which can be used as an ablative material.
Yet another object of the invention is to provide a process of preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins which can be stored at room temperature.
Still another object of the invention is to provide a process of preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resins which have higher shelf life.
Still further object of the invention is to provide Bis (3-amino phenyl ) methyl phosphine oxide based hexachloronadicimide resins which dissolve in solvent with low boiling temperature like acetone thereby not causing voids in the composite during its fabrication at higher temperature as the solvent goes off completely while drying in oven.
Yet further object of the invention is to provide a process for preparing chain extended Bis (3—amino phenyl) methyl phosphine oxide based hexachloronadicimide resins with modified mechanical and thermal properties.
Still another object of the invention is to provide a process for preparing chain extended Bis (3—amino phenyl) methyl phosphine oxide based hexachloronadicimide resins which have higher impact strength.
Still further object of the invention is to provide a process for preparing Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resin which can be utilised as planarising coating material for electronic components.
Yet further object of the invention is to provide a process for preparing Bis (3—amino phenyl) methyl phosphine oxide based hexachloronadicimide resin which is transparent to electromagnetic radiation pertaining to radar wavelength (2-18 GHz). DESCRIPTION OFTHE DRAWINGS
Fig. (1) shows reaction scheme for the synthesis of Bis (3-amino phenyl) methyl phosphine oxide based mono hexachloronadicimide resin
Fig. (2) shows reaction scheme for the synthesis of 3,3', 4,4'-benzophenone tetra carboxylic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide
Fig. (3) shows reaction scheme for the synthesis of Pyromellitic chain extended Bis (3-amino Phenyl) methyl hexachloronadicimide.
SUMMARY OF THE INVENTION
According to this present invention there is provided a process for preparation of Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide comprising of:
(i) reacting hexachlornadic anhydride recrystallised from acetic anhydride with Bis (3-amino phenyl) methyl phosphine oxide in
glacial acetic acid; (ii) refluxing solution of Bis (3-amino phenyl) methyl phosphine
oxide dissolved in acetic acid and then adding hexachloronadic
anhydride; (iii) precipitating the resultant nadicimide resin in 100 ml ice
water;
(b) preparation of 3.3', 4.4'-benzophenone tetracarboxylic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide involves:
(i) dissolving mononadicimide in dried acetone;
(ii) addition of 3.3', 4.4'-benzophenorie tetracarboxylic acid di-anhydride;
(iii) re fluxing the solution;
(iv) chemical cyclisation of amic acid to imide using preferably fused sodium acetate and acetic acid as cyclo-dehydrating agent;
(v) precipilating the resultant resin on crushed ice and water;
(c ) prepration of pyromellitic chain extended Bis (3-amino phenyl)
methyl hexachloronadicimide involving: (i) dissolving mono hexachloronadicimide in dry acetone; (ii) adding pyromellitic dianhydride; fiii) refluxing the solution; iiv) chemical cyclisation of amic acid to imide using fused sodium
acetate and acetic acid as cyclodehydrating agent; (v) precipating the resin on crushed ice and water;
In accordance with this invention there is provided a process for preparing a new type of Nadicimide i.e. mono Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resin and Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide resin with extended chains which are prepared using performed oligomeric approach. Composite materials reinforced through such nadicimide resins, show better combination of mechanical and thermal properties. These nadicimide resins are basically prepared by polymerisation of monomeric reactants like monomethyl ester of nadic dicarboxylic acid and diamine in a solvent viz. alcohol, acetone, THF etc.
In accordance with this invention, Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide is prepared by condensation of Bis (3-amino phenyl) methyl phosphine oxide with hexachloronadic anhydride in glacial acetic acid. This resin
could be chain extended by molecular engineering using 3,3', 4,4' —
benzophenone tetracarboxylic acid dianhydride and pyromellitic dianhydride. These chain extended Bis (3-aminophenyl) methyl
phosphine oxide based hexachloronadicimides have modified mechanical and thermal properties. The impact strength of chain
extended Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimides is more than that of Bis (3—aminophenyl)
methyl phosphine oxide based monohexachloro nadicimide. The prepared hexachloronadicimides can be kept at room temperature and
has longer shelf life. The composite materials resulting from reinforcement with these hexachloronadicimide resins have better
combination of mechanical and thermal resistant properties. DESCRIPTION OF THE INVENTION
According to present invention, Bis (3—aminophenyl) methyl
phosphine oxide based mono hexachloronadicimide and chain extended Bis (3—aminophenyl) methyl phosphine oxide based
hexachloronadicimides are prepared by following steps s (A) Preparationof Bis (3-amino phenyl) methyl phosphine oxide
based mono hexachloronadicitnide
1 mole hexachloronadic anhydride recrystallised from acetic
anhydride is reacted with 1 mole Bis (3-amino phenyl) methyl
o phosphine oxide in 20 ml glacial acetic acid and refluxed at 120 C
and atmospheric pressure for approximate 8 hours. The resultant mono hexachloronadicimide is precipitated on
crushed ice & cold water. The precipitated mono hexachloronadicimide resin is washed several times with
water and aqueous sodium bicarbonate and dried under vacuum at 60 mm of mercury. The mono hexachloronadicimide resin thus obtained is purified by dissolving it in chloroform and precipitating in methanol.
(B) Preparation of chain extended Bis (3-amino phenyl ) methyl phosphine oxide based hexachloronadicimides
The mono hexachloronadicimide, prepared in above manner, can be chain extended by allowing it to react with different anhydrides.
(i) 3,3'. 4,4'-benzophenone tetra carboxvlic chain extended Bis (3-amino phenyl) Methyl Hexachloronadicimide
The mono hexachloronadicimide is dissolved in dried acetone (20 ml) at 60°C and then 0.005 mole of 3,3', 4,4'-benzophenone tera carboxvlic acid dianhydride is added to this portion. The solution is refluxed at 60 °C for four hours. This is again followed by chemical cyclisation of the amic acid to imide using fused sodium acetate (0.1 gm) and acetic anhydride (2 ml) as the cyclodehydrating agent and refluxed for 1 more hour. Again the resultant resin is precipitated on crushed ice and 100 ml water. The precipitated resin is washed several times with water and aqueous sodium bicarbonate.
(ii) Pvromellitic chain extended Bis (3-amino phenyl) Methyl Hexachloronadicimide
.01 mole of mono hexachloronadicimide is dissolved in 20 ml dry acetone at 60°C and .005 mole of pyromellitic dianhydride was added in portion. The solution was refluxed at 60°C for 4 hours followed by chemical cyclisation of amic acid to imide using 0.1 gm fused sodium acetate and 2 ml acetic acid as the cyclodehydrating agent. Again the resultant resin is precipitated on crushed ice and 100 ml water. Finally, this precipitated chain extended Bis (3-amino phenyl) methyl hexachloronadicimide is washed several times with water and aqueous sodium bicarbonate and dried under vacuum.
After completion of chemical process, structural characteristics of these hexachloronadicimides are determined with the help of Infrared Spectroscopy and Nuclear Magnetic Resonance Spectroscopy whereas thennal characteristics of these hexachloronadicimides are determined with
the help of Differential Scanning Calorometery and Thermo Gravimetric Analysis technique.
The process of the present invention will now be illustrated with working examples which are intended to be typical examples to illustrate the working of the invention and are not intended to be taken restrictively to imply any limitation on the scope of the present invention.
WORKING EXAMPLES:
(a) Preparation of Bis (3-amino phenyl) methyl phosphine oxide based
mono hexachloronadicimide resin
24.8 gm of bis (3-aminophenyl) methyl phosphine oxide was dissolved in 100 ml glacial acetic acid taken in a three necked flask equipped with a reflux condenser having calcium chloride guard tube and a solid transfer tube. Next, 37.0 gm of hexachloronadic anhydride was added with constant stirring in 2-3 portions. The solution was refluxed for 12 hours at 120°C. The resultant nadicimide resin was precipitated in 1000 ml ice water. The precipitated mono hexachloronadicimide was washed several times and dried under vacuum. Finally, the prepared mono hexachloronadicimide resin was purified by dissolving in chloroform and precipitating in methanol.
(b) Preparation of 3,3, 4.4'-benzophenone tera carboxylic chain extended
Bis (3-amino phenvl) Methyl Hexachloronadicimide
12 gm mono hexachloronadicimide prepared by above process is dissolved in 20 ml dried acetone and the solution is taken in three necked flask equipped with a reflux condenser having calcium chloride guard tube and a solid transfer tube. Next, 3.22 gm of 3,3', 4,4'-benzophenone tera carboxylic acid dianhydride is added to this portion. The solution is refluxed at 60 °C for four hours. This is followed by chemical cyclisation of the amic acid to imide using fused sodium acetate (0.1 gm) and acetic anhydride (2 ml) as the cyclodehydrating agent. Again the resultant resin is precipitated on crushed ice and 100 ml water. The precipitated resin is washed several times with water and aqueous sodium bicarbonate.
(c) Preparation of pvromelh'tic chain extended Bis (3-amino phenvl) Methyl
Hexachloronadicimi de
12 gm mono hexachloronadicimide resin is dissolved in 20 ml dried acetone and the solution is taken in three necked flask equipped with a reflux condenser having calcium chloride guard tube and a solid transfer tube. Next 2.18 gm of pyromellitic dianhydride is added in portion. The solution is refluxed at 60 °C for four hours. This is followed by chemical cyclisation of the amic acid to imide using fused sodium acetate (0.5 gm) and acetic anhydride (2 ml) as the cyclodehydrating agent. Again, the resultant chain extended hexachloro nadicimide resin is precipitated on crushed ice and 100 ml water. Finally, precipitated resin is washed several times with water and aqueous sodium bicarbonate
The structural characteristics of these hexachloronadicimides. prepared by above mentioned processes are determined with the help of Infrared Spectroscopy and Nuclear Magnetic Resonance Spectroscopy whereas thermal characterisation of these hexachloronadicimides are determined with the help of Differential Scanning Calorimetry and Thermo Gravimetric Analysis technique.
It is to be understood that the process of the present invention is susceptible to adaptations, changes, modifications by those skilled in the art. Such adaptations, changes, modifications are intended to be within the scope of the present invention which is further set forth by following claims.

WE CLAIM:
1. A process for preparation of Bis (3-amino phenyl) methyl phosphine oxide based hexachloronadicimide comprising of :
(i) reacting hexachlornadic anhydride recrystallised from acetic anhydride with Bis (3-amino phenyl) methyl phosphine oxide in glacial acetic acid;
(ii) refluxing solution of Bis (3-amino phenyl) methyl phosphine oxide dissolved in acetic acid and then adding hexachlororiadic anhydride;
(iii) precipitating the resultant nadicimide resin in 100 ml ice water;
(b) preparation of 3,3', 4.4'-benzophenone tetracarboxylic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide involves:
(i) dissolving mononadicimide in dried acetone; (ii) addition of 3.3', 4-4'-benzophenone tetracarboxylic acid di-
anhydride;
(iii) refluxing the solution;
(iv) chemical cyclisation of amic acid to imide using preferably fused sodium acetate and acetic acid as cyclo-dehydrating agent;
(v) precipilating the resultant resin on crushed ice and water;
(c ) prepration of pyromellitic chain extended Bis (3-amino phenyl) methyl hexachloronadicimide involving:
(i) dissolving mono hexachloronadicimide in dry acetone;
i
(ii) adding pyromellitic dianhydride;
(iii) refluxing the solution;
liv) chemical cyclisation of amic acid to imide using fused sodium
acetate and acetic acid as cyclodehydrating agent; (v) precipating the resin; on crushed ice and water;
2. A process for preparation of Bis (3-amino phenyl) methyl
phosphine oxide based hexachloronadicimide

as substantially described and illustrated herein.

Documents:

307-del-2000-abstract.pdf

307-del-2000-claims.pdf

307-del-2000-correspondence-others.pdf

307-del-2000-correspondence-po.pdf

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

307-del-2000-drawings.pdf

307-del-2000-form-1.pdf

307-del-2000-form-19.pdf

307-del-2000-form-2.pdf

307-del-2000-form-26.pdf

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Patent Number

220188

Indian Patent Application Number

307/DEL/2000

PG Journal Number

28/2008

Publication Date

11-Jul-2008

Grant Date

16-May-2008

Date of Filing

23-Mar-2000

Name of Patentee

THE CHIEF CONTROLLER, RESEARCH AND DEVELOPMENT

Applicant Address

Inventors:

#	Inventor's Name	Inventor's Address
1	SARFARAZ ALAM
2	LAXMI DUTT KANDPAL

PCT International Classification Number

C07F 9/53

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA