Title of Invention	"A PROCESS FOR THE PREPARATION OF TRANSPARENT OR CLEAR RESIN FILM FROM CASHEW NUT SHELL LIQUED AND ITS COMPONENTS"
Abstract	A process for the preparation of transparent or clear resin film from cashew nut shell liquid and its CSNL components by reacting CSNL or its components such as cardanol, anacardic acid, cardol at ice bath temperature with acryloyl or methacryloyl chloride in the presence of a base and an organic solvent, distilling the crude product so obtained to get the monomer, subjecting the monomer to column chromatography then, polymerising the monomer with or without conventional comonomer in the presence of conventional free radical initiator and solvent at a temperature in the range of 70-80°C over a period in the range of 20- 24 hrs. and evaporating the solvent to obtain a transparent, clear and colourless resin and if desired, adding known curing agents and heated upto 75 to 85°C followed by drying to get a tough, transparent, clear and colourless film.

Title of Invention

"A PROCESS FOR THE PREPARATION OF TRANSPARENT OR CLEAR RESIN FILM FROM CASHEW NUT SHELL LIQUED AND ITS COMPONENTS"

Abstract

A process for the preparation of transparent or clear resin film from cashew nut shell liquid and its CSNL components by reacting CSNL or its components such as cardanol, anacardic acid, cardol at ice bath temperature with acryloyl or methacryloyl chloride in the presence of a base and an organic solvent, distilling the crude product so obtained to get the monomer, subjecting the monomer to column chromatography then, polymerising the monomer with or without conventional comonomer in the presence of conventional free radical initiator and solvent at a temperature in the range of 70-80°C over a period in the range of 20- 24 hrs. and evaporating the solvent to obtain a transparent, clear and colourless resin and if desired, adding known curing agents and heated upto 75 to 85°C followed by drying to get a tough, transparent, clear and colourless film.

Full Text	The present invention provides a process for the preparation of transparent or clear resin film from cashew nut shell liquid and its components. As the resin prepared by the process of the present invention is transparent and gets dried to a solid film, it can be used as a base resin for the preparation of paints of all shades of colour for both interior and exterior decorations, industrial coatings, moreover as speciality coating in specific applications. So the industries to which this invention can be applied are paint industries, lacquers and varnishes, protective coatings, speciality surface coatings and related industries. The resin prepared by the process of the present invention can be processed into acrylate substrate for photoresist materials and so could be used in electronic industries. CNSL and resins based on the components of CNSL are generally brown or dark brown or black in colour and it is difficult to make transparent / clear or colourless resin from CNSL (C.K.S.Pillai, V.S. Prasad, J.D.Sudha, S.C.Bera and A.R.R.Menon, J.Appl.Polym.Sci., 41, 2487 (1990), A.R.R.Menon, C.K.S.Pillai, J.D.Sudha and A.G.Mathew, J.Scient.lnd.Res. , 44, 324 (1985)). Earlier attempts to blend resins resulting from CNSL and its components with phenolic resin succeeded only in partly removing its opaqueness and the resin still was coloured. There is no published literature regarding the production of any transparent resin from CNSL or its components. When cardanol was hydrogenated, the product obtained namely pentadecyl phenol is white in colour. However, when this material was converted to a resin by polycondensation with formaldehyde, the product was still coloured and the colour was difficult to remove. Apart from the above information, published literature or report orjpatent j on preparation of transparent or clear or colourless resin from CNSL and its components such as cardanol, cardol, anacardic acid or related compounds is not available. Since the colourless films produced from CNSL and its components find use in paints and lacquers and due to the great demands for such products, it was felt to develop a process for the preparation of colourless waterlike transparent films from CNSL and its components. The main object of the invention is, therefore, to provide a process for the preparation of transparent clear/ colourless resin from CNSL or its components such as cardanol, anacardic acid, cardol. The main finding underlying the invention is our observation that acryloylation or methacryloylation of the hydroxyl group of the components present in CNSL such as cardanol/ anacardic acid/ cardol lead to free radically polymerizable acrylic or methacrylic monomers that on free radical polymerization yields polymers which on silica gel column separation gives resins of water like clarity and transparency which is colourless. The acrylate or methacrylate monomers obtained from CNSL and its components such as cardanol/ anacardic acid/ cardol by method of acryloylation or methacryloylation can also undergo copolymerisation with vinyl monomers such as acryl amide, acrylic acid, acrylo nitile, methyl methacrylate, ethyl acrylate, 2-hydroxy ethylmetharylate and butyl acrylate to obtain copolymers that on separation by column chromatography give rise to transparent and clear resins without colour. The process of the present invention has essentially the following steps: (1) Acryloylation or methacryloylation of CNSL and its components such as cardanol, anacardic acid, cardol, (2) Purification of the monomers by column separation and (3) polymerization of the monomers using free radical initiators. The formulation of the paint can be made using any conventional formulation. Accordingly, the present invention provides a process for the preparation of transparent or clear resin film from cashew nut shell liquid and its components which comprises reacting CNSL or its components such as cardanol, anacardic acid, cardol at ice bath temperature with acryloyl or methacryloyl chloride in the presence of a base and an organic solvent, distilling the crude product so obtained to get the monomer, subjecting the monomer to column chromatography then, polymerising the monomer with or without conventional comonomer in the presence of conventional free radical initiator and solvent at a temperature in the range of 70-80 °C over a period in the range of 20- 24 hrs. and evaporating the solvent to obtain a transparent, clear and colourless resin and if desired, adding known curing agents such as herein described and heated upto 75 to 85°C followed by drying to get a tough, transparent, clear and colourless film. The advantages of the present invention. The process produces a resin in the form of a film of water like clarity whereas the film obtained by the hithertoknown processes is coloured brown or dark brown. The film of resin obtained process is fully transparent and can not be scratched with a nail. It is the first time a fully transparent or water clear resin has been prepared from CNSL which is a dark brown coloured material. The film of the resin produced can be used directly for applications in surface coatings with shades of all coloures. The film of the resin obtained is also tough. The resin is compatible with the conventional pigments and hence the use of compatibilizers can be avoided. The resin undergoes proper blending with the additives and pigments and gives a paint with smooth flow and high glow. The new resin obtained by the process of the present invention can also be used in other applications such as in photo-resist material as substrate replacing the existing costly acrylate resin. The resin obtained by the process is acrylate based and as the side of the components of CNSL such as cardanol, anacardic acid, cardol possesses unsaturation, it can undergo - photo cross-linking. azobisisobutyro nitrile, benzoyl peroxide, terbutyl hydroperoxide, dicumine peroxide, hydrogen peroxide or similar peroxies. The solvents employed in the polymerisation step may be selected from toluene or tetrahydrofuran or dimethylformamide or dioxane or carbontetrachloride. If preparation of the films of the copolymers are desired during the polymerisation, appropriate comonomers such as acryl amide, acrylic acid, acrylonitrile, and the like may be added to the mixture. The advantages of the present invention. The process produces a resin in the form of a film of water like clarity whereas the film obtained by the hithertoknown processes is coloured brown or dark brown. The film of resin obtained process is fully transparent and can not be scratched with a nail. It is the first time a fully transparent or water clear resin has been prepared from CNSL which is a dark brown coloured material. The film of the resin produced can be used directly for applications in surface coatings with shades of all coloures. The film of the resin obtained is also tough. The resin is compatible with the conventional pigments and hence the use of compatibilizers can be avoided. The resin undergoes proper blending with the additives and pigments and gives a paint with smooth flow and high glow. The new resin obtained by the process of the present invention can also be used in other applications such as in photo-resist material as substrate replacing the existing costly acrylate resin. The resin obtained by the process is acrylate based and as the side of the components of CNSL such as cardanol, anacardic acid, cardol possesses unsaturation, it can undergo - photo cross-linking. The invention is described in detail in the following examples which are provided by way of illustration only and should not be construed to limit the scope of the invention.. Example 1. One hundred and eighty gms of CNSL in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 57.6 gm of acryloyl was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 35.5 gms of the acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained after 7 hrs. exposure to ambient temperature. Example 2. Ninety gms of cardanol in 150 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 8.16 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 28.8 gm of acryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillatiounder vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 17.8 gms of cardanyl acrylate was dissolved in 50 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained after 8 hrs. exposure to ambient temperature. Example 3. One hundred and eighty six gmsofCardol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.52 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 60.6 gm of acryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 35.5 gms of cardyl acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained after 6 hrs. exposure to ambient temperature. Example 4. One hundred and eighty gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 57.6 gm of acryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 35.5 gms of cardanyl acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained on heating the film at 75 °C for 30 min. in a hot air oven. Example 5. One hundred and eighty gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 57.6 gm of acryloyl was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 35.5 gms of cardanyl acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and 10 % by weight of a mixture of manganese octanoate and lead naphthanate were added and the mixture spread on a glass plate. A transparent and clear film was obtained after 4 hrs. and 30 min. on exposure to ambient temperature. Example 6. One hundred and eighty gms of CNSL in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 66.88 gm of acryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 73.2 gms of the methacrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained after 10 hrs. exposure to ambient temperature. Example 7. Ninety gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 8.16 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 33.44 gm of acryloyl was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 35.5 gms of cardanyl methacrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained after 9 hrs. exposure to ambient temperature. Example 8 One hundred and eighty six gms of cardol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 70.9 gm of methacryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 75 gms of cardyl methacrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained after 7 hrs. exposure to ambient temperature. Example 9 One hundred and eighty gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 66.8 gm of methacryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 70 gms of cardanyl acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature. 10 % by weight of a mixture of manganese octanoate and lead naphthanate were added and the mixture spread on a glass plate. A transparent and clear film was obtained after 4 hrs. and 50 min. on exposure to ambient temperature. Example 10 One hundred and eighty gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 66.8 gm of acryloyl was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 70 gms of cardanyl acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained on heating the film at 70 °C for 25 min. in a hot air oven. Example 11 One hundred and eighty gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 66.8 gm of methacryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 35.5 gms of cardanyl acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature. 10 % by weight of a mixture of manganese octanoate and lead naphthanate were added and mixed well. 250 gms of lead chrome was added again mixed and the mixture spread on a glass plate. An yellow coloured paint coating was obtained after 4 hrs. and 50 min. on exposure to ambient temperature. Example 12 One hundred and eighty gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 66.8 gm of methacryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 35.5 gms of cardanyl acrylate and 7.2 gm acrylic acid were dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature. 10 % by weight of a mixture of manganese octanoate and lead naphthanate were added and mixed well. 250 gms of lead chrome was added, mixed and the mixture spread on We claim : 1. A process for the preparation of transparent or clear resin film from cashew nut shell liquid and its components which comprises reacting CNSL or its components such as cardanol, anacardic acid, cardol at ice bath temperature with acryloyl or methacryloyl chloride in the presence of a base and an organic solvent, distilling the crude product so obtained to get the monomer, subjecting the monomer to column chromatography then, polymerising the monomer with or without conventional comonomer in the presence of conventional free radical initiator and solvent at a temperature in the range of 70-80°C over a period in the range of 20- 24 hrs. and evaporating the solvent to obtain a transparent, clear and colourless resin and if desired, adding known curing agents such as herein described and heated upto 75 to 85°C followed by drying to get a tough, transparent, clear and colourless film. 2. A process as claimed in claim 1 wherein the base used is selected from pyridine , sodium hydroxide, sodium hydride. 3. A process as claimed in claims I and 2 wherein solvent used for the first step is selected from toluene, carbontertrachioride, methylene chloride. 4. A process as claimed in claims 1 to 3 wherein the free radicle initiator used is selected from azobisisobutyronitrile, benzoyl peroxide, ter-bulyl hydroperoxide, dicumene peroxide, hydrogen peroxide, 5. A process as claimed in claims 1 to 4 wherein the solvent used in the polymerisation step is selected from toluene, hexane, xylene. tetrahydrofuran, dimethylformamide, dioxane, carbontetrachloride. 6. A process as claimed in claims 1 to 5 wherein the comonomer used is selected from vinyl monomers such as acryl amide, acrylic acid, acrylonitrile, methyl methacrylate, styrene, vinyl acetate, 2-hydroxyethyl methacrylate, butyl methacrylate. 7. A process as claimed in claims 1 to 6 wherein curing agent used is manganese octoate, lead oleate, cobalt naphthanate, cumine diperoxide, dichlorobenzoyl peroxide. 8. A process for the preparation of transparent or clear resin film from cashew nut shell liquid and its components substantially as herein described with reference to the examples.

Full Text

The present invention provides a process for the preparation of transparent or clear resin film from cashew nut shell liquid and its components. As the resin prepared by the process of the present invention is transparent and gets dried to a solid film, it can be used as a base resin for the preparation of paints of all shades of colour for both interior and exterior decorations, industrial coatings, moreover as speciality coating in specific applications. So the industries to which this invention can be applied are paint industries, lacquers and varnishes, protective coatings, speciality surface coatings and related industries. The resin prepared by the process of the present invention can be processed into acrylate substrate for photoresist materials and so could be used in electronic industries.
CNSL and resins based on the components of CNSL are generally brown or dark brown or black in colour and it is difficult to make transparent / clear or colourless resin from CNSL (C.K.S.Pillai, V.S. Prasad, J.D.Sudha, S.C.Bera and A.R.R.Menon, J.Appl.Polym.Sci., 41, 2487 (1990), A.R.R.Menon, C.K.S.Pillai, J.D.Sudha and A.G.Mathew, J.Scient.lnd.Res. , 44, 324 (1985)). Earlier attempts to blend resins resulting from CNSL and its components with phenolic resin succeeded only in partly removing its opaqueness and the resin still was coloured. There is no published literature regarding the production of any transparent resin from CNSL or its components. When cardanol was hydrogenated, the product obtained namely pentadecyl phenol is white in colour. However, when this material was converted to a resin by polycondensation with formaldehyde, the product was still coloured and the colour was difficult to remove. Apart from the above
information, published literature or report orjpatent j on preparation of transparent or clear or colourless resin from CNSL and its components such as cardanol, cardol, anacardic acid or related compounds is not available. Since the colourless films produced from CNSL and its components find use in paints and lacquers and due to the great demands for such products, it was felt to develop a process for the preparation of colourless waterlike transparent films from CNSL and its components.
The main object of the invention is, therefore, to provide a process for the preparation of transparent clear/ colourless resin from CNSL or its components such as cardanol, anacardic acid, cardol.
The main finding underlying the invention is our observation that acryloylation or methacryloylation of the hydroxyl group of the components present in CNSL such as cardanol/ anacardic acid/ cardol lead to free radically polymerizable acrylic or methacrylic monomers that on free radical polymerization yields polymers which on silica gel column separation gives resins of water like clarity and transparency which is colourless. The acrylate or methacrylate monomers obtained from CNSL and its components such as cardanol/ anacardic acid/ cardol by method of acryloylation or methacryloylation can also undergo copolymerisation with vinyl monomers such as acryl amide, acrylic acid, acrylo nitile, methyl methacrylate, ethyl acrylate, 2-hydroxy ethylmetharylate and butyl acrylate to obtain copolymers that on separation by column chromatography give rise to transparent and clear resins without colour.
The process of the present invention has essentially the following steps: (1) Acryloylation or methacryloylation of CNSL and its components such as cardanol, anacardic acid, cardol, (2) Purification of the monomers by column separation and (3) polymerization of the monomers using free radical initiators. The formulation of the paint can be made using any conventional formulation.
Accordingly, the present invention provides a process for the preparation of
transparent or clear resin film from cashew nut shell liquid and its components
which comprises reacting CNSL or its components such as cardanol, anacardic acid, cardol at ice bath temperature with acryloyl or methacryloyl chloride in the presence of a base and an organic solvent, distilling the crude product so obtained to get the monomer, subjecting the monomer to column chromatography then, polymerising the monomer with or without conventional comonomer in the presence of conventional free radical initiator and solvent at a temperature in the range of 70-80 °C over a period in the range of 20- 24 hrs. and evaporating the solvent to obtain a transparent, clear and colourless resin and if desired, adding known curing agents such as herein described and heated upto 75 to 85°C followed by drying to get a tough, transparent, clear and colourless film.
The advantages of the present invention. The process produces a resin in the form of a film of water like clarity whereas the film obtained by the hithertoknown processes is coloured brown or dark brown. The film of resin obtained process is fully transparent and can not be scratched with a nail. It is the first time a fully transparent or water clear resin has been prepared from CNSL which is a dark brown coloured material. The film of the resin produced can be used directly for applications in surface coatings with shades of all coloures. The film of the resin obtained is also tough. The resin is compatible with the conventional pigments and hence the use of compatibilizers can be avoided. The resin undergoes proper blending with the additives and pigments and gives a paint with smooth flow and high glow. The new resin obtained by the process of the present invention can also be used in other applications such as in photo-resist material as substrate replacing the existing costly acrylate resin. The resin obtained by the process is acrylate based and as the side of the components of CNSL such as cardanol, anacardic acid, cardol possesses unsaturation, it can undergo - photo cross-linking.
azobisisobutyro nitrile, benzoyl peroxide, terbutyl hydroperoxide, dicumine peroxide, hydrogen peroxide or similar peroxies. The solvents employed in the polymerisation step may be selected from toluene or tetrahydrofuran or dimethylformamide or dioxane or carbontetrachloride. If preparation of the films of the copolymers are desired during the polymerisation, appropriate comonomers such as acryl amide, acrylic acid, acrylonitrile, and the like may be added to the mixture.
The advantages of the present invention. The process produces a resin in the form of a film of water like clarity whereas the film obtained by the hithertoknown processes is coloured brown or dark brown. The film of resin obtained process is fully transparent and can not be scratched with a nail. It is the first time a fully transparent or water clear resin has been prepared from CNSL which is a dark brown coloured material. The film of the resin
produced can be used directly for applications in surface coatings with shades of all coloures.
The film of the resin obtained is also tough. The resin is compatible with the conventional
pigments and hence the use of compatibilizers can be avoided. The resin undergoes proper blending with the additives and pigments and gives a paint with smooth flow and high glow. The new resin obtained by the process of the present invention can also be used in other applications such as in photo-resist material as substrate replacing the existing costly acrylate resin. The resin obtained by the process is acrylate based and as the side of the components of CNSL such as cardanol, anacardic acid, cardol possesses unsaturation, it can undergo - photo cross-linking.
The invention is described in detail in the following examples which are provided by way of illustration only and should not be construed to limit the scope of the invention..
Example 1.
One hundred and eighty gms of CNSL in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 57.6 gm of acryloyl was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 35.5 gms of the acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained after 7 hrs. exposure to ambient temperature.
Example 2.
Ninety gms of cardanol in 150 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 8.16 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 28.8 gm of acryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillatiounder
vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 17.8 gms of cardanyl acrylate was dissolved in 50 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained after 8 hrs. exposure to ambient temperature.
Example 3.
One hundred and eighty six gmsofCardol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.52 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 60.6 gm of acryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 35.5 gms of cardyl acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained after 6 hrs. exposure to ambient temperature.
Example 4.
One hundred and eighty gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 57.6 gm of acryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 35.5 gms of cardanyl acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained on heating the film at 75 °C for 30 min. in a hot air oven.
Example 5.
One hundred and eighty gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 57.6 gm of acryloyl was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a
silica column to improve its clarity. Yield- 70%. 35.5 gms of cardanyl acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and 10 % by weight of a mixture of manganese octanoate and lead naphthanate were added and the mixture spread on a glass plate. A transparent and clear film was obtained after 4 hrs. and 30 min. on exposure to ambient temperature.
Example 6.
One hundred and eighty gms of CNSL in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 66.88 gm of acryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 73.2 gms of the methacrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained after 10 hrs. exposure to ambient temperature.
Example 7.
Ninety gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 8.16 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 33.44 gm of acryloyl was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 35.5 gms of cardanyl methacrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained after 9 hrs. exposure to ambient temperature.
Example 8
One hundred and eighty six gms of cardol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 70.9 gm of methacryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 75 gms of cardyl methacrylate was
dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained after 7 hrs. exposure to ambient temperature.
Example 9
One hundred and eighty gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 66.8 gm of methacryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 70 gms of cardanyl acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature. 10 % by weight of a mixture of manganese octanoate and lead naphthanate were added and the mixture spread on a glass plate. A transparent and clear film was obtained after 4 hrs. and 50 min. on exposure to ambient temperature.
Example 10
One hundred and eighty gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 66.8 gm of acryloyl was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 70 gms of cardanyl acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature and spread on a glass plate. A transparent and clear film was obtained on heating the film at 70 °C for 25 min. in a hot air oven.
Example 11
One hundred and eighty gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 66.8 gm of methacryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through
a silica column to improve its clarity. Yield- 70%. 35.5 gms of cardanyl acrylate was dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature. 10 % by weight of a mixture of manganese octanoate and lead naphthanate were added and mixed well. 250 gms of lead chrome was added again mixed and the mixture spread on a glass plate. An yellow coloured paint coating was obtained after 4 hrs. and 50 min. on exposure to ambient temperature.
Example 12
One hundred and eighty gms of cardanol in 300 ml of dry dimethylformamide was taken in a 3 necked flask fitted with a condenser, stirrer and thermometer and 16.32 gm of sodium hydride was added with stirring. Keeping the reaction mixture in ice bath, 66.8 gm of methacryloyl chloride was added and the stirring continued for 3 hrs. DMF was removed by distillation under vacuum and the contents of the flask were poured into ice bath to precipitate the acrylate. Methylene chloride was added to the acrylate and the mixture is passed through a silica column to improve its clarity. Yield- 70%. 35.5 gms of cardanyl acrylate and 7.2 gm acrylic acid were dissolved in 100 ml of dioxane in a 500 ml round bottomed flask and 0.5 % (wt/wt) benzoyl peroxide was added to the solution. The polymerization was carried out at 70-80 °C under nitrogen atmosphere for 20 hrs. The reaction mixture was cooled to room temperature. 10 % by weight of a mixture of manganese octanoate and lead naphthanate were added and mixed well. 250 gms of lead chrome was added, mixed and the mixture spread on

We claim :
1. A process for the preparation of transparent or clear resin film from cashew
nut shell liquid and its components which comprises reacting CNSL or its
components such as cardanol, anacardic acid, cardol at ice bath temperature with acryloyl or methacryloyl chloride in the presence of a base and an organic solvent, distilling the crude product so obtained to get the monomer, subjecting the monomer to column chromatography then, polymerising the monomer with or without conventional comonomer in the presence of conventional free radical initiator and solvent at a temperature in the range of 70-80°C over a period in the range of 20- 24 hrs. and evaporating the solvent to obtain a transparent, clear and colourless resin and if desired, adding known curing agents such as herein described and heated upto 75 to 85°C followed by drying to get a tough, transparent, clear and colourless film.
2. A process as claimed in claim 1 wherein the base used is selected from
pyridine , sodium hydroxide, sodium hydride.
3. A process as claimed in claims I and 2 wherein solvent used for the first step
is selected from toluene, carbontertrachioride, methylene chloride.
4. A process as claimed in claims 1 to 3 wherein the free radicle initiator used
is selected from azobisisobutyronitrile, benzoyl peroxide, ter-bulyl
hydroperoxide, dicumene peroxide, hydrogen peroxide,
5. A process as claimed in claims 1 to 4 wherein the solvent used in the
polymerisation step is selected from toluene, hexane, xylene.
tetrahydrofuran, dimethylformamide, dioxane, carbontetrachloride.
6. A process as claimed in claims 1 to 5 wherein the comonomer used is
selected from vinyl monomers such as acryl amide, acrylic acid, acrylonitrile,
methyl methacrylate, styrene, vinyl acetate, 2-hydroxyethyl methacrylate,
butyl methacrylate.
7. A process as claimed in claims 1 to 6 wherein curing agent used is
manganese octoate, lead oleate, cobalt naphthanate, cumine diperoxide,
dichlorobenzoyl peroxide.
8. A process for the preparation of transparent or clear resin film from cashew
nut shell liquid and its components substantially as herein described with
reference to the examples.

Documents:

636-del-1996-abstract.pdf

636-del-1996-claims.pdf

636-del-1996-complete specification (granted).pdf

636-del-1996-correspondence-others.pdf

636-del-1996-correspondence-po.pdf

636-del-1996-description (complete).pdf

636-del-1996-form-1.pdf

636-del-1996-form-2.pdf

636-del-1996-form-3.pdf

636-del-1996-form-5.pdf

636-del-1996-form-6.pdf

« Previous Patent

Next Patent »

Patent Number

197453

Indian Patent Application Number

636/DEL/1996

PG Journal Number

N/A

Publication Date

08-Apr-2006

Grant Date

07-Jul-2006

Date of Filing

27-Mar-1996

Name of Patentee

COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH

Applicant Address

RAFI MARG,NEW DELHI-110001,INDIA

Inventors:

#	Inventor's Name	Inventor's Address
1	DR.CHENNAKKTTU KRISHNA SADASIVAN PILLAI	REGIONAL RESEARCH LABORATORY,THIRU-VANANTHAPURAM,KERALA,INDIA
2	SHRI GANGADHARAN LALITHA SUNU BOTH	M/S.VIJAYALEKSMI CASHEW COMPANY,KOLLAM,KERALA,INDIA
3	DR.MADHAVAN NAIR SURESH	M/S.VIJAYALEKSMI CASHEW COMPANY,KOLLAM,KERALA,INDIA
4	MISS BIJYMOL JACOB	REGIONAL RESEARCH LABORATORY,THIRUVANANTHAPURAM,KERALA,INDIA
5	DR.ALATHUR DAMODARAN DAMODARAN	REGIONAL RESEARCH LABORATORY,THIRU-VANANTHAPURAM,KERALA,INDIA

PCT International Classification Number

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA