Indian Patents. 204220:A PROCESS FOR THE PREPARATION OF POLYMERS FROM VINYLIC MONOMERS USING TETRAETHYLTHIURIUM MONOSULFIDE (MONOSULFIRAM) AS PHOTO INITIATOR

Title of Invention	A PROCESS FOR THE PREPARATION OF POLYMERS FROM VINYLIC MONOMERS USING TETRAETHYLTHIURIUM MONOSULFIDE (MONOSULFIRAM) AS PHOTO INITIATOR
Abstract	A process for the preparation of polymers from vinylic monomers using tetraethylthiurium moriosulfide (monosulfiram) as photo initiator comprising polymerising the vinylic monomers with monosulfiram of the formula 1: Formula 1 in 0.01 -1% by weight, under irradiation with visible light.

Full Text	FORM 2 THEPATENTS ACT 1970 (39 of 1970) COMPLETE SPECIFICATION (See Section 10; rule 13) TITLE A process for the preparation of polymers from vinylic monomers using tetraethylthiurium monosulfide (monosulfiram) as photo initiator APPLICANTS IIT Bombay, Indian Institute of Technology, Powai, Mumbai - 400076, Maharashtra, India and ICI India Limited, an Indian Company having the registered office at ICI House, 34 Chowringhee Road, Calcutta - 700071, West Bengal, India INVENTORS Under Section 28(2) Prof Anil Kumar Singh, Department of Chemistry, IIT Bombay, Powai, Mumbai 400076, Maharashtra, India and Dr Challa Siva Sai Raman Kumar and Dr Sudhir Achar, both of ICI India Research & Technology Centre,Thane-Belapur Road, Thane 400601 Maharashtra, India, all Indian nationals 9-12-2004 The following specification particularly describes the nature of this invention and the manner in which it is to be performed : This invention relates to a process for the preparation of polymers from vinylic monomers using tetraethyltmurium monosulfide, commonly known as monosulfiram of the formula I. Formula I as photo initiator. These polymers find applications in moulding, extrusion, coating, adhesives and plastics. Formula II Monosulfiram of the Formula I belongs to the class of dithiocarbamates and is used in the treatment of scabies. Monosulfiram on exposure to sunlight is reported to form a compound disulfiram of the Formula II: which has been reported to be effective in the treatment of chronic alcoholism. The polymers of vinylic monomers like methylmethacrylate, acrylate, vinyl chloride, vinyl acetate, vinyl versatate or styrene are prepared by treating the vinylic monomers with an initiator like benzoyl peroxide, azoisobutyronitrile, t-butylhydroperoxide, azobis(dialkylamino)thiocarbonyl thioalkanes, ammonium persulfate, benzyl-N,N-dialkyldithiocarbamates, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) free radicals at room temperature to ~ 100°C. Some polymers of the above vinylic monomers are prepared by irradiation of the vinylic monomers with UV radiation, in the presence of initiators as aforesaid at room temperature to 100°C. The above reactions in general make use of hazardous initiators like benzoyl peroxide. Besides, these are specialised initiators which are difficult to synthesise and expensive. Polymerisation at high temperature consumes considerable thermal energy making these processes uneconomical. It is practically impossible to exercise any control on the heat evolved during the exothermic polymerisation reactions carried out at elevated temperatures. Therefore, the rate of propagation of the reaction is faster than the rate of termination of the polymerisation reaction because of which termination of the reaction at a desired stage is difficult and polydispersed by-products are formed leading to an inefficient polymerisation. An object of the invention is to provide a process for the preparation of polymers from vinylic monomers using monosulfiram as photo initiator, which is safe and uses visible light. Another object of the invention is to provide a process for the preparation of polymers from vinylic monomers using monosulfiram as photo initiator, which can be carried out at ambient temperatures and thus saves considerable thermal energy. Another object of the invention is to provide a process for the preparation of polymers from vinylic monomers using monosulfiram as photo initiator which is inexpensive and easy to synthesize. Another object of the invention is to provide a process for the preparation of polymers from vinylic monomers using monosulfiram as photo initiator, which is efficient and economical. Another object of the invention is to provide a process for the preparation of polymers from vinylic monomers using monosulfiram as photo initiator, which is convenient to carry out. According to the invention, there is provided a process for the preparation of polymers from vinylic monomers using tetraethylthiurium monosulfide (monosulfiram) as photo initiator comprising polymerising the vinylic monomers with monosulfiram of the formula I: Formula I in 0.01 -1% by weight, under irradiation with visible light. The vinylic monomers may be preferably acrylate, methylmethacrylate, vinyl acetate, vinyl chloride, vinyl versatate, styrene, epoxy and/or chloropropene or mixture thereof. Sun light or any other photon source such as solar reactors which are easy to contruct and inexpensive, may be used for irradiation. Irradiation may be carried out with UV radiation ie lower wavelengths from 254 nm to 300 nm, but the efficiency of the reaction increases when the wavelength lies in the visible region. The scope of the invention may be construed to include irradiation with UV light. The reactor may be made of borosilicate glass or quartz, preferably borosilicate glass. The borosilicate glass transmits light of only the preferred range of wavelengths viz 430 nm to 450 nm, ie visible light, thus filtering off other raditions. Preferably, the weight percent of monosulfiram is 1%. According to the invention on irradiation, monosulfiram of the formula I gets activated and generates free radicals which catalyse the polymerisation of vinylic monomers, thereby preventing further conversion of activated monosulfiram to disulfiram. The process of the invention does not require elevated temperatures and can be conveniently carried out at ambient temperatures thus saving considerable thermal energy. Thus, there is no heat evolved in the process as a result of which by-products are not formed. By controlling the wavelength of the radiation by using appropriate filters, the reaction is further controlled and the polymerisation is made efficient. The process of the invention can also be conveniently carried out in the presence of sunlight or any other appropriate photon source which is easy to construct and operate. Moreover, monosulfiram is safe, simple to synthesise and inexpensive. Therefore, the process of the invention is safe and economical. The following experimental examples are illustrative of the invention but not limitative of the scope thereof. Example 1 Methylmethacrylate (100.0 g) and monosulfiram (1.0 g) were taken in a sealed borosilicate tube and exposed to bright sunlight for 12 hrs. The product obtained contained polymethylmethacrylate. Example 2 The procedure of Example 1 was followed using acrylate (100.0 g) to obtain polyacrylate. Example 3 The procedure of Example 1 was followed using styrene (100.0 g) to obtain polystyrene. Example 4 The procedure of Example 1 was followed using vinyl acetate (100 .0 g) to obtain polyvinylacetate. Example 5 The procedure of Example 1 was followed using vinyl chloride (100.0 g) to obtain polyvinylchloride. Example 6 The procedure of Example 1 was followed using a mixture of methylmethacrylate (80.0 g) and styrene (20.0 g) to obtain a copolymer of methylmethaacrylate and styrene. Example 7 The procedure of Example 1 was followed using a mixture of styrene (80.0 g) and acrylate (20.0 g) to obtain a copolymer of styrene and acrylate. Example 8 The procedure of Example 1 was followed using a mixture of acrylate (80.0 g) and vinyl acetate (20.0 g) to obtain a copolymer of acrylate and vinyl acetate. Example 9 The procedure of Example 1 was followed using a mixture of acrylate (80.0 g) and epoxy (80.0 g) to obtain a copolymer of acrylate and epoxy. Example 10 The procedure of Example 1 was followed using a mixture of vinyl acetate (80.0 g) and vinyl versatate (20.0 g) to obtain a copolymer of vinyl acetate and vinyl versatate. We Claim: 1. A process for the preparation of polymers from vinylic monomers using tetraethylthiurium moriosulfide (monosulfiram) as photo initiator comprising polymerising the vinylic monomers with monosulfiram of the formula 1: Formula 1 in 0.01 -1% by weight, under irradiation with visible light. 2. A process as claimed in claim 1, wherein the vinylic monomer is methylmethacrylate, acrylate, styrene, epoxy, vinyl versatate, vinyl acetate or vinyl chloride or mixture thereof. 3 A process as claimed in claims 1 or 2, wherein the process is carried out in a reactor made of borosilicate. 4. A process as claimed in anyone of claims 1 to 3, wherein the weight percent of monosulfiram is 1%. 5. A process for the preparation of polymers using tetraethylthiurium monosulfide (monosulfiram) of the formula I: Formula as initiator substantially as herein described particularly with reference to Examples 1 to 10. Dated this 7th day of July 2000 (Karuna Goleria) of DePENNING & DePENNING Agent for the Applicants

Full Text

FORM 2
THEPATENTS ACT 1970 (39 of 1970)
COMPLETE SPECIFICATION
(See Section 10; rule 13)
TITLE
A process for the preparation of polymers from vinylic monomers using tetraethylthiurium monosulfide (monosulfiram) as photo initiator
APPLICANTS
IIT Bombay, Indian Institute of Technology, Powai, Mumbai - 400076, Maharashtra, India and ICI India Limited, an Indian Company having the registered office at ICI House, 34 Chowringhee Road, Calcutta - 700071, West Bengal, India
INVENTORS
Under Section 28(2)
Prof Anil Kumar Singh, Department of Chemistry,
IIT Bombay, Powai, Mumbai 400076, Maharashtra,
India and Dr Challa Siva Sai Raman Kumar and Dr Sudhir Achar, both of ICI India Research & Technology Centre,Thane-Belapur Road, Thane 400601 Maharashtra, India, all Indian nationals
9-12-2004
The following specification particularly describes the nature of this invention and the manner in which it is to be performed :

This invention relates to a process for the preparation of polymers from vinylic monomers using tetraethyltmurium monosulfide, commonly known as monosulfiram of the formula I.

Formula I as photo initiator.
These polymers find applications in moulding, extrusion, coating, adhesives and plastics.
Formula II

Monosulfiram of the Formula I belongs to the class of dithiocarbamates and is used in the treatment of scabies. Monosulfiram on exposure to sunlight is reported to form a compound disulfiram of the Formula II:

which has been reported to be effective in the treatment of chronic alcoholism.
The polymers of vinylic monomers like methylmethacrylate, acrylate, vinyl chloride, vinyl acetate, vinyl versatate or styrene are prepared by treating the vinylic monomers with an initiator like benzoyl peroxide, azoisobutyronitrile, t-butylhydroperoxide, azobis(dialkylamino)thiocarbonyl thioalkanes, ammonium persulfate, benzyl-N,N-dialkyldithiocarbamates, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) free radicals at room temperature to ~ 100°C. Some polymers of the above vinylic monomers are prepared by irradiation of the vinylic monomers with UV radiation, in the presence of initiators as aforesaid at room temperature to 100°C.
The above reactions in general make use of hazardous initiators like benzoyl peroxide. Besides, these are specialised initiators which are difficult to synthesise and expensive. Polymerisation at high temperature consumes considerable thermal energy making these processes uneconomical. It is practically impossible to exercise any control on the heat evolved during the exothermic polymerisation reactions carried out at elevated temperatures. Therefore, the rate of propagation of the reaction is faster than the rate of

termination of the polymerisation reaction because of which termination of the reaction at a desired stage is difficult and polydispersed by-products are formed leading to an inefficient polymerisation.
An object of the invention is to provide a process for the preparation of polymers from vinylic monomers using monosulfiram as photo initiator, which is safe and uses visible light.
Another object of the invention is to provide a process for the preparation of polymers from vinylic monomers using monosulfiram as photo initiator, which can be carried out at ambient temperatures and thus saves considerable thermal energy.
Another object of the invention is to provide a process for the preparation of polymers from vinylic monomers using monosulfiram as photo initiator which is inexpensive and easy to synthesize.

Another object of the invention is to provide a process for the preparation of polymers from vinylic monomers using monosulfiram as photo initiator, which is efficient and economical.
Another object of the invention is to provide a process for the preparation of polymers from vinylic monomers using monosulfiram as photo initiator, which is convenient to carry out.
According to the invention, there is provided a process for the preparation of polymers from vinylic monomers using tetraethylthiurium monosulfide (monosulfiram) as photo initiator comprising polymerising the vinylic monomers with monosulfiram of the formula I:

Formula I in 0.01 -1% by weight, under irradiation with visible light.

The vinylic monomers may be preferably acrylate, methylmethacrylate, vinyl acetate, vinyl chloride, vinyl versatate, styrene, epoxy and/or chloropropene or mixture thereof.
Sun light or any other photon source such as solar reactors which are easy to contruct and inexpensive, may be used for irradiation. Irradiation may be carried out with UV radiation ie lower wavelengths from 254 nm to 300 nm, but the efficiency of the reaction increases when the wavelength lies in the visible region. The scope of the invention may be construed to include irradiation with UV light.
The reactor may be made of borosilicate glass or quartz, preferably borosilicate glass. The borosilicate glass transmits light of only the preferred range of wavelengths viz 430 nm to 450 nm, ie visible light, thus filtering off other raditions.
Preferably, the weight percent of monosulfiram is 1%.

According to the invention on irradiation, monosulfiram of the formula I gets activated and generates free radicals which catalyse the polymerisation of vinylic monomers, thereby preventing further conversion of activated monosulfiram to disulfiram. The process of the invention does not require elevated temperatures and can be conveniently carried out at ambient temperatures thus saving considerable thermal energy. Thus, there is no heat evolved in the process as a result of which by-products are not formed. By controlling the wavelength of the radiation by using appropriate filters, the reaction is further controlled and the polymerisation is made efficient. The process of the invention can also be conveniently carried out in the presence of sunlight or any other appropriate photon source which is easy to construct and operate. Moreover, monosulfiram is safe, simple to synthesise and inexpensive. Therefore, the process of the invention is safe and economical.
The following experimental examples are illustrative of the invention but not limitative of the scope thereof.

Example 1 Methylmethacrylate (100.0 g) and monosulfiram (1.0 g) were taken in a sealed borosilicate tube and exposed to bright sunlight for 12 hrs. The product obtained contained polymethylmethacrylate.
Example 2 The procedure of Example 1 was followed using acrylate (100.0 g) to obtain polyacrylate.
Example 3
The procedure of Example 1 was followed using styrene (100.0 g) to obtain polystyrene.
Example 4 The procedure of Example 1 was followed using vinyl acetate (100 .0 g) to obtain polyvinylacetate.

Example 5 The procedure of Example 1 was followed using vinyl chloride (100.0 g) to obtain polyvinylchloride.
Example 6 The procedure of Example 1 was followed using a mixture of methylmethacrylate (80.0 g) and styrene (20.0 g) to obtain a copolymer of methylmethaacrylate and styrene.
Example 7 The procedure of Example 1 was followed using a mixture of styrene (80.0 g) and acrylate (20.0 g) to obtain a copolymer of styrene and acrylate.
Example 8 The procedure of Example 1 was followed using a mixture of acrylate (80.0 g) and vinyl acetate (20.0 g) to obtain a copolymer of acrylate and vinyl acetate.

Example 9 The procedure of Example 1 was followed using a mixture of acrylate (80.0 g) and epoxy (80.0 g) to obtain a copolymer of acrylate and epoxy.
Example 10

The procedure of Example 1 was followed using a mixture of vinyl acetate (80.0 g) and vinyl versatate (20.0 g) to obtain a copolymer of vinyl acetate and vinyl versatate.

We Claim:
1. A process for the preparation of polymers from vinylic monomers using tetraethylthiurium moriosulfide (monosulfiram) as photo initiator comprising polymerising the vinylic monomers with monosulfiram of the formula 1:

Formula 1 in 0.01 -1% by weight, under irradiation with visible light.
2. A process as claimed in claim 1, wherein the vinylic monomer is methylmethacrylate, acrylate, styrene, epoxy, vinyl versatate, vinyl acetate or vinyl chloride or mixture thereof.
3 A process as claimed in claims 1 or 2, wherein the process is carried out in a reactor made of borosilicate.

4. A process as claimed in anyone of claims 1 to 3, wherein the weight percent of monosulfiram is 1%.
5. A process for the preparation of polymers using tetraethylthiurium monosulfide (monosulfiram) of the formula I:

Formula
as initiator substantially as herein described particularly with reference to Examples 1 to 10.
Dated this 7th day of July 2000
(Karuna Goleria) of DePENNING & DePENNING Agent for the Applicants

Documents:

638-mum-2000-claims(granted)-(09-12-2004).doc

638-mum-2000-claims(granted)-(09-12-2004).pdf

638-mum-2000-correspondence(13-12-2004).pdf

638-mum-2000-correspondence(ipo)-(11-12-2003).pdf

638-mum-2000-form 1(10-07-2000).pdf

638-mum-2000-form 19(28-08-2003).pdf

638-mum-2000-form 2 (granted)-(09-12-2004).doc

638-mum-2000-form 2(granted)-(09-12-2004).pdf

638-mum-2000-form 26(10-07-2000).pdf

638-mum-2000-form 3(10-07-2000).pdf

638-mum-2000-form 8(08-04-2004).pdf

638-mum-2000-form 8(09-12-2004).pdf

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Patent Number

204220

Indian Patent Application Number

638/MUM/2000

PG Journal Number

43/2008

Publication Date

24-Oct-2008

Grant Date

24-Jan-2007

Date of Filing

10-Jul-2000

Name of Patentee

INDIAN INSTITUTE OF TECHNOLOGY

Applicant Address

ICI HOUSE, 34 CHOWRINGHEE ROAD, CALCUTTA, WEST BENGAL, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	PROF ANIL KUMAR SINGH	DEPARTMENT OF CHEMISTRY, IIT BOMBAY, POWAI, MUMBAI 400076, MAHARASHTRA, INDIA.
2	DR.CHALLA SIVA SAI RAMAN KUMAR	ICI INDIA RESEARCH AND TECHNOLOGY CENTRE, THANE-BELAPUR ROAD, THANE 400601, MAHARASHTRA, INDIA.
3	DR SUDHIR ACHAR	ICI INDIA RESEARCH AND TECHNOLOGY CENTRE, THANE-BELAPUR ROAD, THANE 400601,

PCT International Classification Number

C 08 F 2/48

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA