Title of Invention

"A PROCESS FOR THE PREPARATION OF PHOSPHO SULFURISED DERIVATIVES OF HYDROGENATED CARDANOL"

Abstract A process for the preparation of phosphosulphurised derivatives of hydrogenated cardanol.The present invention relates to a process for the preparation of sulphurised derivatives of hydrogenated cardanol using cashewnut shell liquid.It"s a three stage process consisting of hydrogenation, sulphurisation and phosphosulphurisation.The compound formed as product act as an additive which enhances the industrial properties.Being cost effective and biodegradable it"s of high use.
Full Text The present invention relates to a process for the preparation of phospho sulfurised derivatives of hydrogenated cardanol useful as antiwear, antifriction and extreme pressure additives. The present invention particularly relates to preparation of phosphosulfurised derivatives of hydrogenated cardanol obtained from cashew nut shell liquid useful as antiwear, antifriction and extreme pressure additives and components. Most of the alkyl aryl phosphorothioates used as antiwear and e.p. additives have high toxicity, low biodegradability and poor antifriction characteristics at higher loads prevalent in e.p. regime. These products show high copper corrosion ratings and require amines and metal deactivators to reduce this ratings to acceptable values. This usually depresses their performance characteristics. While the antiwear characteristics are satisfactory the friction co-efficient are not substantially reduced this can cause higher energy consumption. Reference may be made to Ger. Offen. DE 4,242, 501, Ger Offen

DE 4242, 502 and Ger. Offens DE 4242, 503 respectively wherein either vegetable oil based epoxides from rape oil or turnip seed oils have been reacted with dialkyl
dithiophosphoric acids or 2-ethyl hexyl dithiophosphoric acid has been reacted with dicyclopentadiene diepoxide.
In another reference of Ger Offen DE 4,317, 911, trialkyl amine phosphine reacted with phosphorus acid sulfur and diisotridecylamine gave di-isodecyl amine salt of (R2N)2 P(S) OP(S) (NR2) OH to give an antiwear and antifriction compound which reduced friction in 1% concentration in mineral oil.
In yet another reference of Ger Offen DE 4,317, 943 dithiophosphates of poly oxyalkylene carbon (alko) oxy methyl have been prepared which give at 2%

concentration friction co-efficient of 0.093 and 0.083 at 150 and 100°C respectively as
compared to mineral oil blank of 0.122 and 0.121 respectively.
These additives have been prepared from epoxides of vegetable oils or hydrocarbons,
polyalkylene glycols and their esters, amines and phosphoric acids which make them
much more expensive than the naturally occuring cardanol which is obtained from
cashew nut shell liquid as a bye product. Unlike the present invention these prdoucts are
highly corrosive to copper and require either metal passivators or amine derivatives
which supress their antiwear and antifriction activity. The epoxide products of olefines
are toxic and the derivatives are not environment friendly.
The phosphosulfurised derivatives prepared in the present invention from cardanol are
novel additives of low toxicity, high biodegradability made from low cost renewable raw
materials and have low corrosivity towards copper and does not require any passivators
or amines. The friction co-efficient and wear scar diameters are also comparatively lower
than most of non mettalic phosphorothio derivatives.
The main object of the present invention is to provide a process for the preparation of
phosphosulfurised derivatives of hydrogenated cardanol useful as antiwear, antifriction
and extreme pressure additives which obviates the draw backs of hither to known
processes.
Another object is to provide a process which uses a naturally occuring alkyl phenol
namely cardanol.
Yet another object is to provide a process for the preparation of additive components
having low toxicity and high bio degradability as compared to petroleum based alkyl
phenols.

Still another object is to provide a process which utilize low cost renewable resource such as cashew nut shell liquid.
Another object is to provide a non metallic additive component which is not only environment friendly but also gives energy gear oil formulations.
Accordingly the present A process for the preparation of phosphosulfurised derivatives of hydrogenated cardanol useful as antiwear, antifriction and extreme additives, which comprises hydrogenation of cardanol iodine no. 105-110 to iodine value 10-225 using hydrogen at pressure of 60-250 psi in presence of raney nickel catalyst at temperatures between 50 to 150°C, sulfurising the hydrogenated cardanol with sulfur monochloride in a ratio ranging 9.1 to 9.4 and at temperature ranging from 20°C to 100°C; after removing the catalyst to a sulfur content of 7 to 10 percent , treating the sulfurised hydrogenated cardanol with phosphorous pentasulfide at temperatures of 85 to 150°C for 3 to 8 hours to obtain phosphosulfurised hydrogenated cardanol through which nitrogen blown at a temperature of 155- 180°C till evolution of hydrogen sulfide ceases, optionally treating the product, with metal powder such as copper, zinc or tin to obtain a product with copper corrosion rating of Ib at 120°C, phosphorous content 3 to 5 per-cent and sulfur content 12 to 15 per-cent.
In an embodiment of the present invention cardanol to catalyst ratio may be 100-300:3-10 by weight.
In another embodiment of the process hydrogenated cardanol to sulfur monochloride used sulfurisation may be between 9:1 to 9:4 by weight and the reaction temperature may vary between 20 to 100°c. In yet another embodiment of the process the moles of phosphorous penta sulfide used per mole of the hydrogenated cardanol may vary between 0.2 to 0.4.
In yet another embodiment the rate at which nitrogen is blown through the phosphosulfurised reaction mass after removal of unreacted phosphorous pentasulfide till hydrogen sulfide evolution ceased varied from 50 ml/min to 150 ml/min.

In another embodiment of the process the metal powder used to reduce the copper corrosion rating to Ib at 120°C for 3 hours may vary between 1 to 5% of the phospho sulfurised product by weight.
The process of the present invention is illustrated by following examples, however, these should not limit the scope of the invention :
Example 1
Raw cardanol of iodine value 105 is dissolved in heptane allowed to stand for six hours and filtered. The heptane is recovered by distillation. 120 gm of the refined cardanol is treated with hydrogen at a pressure of 100 psi at 80°C with 3% by weight of the metal catalyst with constant agitation till absorption of hydrogen ceases. The catalyst is removed from hydrogenatecl cardanol. The iodine value of hydrogenated cardanol is found to be 40. 100 gm of hydrogenated cardanol is treated with 22 gm of sulfur monochloride till all the hydrochloric acid evolved is removed. The sulfurised hydrogenated cardanol is washed with water to remove remaining hydrochloric acid from organic layer. Sulfurised hydrogenated cardanol (% S 9.5 by wt.) is treated with 18 gm of phosphorus penta sulfidc at 100°C while the temperature is gradually raised to 140°C over a period of four hours. Phosphorus penta sulfide is added in several portions during this period. The reaction is continued at 140°C till evolution of hydrogen sulfide practically ceases. The contents are allowed to stand for 4 hours. The heptane is removed by distillation and remaining contents are treated with 2 gm of copper powder at 140°C for 2 hours. The contents are filtered to remove copper powder and nitrogen is blown through the product at 160°C till no more hydrogen sulfide evolved. The contents are redissolved in heptane allowed to stand for 4 hours and filtered and heptane removed

by distillation and evaporation under vacuum at 100°C. The product so obtained is a highly viscous dark brown liquid. The sulfur content is 17% by wt and phosphorus content 3% by weight. A 5% blend of phosphosulfurised hydrogenated cardanol in gear oil base stock gave a copper corrosion rating of Ib at 120°C for 3 hours. The same blend gave welding load 260 Kg., wear scar dia 0.3 mm and co-efficient of friction 0.075.
Example 2
120 gm of refined cardanol prepared by dissolving the raw cardanol in heptane followed by filtration and removal of heptane from filtrate having an iodine value of 105 is treated with hydrogen at a pressure of 250 psi at 105°C with 5% metal catalyst with constant stirring till absorption of hydrogen ceases. The catalyst is removed and iodine value of hydrogenated cardanol is found to be 15. 100 gm of hydrogenated cardanol is treated with 23 gm of sulfur monochloride in carbon tetrachloride solution over a period of 2 hours at 20°C. The temperature is raised to 90°C to distill of most of the carbon tetrachloride. The temperature is further raised to 120°C to drive of all the hydrochloric acid. The sulfurised hydrogenated cardanol so obtained having a sulfur content of 10% is treated with 25 gm of phosphorus pentasulfide in several portion of 2.5 gm each at 80°C with constant stirring. Each fresh portion is added after hydrogen sulfide evolution becomes practically negligible from a portion added prior to it. The addition is completed over a period of 8 hours. The contents are diluted with 25 gm of xylene or light mineral oil and temperature raised to 140°C and maintained till evolution of hydrogen sulfide almost ceases. The contents are dissolved in a parrafinic solvent and allowed to stand for 4 hours and filtered. The solvent is removed from filtrate by distillation and nitrogen is vigorously blown through the remaining contents at 165°C till

the evolution of hydrogen sulfide completely ceases. The contents are diluted with a
paraffmic solvent and allowed to stand for 4 hours and filtered. The solvent is removed
from filtrate by distillation and nitrogen is vigorously blown through the remaining
contents at 165°C till the evolution of hydrogen sulfide completely ceases. The contents
are diluted with a paraffmic solvent and allowed to stand for 4 hours and filtered. The
solvent is removed from filtrate by distillation and evaporation under vacuum. The
product so obtained has sulfur content 15% and phosphorous content 2.8 percent. The
copper corrosion ratings of a 5% blend at 120°C for 3 hours is 2b which is reduced to Ib
when blended with 300 ppm of a hetrocyclic nitrogen derivative. The values of welding
load, wear scar diameter and co-efficient of friction are 300 kg., 0.32 and 0.08
respectively.
The main advantages of the process of the present invention are :
The alkyl phenols from an agricultural source may be converted into value added, energy
efficient environment friendly additive component with antiwear, antifriction and load
carrying e.p.properties useful for industrial gear oils.
The hydrogenation of cardanol may imparts thermal stability and prevents polymerisation
and deposit forming tendencies of cardanol derivatives.
The manner in which the reaction with phosphorus pentasulflde is carried over a period of
time at increasing temperature intervals and addition is done in several portions such that
each fresh portion may be added till evolution of hydrogen sulfide ceases from portion
added prior to it may give product which is more thermally stable having lower copper
corrosion rating.

The'treatment with metal powder and blowing of nitrogen removed corrosive sulfur may
obviate the necessity of using the metal passivators to obtain lower copper corrosion
rating of Ib which seriously effect the antifriction and antiwear properties.
The product obtained after treatment with metal powder and nitrogen blowing has
enhanced performance compared to conventional phsophorothio derivatives of alkyl
phenols.



WE CLAIM:
1. A process for the preparation of phosphosulfurised derivatives of hydrogenated cardanol useful as antiwear, antifriction and extreme additives, which comprises hydrogenation of cardanol iodine no. 105-110 to iodine value 10-225 using hydrogen at pressure of 60-250 psi in presence of raney nickel catalyst at temperatures between 50 to 150°C, sulfurising the hydrogenated cardanol with sulfur monochloride in a ratio ranging 9.1 to 9.4 and at temperature ranging from 20°C to 100°C; after removing the catalyst to a sulfur content of 7 to 10 percent , treating the sulfurised hydrogenated cardanol with phosphorous pentasulfide at temperatures of 85 to 150°C for 3 to 8 hours to obtain phosphosulfurised hydrogenated cardanol through which nitrogen blown at a temperature of 155- 180°C till evolution of hydrogen sulfide ceases, optionally treating the product, with metal powder such as copper, zinc or tin to obtain a product with copper corrosion rating of Ib at 120°C, phosphorous content 3 to 5 per-cent and sulfur content 12 to 15 per-cent.
2. A process as claimed in claim 1 wherein, cardanol to catalyst ratio varies between 100-300:3-10 by weight for hydrogenation.
3. A process as claimed in claims 1 & 2 wherein ,mole of phosphorous penta sulfide used per mole of the hydrogenated cardanol varies between 0.2 to 0.4.
4. A process as claimed in claims 1 to 3 wherein , the rate at which nitrogen is blown through the phosphosulfurised reaction mass after removal of unreacted phosphorous pentasulfide till hydrogen sulfide evolution ceased varied from 50 mi/min to 150 ml/min.
5. A process as claimed in claims 1 to 4 wherein , the metal powder used to reduce the copper corrosion rating to Ib at 120°C for 3 hours varies from 1 to 5 % by wt of the phosphosulfurised hydrogenated cardanol.
6. A process for the preparation of phosphosulfurised derivatives of hydrogenated cardanol useful as antiwear, antifriction and extreme pressure additives substantially as herein described with reference to examples.



Documents:

2522-del-1998-abstract.pdf

2522-del-1998-claims.pdf

2522-del-1998-correspondence-others.pdf

2522-del-1998-correspondence-po.pdf

2522-del-1998-description (complete).pdf

2522-del-1998-form-1.pdf

2522-del-1998-form-19.pdf

2522-del-1998-form-2.pdf


Patent Number 215707
Indian Patent Application Number 2522/DEL/1998
PG Journal Number 12/2008
Publication Date 21-Mar-2008
Grant Date 03-Mar-2008
Date of Filing 26-Aug-1998
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 ONKAR NATH ANAND INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
2 VIJAY KUMAR CHHIBBER INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
3 KALYAN DUTT NEEMLA INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
4 NAVAL KISHORE PANDEY INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
5 RAJPAL SINGH BISHT INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
6 ASHOK KUMAR GUPTA INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
PCT International Classification Number C08F 16/24
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA