IL25198A - Process of preparing polymerizable di-and tri-acrylates and the products obtained - Google Patents

Description

of the products obtained This invention is concerned with preparation of dimers and trimers of having the formulas in which R is a to alkyl the dimers and trimers so mixtures containing processes for polymerizing such mixtures and the polymer so The process of the invention is particularly useful in by comparison with prior art it enables high yields of the desired products to be attained with the use of a relatively inexpensive the invention provides a process for the preparation of a dimeric trimeric in which an acrylate of the formulas in which R is an alkyl group containing from 1 to 18 carbon is in the presence of a catalyst of the 1 in which R and R are the same or different substituted phenyl in which the alkyl a total of from 1 to 8 carbon or to alkyl 2 3 and R and R are the same or different discrete optionally containing one or more inert 2 3 R and each being joined to the nitrogen atom at a primary carbon or together with the nitrogen at to which they are attached form a cyclic group containing up to 5 carbon and an oxygen or sulphur in the ring which may contain one or more substituents having a total of up to 6 carbon The products obtained by process of the invention may be represented by the and COOK where R is a to alkyl In particularly preferred processes according to the the monomer is chosen so as to yield diaers and in which is a to alkyl may typically represent a tetradecyl or octadecyl structural isomers in any of the iso and Typical acrylate monomer reactants include methyl ethyl isopropyl acrylate and 2 The inert substituents may be present in the R and groups for and carbalkoxy 1 R and may represent hen i or Typicall discrete may be or octadecyl groups and the and collectively with the nitrogen atom to which they are ethylpiperazino or Typical embodiments of catalyst having the phosphine and phcs Typical useful of the having the include dioctylphenylphosphinc s phosphine and l The catalyst of formula may effectively be employed in the process of the in l as about but mole per preferably present in amount in range of from to per with respect to the acrylate Greater amounts can be if but g nerally thero is no The catalyst of formula may suitably be used in amounts of up to about 8 mole per preferably from 3 to 5 per with respect to the acrylate monomer the upper amount of catalyst used is dictated largely by the economics of the process preferably at least 3 mole per cent is The catalyst may be employed as such or prepared in as If preparation in situ is one may emplo the dichlorophosphine or as the case may and the appropriate as will be understood by those skilled in the If ous is to be then 4 moles of the amine may suitably be employed per mole of the If the phosphinous amide is to be there is preferably 2 moles of the amine per mole of the In either the n situ preparation involves the formation of an amine salt which must be substantially completely such as by filtration or as The present process may conveniently be carried out at a temperature the range of from to preferably to The pressure is not critical and the reaction is generally performed at atmospheric although atmospheric and pressures are If nitrogen or another inert gas may be used to provide an inert atmosphere and in some instances is particularly when amides employed are derived from low molecular weight such as A solvent is not essential in the present although it may frequently be convenient to employ an organic solvent such as benzene The reaction may be carried out by adding the acrylate to the catalyst or the as It is preferred to add the acrylate incrementally to the with or without a at a rate consistent with the rate of The reaction is somewhat exothermic in nature and the incremental addition of the acrylate to the catalyst can be regulated to moderate the rate of heat Small amounts of water can be tolerated in the reaction mixture without any noticeable adverse larger amounts of such as 5 to by based on the may be enough to considerably inhibit the desired This should be kept in mind particularly if salt formed from an in preparation of the catalyst removed from the reaction mixture by washing with At the conclusion of the the desired product may conveniently be separated by distillation Unreacted if and if e is are preferably removed first and then may be isolated followed finally by the the dimer is formed in greater amounts than the trimer and typically the product will be 60 to or more dimer and 8 to The dimer and triraer may be readily separated by The dimer and trimer are useful chemical intermediates and units for further The trimer is particularly useful in the production of especially with methyl methacrylate and as well as other where the trimer also provides valuable plasticizing properties to the Eecause of its unique the trimer may be used to provide linking to such a polymer system to form useful resins for to a stirred solution containing of dissolved in 150 of The reaction mixture maintained at to during the addition and then stirred for an additional two hours at room The reaction mixture comprising amide and was suction filtered and the hydrochloride residue thus obtained washed with 25 Ethyl acrylate containing the of was added slowly over a period of one hour to the filtered hexane solution of the catalyst maintained at to After permitting the reaction to proceed for four hours at after the addition had been 296 of ethyl acrylate was recovered by of diethyl and of diethyl were obtained by vacuum Example 5 of phosphine dissolved in 50 of benzene were added slowly to a solution at to containing 15 of dissolved in 50 of After completion of the mixture was heated to reflux under nitrogen for two After cooling the reaction mixture comprising nous amide and hydrochloride to temperature the diethylainine hydrochloride salt was extracted with 75 of The organic layer was again washed with 50 of water and 200 of ethyl acrylate inhibited with the of was then added to the benzene solution of the catalyst maintained at After a reaction period of two at the reaction solution was distilled yielding 172 of ethyl On of diethyl and of diethyl were obtained from the This was then repeated that diphenyl in a further dioetyl used as Similar results and yields obtained in both insufficientOCRQuality

Claims (1)

1. 1 A process for the of a or ia an aeryla monomer of the ia group containing 1 to 18 carbon ft is in the presence of a catalyst of in which and are the o different substituted ia which the total of 1 to 8 carbon or to J and B are the or different di alkyl containing or inert 2 and each being joined to the nitrogen a a carbon or together the nitrogen om to which they are attached a saturated cyclic amine group containing up to 5 carbon and optionally oxygen a in the ring which one or alkyl having a total of up to 6 carbo 12 A process as claimed in which catalyst of formula is in amount of at least mole per cent with respect to acrylate monomer actant and the reaction is carried out in the range of to A process as claimed in Claim in which catalyst of formula is used ia aa amount of at least 3 per cent with respect to the monomer reactant and the reaction is carried out in the range of about to A process as daisied Claim ia catalyst of formula is used in an amount from to mole per cent with respect to the acrylate reactant and the is carried out in the range of to A process as claimed in Claim ia which catalyst of formula is used in an amount o from 3 to 5 per cent with respect to the acrylate monomer reactant and the reaction is out in the range of to Λ claimed in Claim 2 or wherein catalyst phenyldipiperidyl A process as i 2 or wherein the catalyst is A process as claimed in Claim 2 or wherein the catalyst is he A process as claimed in 3 or wherein the catalyst is 13 A process as in 3 or A as claimed in any preceding claims in which is to Λ process for the preparation of a acrylate substantially as described in any ono of the foregoing A dime ic triraeric whenever prepared by a as claimed in any the preceding A mixture comprising a ditneric acrylate claimed in as claimed in 14 also containing polymerization process which comprises polymerizing a mixture as in 14 o A produced by a process as claimed Claim For tho Applicants PARTNERS insufficientOCRQuality