Patent GB-611529-A (GB)
Title: Improvements relating to the production of unsaturated polyesters and polymers thereof
IPC: C08G64/04
Filed: 1946-02-01
Abstract: Unsaturated polyesters are prepared by reacting two or more molecular proportions of an alkenyl chloroformate in which the alkenyl group is derived from an alkenol having a methylene group attached by a double bond to a carbon atom, with a polyhydroxy compound in which the hydroxyl groups are directly attached to an aromatic nucleus.  The polyesters have the general formula <FORM:0611529/IV(a)/1> wherein R is the alkenyl group containing a methylene group attached by a double bond to a carbon atom.  The unsaturated esters may be polymerized, if necessary in the presence of a catalyst, e.g. actinic light, per compounds especially organic peroxides such as diacetyl-, acetyl-benzoyl-, dibenzoyl-, dicaprylyl-, di-o-chlorobenzoyl- or ditoluyl peroxide.  Mixtures of two or more of the polyesters may be polymerized as well as mixtures of these polyesters with other polymerizable unsaturated compounds, as well as with plasticizers, pigments, fillers, other polymers or resins or dyes.  4 : 41-Dihydroxy-3 : 31-dichlorodiphenyl sulphone is polymerized in the presence of a solution of diacetyl peroxide in dimethyl phthalate; 1 : 3-di-(allylcarbonato) benzene is polymerized by heating with o : o1-dichlorodibenzoyl peroxide; and triallyl phloroglucinol tricarbonate is polymerized by heating with dibenzoyl peroxide. Specification 585,775 is referred to.ALSO:Unsaturated polyesters are prepared by reacting two or more molecular proportions of an alkenyl chloroformate in which the alkenyl group is derived from an alkenol having a methylene group attached by a double bond to a carbon atom, with a polyhydroxy compound in which the hydroxyl groups are directly attached to an aromatic nucleus.  The polyesters have the general formula <FORM:0611529/IV(b)/1> wherein R is the alkenyl group containing a methylene group attached by a double bond to a carbon atom.  The reaction may be effected in the presence of a strong base and/or an inert solvent and/or at a moderate temperature preferably below 100 DEG  C. and desirably between about 0 DEG  to 20 DEG  C. The said alkenol may be an allyl or beta-alkyl allyl alcohol such as allyl alcohol, methyl-vinyl carbinol, allyl carbinol, vinyl ethyl carbinol, methyl allyl carbinol, beta-allyl ethyl alcohol, betamethyl allyl alcohol or beta-ethyl allyl alcohol.  The polyhydroxy aromatic compound (a large number of which are specified) are those in which two or more hydroxyl groups are attached to nuclear carbon atoms of an aromatic radical.  All of the hydroxyl groups need not be directly attached to the same aromatic nucleus, and, if they are attached to separate nuclei, the nuclei are preferably jointed by a chain of no more than four atoms.  The aromatic nuclei may be substituted with other groups.  When a polyhydroxy aromatic compound contains more than two hydroxy groups, two or more molecular proportions of alkyl chloroformate may be reacted to p  form, for example, either a di- or a tri-alkenylcarbonate benzene. In examples, the following compounds are prepared: 1 - 4 - di -(allyl - carbonate) - 2 : 3-dichlorobenzene, 1 : 3 - di - (allylcarbonato)-4 - chlorobenzene, 4 : 41 - di - (allylcarbonato)-3 : 31 - dichlorodiphenyl sulphone, 3 : 5 - di(allylcarbonato) - 1 - hydroxy benzene, triallyl phloroglucinol tricarbonate, 1 : 4-, 1 : 3-, and 1 : 2-di(allylcarbonato benzene, diallyl phenolphthalein dicarbonate, 1 : 4-di-(allylcarbonato) - 2 - phenyl benzene, 4 : 41 - di(allylcarbonato) benzophenone, 4 : 41 - diallylcarbonato) - diphenyl sulphone, 2 : 2-bis -[4 - (allylcarbonato) phenyl] - propane and 4 : 41 - di - (allylcarbonato) - octachlorodiphenyl.  Alkenyl chloroformates may be prepared by reacting phosgene with the alkenols mentioned above.  Specification 585,775 is referred to.  The Specification as open to inspection under Sect. 91 refers to the preparation of unsaturated polyesters by reacting phosgene with a polyhydroxy aromatic compound in which the hydroxyl groups are directly attached to an aromatic nucleus and with an alkenol having a methylene group attached by a double bond to a carbon atom, said polyhydroxy compound and alkenol being added in any desired sequence or simultaneously, e.g. the alkenol and phosgene may be reacted to form the alkenyl chloroformate which is then reacted with the polyhydroxy compound or phosgene, or the polyhydroxy compound may be reacted to yield a polychloroformate which is then reacted with the alkenol.  4 : 41-Dihydroxy-3 : 5 : 31 : 51-tetrachlorodiphenyl methone is given as an additional example of a suitable polyhydroxy aromatic compound. This subject-matter does not appear in the Specification as accepted.