Patent GB-636429-A (GB)
Title: Improvements in and relating to the production of polymeric esters
IPC: C08G63/19
Filed: 1947-12-01
Abstract: Polymeric esters are produced by condensing (a) an w,w1-dicarboxylic acid or terephthalic acid or an ester or anhydride of such acids with (b) a diester of an aliphatic mono-carboxylic acid and an aromatic di-hydroxy compound in which the hydroxy groups if on the same benzene nucleus are m or p to each other, and if on different benzene nuclei, are in the p and p1 or m and m1 positions.  In a modification, one or more w,w1-aliphatic dihydroxy compounds, or a mono- or diester of such compounds is also included in the reaction mixture, or it may be reacted previously with the acid, or reacted with a precondensate of acid and diester.  Most of the products can be spun into fibres capable of being cold drawn, but those from resorcinol diesters are rubbery.  Specified are w,w1-dicarboxylic acids: acids of formula HOOC-(CH2)n-COOH, where n is an integer from 0 to 12, specifically succinic, adipic, suberic and sebacic acids; di-esters: hydroquinone and resorcinol diacetates, dipropionates and dibutyrates, and compounds having the formul  <FORM:0636429/IV (a)/1> and <FORM:0636429/IV (a)/2> in which R and R1 are alkyl groups and X is a bivalent linking group of the type -CH2-, -(CH2)2-, -O-, -S-, -CO-, -O-CH2 -O, or -O-(CH2)2-O, e.g. p,p1-diacetoxy diphenyl, p,p1-diacetoxy diphenyl methane and p,p1-diacetoxy diphenoxy ethane or the corresponding m,m1 compounds; aliphatic dihydroxy compounds: ethylene glycol, tri- and tetraethylene glycols, propane 1,3-diol, butane 1,4-diol, pentane 1,5-diol and hexane 1,6-diol or their mono- or di-esters, e.g. mono- or diacetates.  The reaction is usually carried out firstly at 200 DEG  C. and then after driving off the fatty acid, at 280-300 DEG  C.  In examples, using p-toluene sulphonic acid as catalyst (except example 7, using sulphuric acid and examples 20 and 21 where a mixture of magnesium and aluminium ethoxides is used), the following reactants are heated together: (1) hydroquinone diacetate and succinic acid, (2) resorcinol diacetate and succinic acid, (3) and (4) ethylene glycol diacetate and succinic acid, followed after a time by the addition of hydroquinone diacetate and further heating, (5) hydroquinone diacetate and suberic acid, (6) hydroquinone diacetate and sebacic acid, (7) hydroquinone dipropionate and sebacic acid, (8) p,p1 - diacetoxy diphenoxy ethane and succinic acid, (9) p,p1-diacetoxy diphenoxy ethane and sebacic acid, (10) diacetoxy diphenyl methane and sebacic acid, (11) hydroquinone dibutyrate and suberic acid, (12) resorcinol dipropionate and adipic acid, (13) resorcinol diacetate and suberic acid, (14) resorcinol dibutyrate and sebacic acid, (15) triethylene glycol diacetate and succinic acid, followed by the addition of hydroquinone diacetate and further heating, (16) pentane 1 : 5-diol diacetate and succinic acid, followed by hydroquinone diacetate and further heating, (17) hexane 1 : 6-diol diacetate and adipic acid, followed by hydroquinone diacetate and further heating, (18) butane 1 : 4-diol and adipic acid, followed by hydroquinone diacetate and further heating, (19) triethylene glycol diacetate, p,p1-diacetoxy diphenyl, and adipic acid, (20) dimethyl succinate and hydroquinone diacetate, (21) dimethyl terephthalate, hydroquinone diacetate and pentane 1 : 5-diol.  The preparation is described (see Group IV (b)) of (8) p,p1-diacetoxy diphenoxy ethane and (10) p,p1-diacetoxy diphenyl methane.  Reference has been directed by the Comptroller to Specification 621,102.ALSO:In example (8) p,p1-diacetoxy diphenoxy ethane is prepared by dissolving hydroquinone in a solution of caustic soda in water and ethanol, followed by ethylene dibromide and refluxing.  The product p,p1-dihydroxy-diphenoxy ethane after acidification is extracted with alcohol, and acetylated with acetic anhydride either in aqueous caustic soda cooled with ice, or by refluxing, and recrystallized; (10) p,p1-diacetoxy diphenyl methane is prepared by diazotizing at 5 DEG  C. p,p1-diamino diphenyl methane dissolved in dilute sulphuric acid.  After boiling and filtering hot, crystals of p,p1-dihydroxy diphenyl methane are formed, and are acetylated in solution in dilute caustic soda cooled with ice, by acetic anhydride.  The products are used in the preparation of polymeric esters (see Group IV (a)).  Reference has been directed by the Comptroller to Specification 621,102, [Group IV (a)].