Patent GB-1077964-A (GB)
Title: Allylic glycidyl ethers and thioethers
Inventor: GURGIOLO ARTHUR EMILIO
IPC: C09B1/40
Filed: 1965-08-20
Abstract: The invention comprises allylic polyethers and thioethers and homopolymers and copolymers prepared therefrom, the allylic compounds having the formula <FORM:1077964/C3/1> where X=O or S, m=0 or an integer from 1 to 5, n=an integer from 1 to 40, R=H, an alkyl group having 1 to 5 carbon atoms, phenyl, benzyl, a fluoro- or chloro- or bromoalkyl group having 1 to 5 carbon atoms and 1 or 2 halogen atoms or an allyloxy-, alkoxy- or phenoxyalkyl group having 1, 2 or 3 carbon atoms in each alkyl portion, and p is an integer from 1 to 4, the groups (XCH2CHR) being different when p is 2, 3 or 4 with n for each group being as defined above but the total not exceeding 40. The compounds are prepared by (1) condensing n moles of one or more alkylene oxides or sulphides, <FORM:1077964/C3/2> with the allylic alcohol or thiol, <FORM:1077964/C3/3> and then (2) making the glycidyl ether or thioether of the resulting compound by reaction with epichlorohydrin and alkali. Many examples are given including Ex.(25):-  <FORM:1077964/C3/4> Ex. (6) A-(EO)15-G, (7) A-(EO)30-G, (8) A-(PO)20-G, where A=the allyloxy group, EO=the oxyethylene group, G=glycidyl group and PO=the 1,2-oxypropylene group. Preferred polymers are the copolymers with propylene oxide, particularly those comprising 3 to 20% by weight of allylic compound and 80-97% by weight of propylene oxide. Example 1A describes the preparation of a copolymer of allyloxy ethyl glycidyl ether with propylene oxide in the presence of a hydrolysed iron alkoxide catalyst and 2,6-di-tert.-butyl-o-cresol and its vulcanization by conventional methods.  Many other copolymers are specified including those of propylene oxide with (22A) A-EO-PO-AGE-G and (24A) A-EO-EpiBr-G where AGE=the 3-allyloxy-1,2-oxypropylene group (derived from allyl glycidyl ether) and EpiBr=the 3-bromo-1,2-oxypropylene group (derived from epibromohydrin).  Zinc diethyl is also used as a catalyst.ALSO:The invention comprises allylic compounds having the formula <FORM:1077964/C2/1> where X=O or S, m=o or an integer from 1 to 5, n=integer from 1 to 40, R=H, an alkyl group having 1 to 5 carbon atoms, phenyl, benzyl, a fluoro- or chloro- or bromo-alkyl group having 1 to 5 carbon atoms and 1 or 2 halogen atoms or an allyloxy-, alkoxy- or phenoxyalkyl group having 1, 2 or 3 carbon atoms in each alkyl portion, and p is an integer from 1 to 4, the groups (XCH2CHR) being different when p is 2, 3 or 4 with n for each group being as defined above but the total not exceeding 40. The compounds are prepared by (1) condensing n moles of one or more alkylene oxides or sulphides, <FORM:1077964/C2/2> with the allylic alcohol, or thiol, <FORM:1077964/C2/3> and then (2) making the glycidyl ether or thio ether of the resulting compound by reaction with epidichlorohydrin and alkali. Particularly preferred is the use of BF3 etherate in (1) and sodium hydroxide in (2).  Specific compounds claimed are <FORM:1077964/C2/4> <FORM:1077964/C2/5> <FORM:1077964/C2/6> <FORM:1077964/C2/7> <FORM:1077964/C2/8> Many others are specified including Ex. (23) <FORM:1077964/C2/9> and Ex. 24 <FORM:1077964/C2/10>