Patent GB-893431-A (GB)
Title: Ethylene oxide adducts of tertiary acetylenic alcohols and diols
IPC: C08G65/26
Filed: 1958-05-22
Abstract: Detergent compositions comprise as active ingredients ethylene oxide adducts of acetylenic tertiary carbinols or glycols, the first class of adducts having the general formula <FORM:0893431/III/1> in which R1 and R2 are joined together to form with the shared carbon atom a cycloalkyl group or R1 is an alkyl radical containing at least 3 carbon atoms or a cycloalkyl, aryl or aralkyl radical and R2 is an alkyl, cyclo alkyl, aryl or aralkyl radical and x is an integer of at least 3 and the second class of adducts having the general formula <FORM:0893431/III/2> in which R1, R2, R3 and R4, which ma be the same or different, are alkyl, cyclo alkyl, aryl or aralkyl radicals or R1 and R2 and/or R3 and R4 respectively are joined together to form with their shared carbon atom or atoms one or two cyclo alkyl groups, any of the R1-4 groups not so joined having the aforesaid meaning, and x and y are integers the sum of which is at least 3 and in all cases in this class of adducts groups R1-4 contain a total of at least 7 carbon atoms.  The preferred adducts are those in which x and x and y respectively amount to 3-20.  The compositions may also comprise builders, other detergents and sequestering agents, mention being made of sodium phosphate, sodium dihydrogen phosphate, sodium hexametaphosphate, sodium tripolyphosphate, sodium carbonate, sodium silicate and sodium metasilicate.  The adducts may be used in toilet soaps, shampoos and laundry detergents.  The preparation of the adducts is described (see Group IV(b) ).  Specification 802,798 is referred to.ALSO:The invention comprises ethylene oxide adducts of tertiary acetylenic carbinols and of tertiary acetylenic glycols, the first class of adducts having the general formula <FORM:0893431/IV (a)/1> in which R1 and R2 are joined together to form with the shared carbon atom a cycloalkyl group, or R1 is an alkyl radical having at least 3 carbon atoms or a cycloalkyl, aryl or aralkyl radical and R2 is an alkyl, cycloalkyl, aryl or aralkyl radical and x is an integer of at least 3; and the second class of adducts has the general formula <FORM:0893431/IV (a)/2> in which R1, R2, R3 and R4, which ma be the same or different, are alkyl, cycloalkyl, aryl or aralkyl radicals or R1 and R2 and/or R3 and R4 respectively are joined together to form with their shared carbon atom or atoms one or two cycloalkyl groups, any of groups R1-4 not being so joined having the aforesaid meaning, and x and y are integers the sum of which is at least 3 and in all cases in this class of adducts, groups R1-4 contain a total of at least 7 carbon atoms.  The invention also comprises mixtures of an adduct from each of the two above classes. The preferred glycol adducts are those derived from symmetrical glycols wherein R1 and R4 are the same and represent an alkyl group containing at least 3 carbon atoms.  The adducts are surfaceactive and may be used in detergent compositions (see Group III).  The adducts may be prepared by reacting the corresponding acetylenic tertiary carbinols and/or glycols with ethylene oxide in the presence of a basic catalyst.  The preferred catalysts are tertiary aliphatic amines; less basic catalysts such as dimethyl-aniline may be used; alkali metal hydroxides are preferably used only to catalyse further reaction with ethylene oxide of an adduct formed using a weaker catalyst.  Temperatures may range from about 50 DEG -160 DEG C. Raised pressures may be used. Solvents may be present.  The adducts containing 60 ethylene oxide units are solid.  Examples describe the preparation of adducts from (1) 2:4:7:9-tetramethyl-5-decyne-4:7-diol, (3) 7:10-dimethyl-8-hexadecyne-7:10-diol alone or (4) in mixture with 3-methyl-1-nonyn-3-ol, (5) 4:7-dimethyl-5-decyne-4:7-diol, (6) 2:5-diphenyl-3-hexyne-2:5-diol, (7) 3-methyl-1-nonyn-3-ol, (8) 1-ethynyl cyclohexanol, the adducts containing about 4 to 30 oxyethylene units.  In Examples (1)-(7), triethylamine is used as catalyst.  In Example 8 caustic soda is used or alternatively, a lower adduct is formed, using triethylamine, and then reacted with more ethylene oxide using caustic soda as catalyst.  Specification 802,798 is referred to.ALSO:The invention comprises ethylene oxide adducts of tertiary acetylenic carbinols and of tertiary acetylenic glycols, the first class of adducts having the general formula <FORM:0893431/IV (b)/1> in which R1 and R2 are joined together to form with the shared carbon atom a cycloalkyl group, or R1 is an alkyl radical having at least 3 carbons atoms or cycloalkyl, aryl or aralkyl radical and R2 is an alkyl, cycloalkyl, aryl or aralkyl radical and x is an integer of at least 3; and the second class of adducts has the general formula <FORM:0893431/IV (b)/2> in which R1, R2, R3 and R4, which may be the same or different, are alkyl, cycloalkyl, aryl or aralkyl radicals or R1 and R2 and/or R3 and R4 respectively, are joined together to form with their shared carbon atom or atoms one or two cycloalkyl groups, any of groups R1-4 not being so joined having the aforesaid meaning, and x and y are integers the sum of which is at least 3 and in all cases in this class of adducts, groups R1-4 contain a total of at least 7 carbon atoms.  The invention also comprises mixtures of an adduct from each of the two above classes.  The preferred diol adducts are those which are derived from symmetrical diols wherein R1 and R4 are the same and represent an alkyl group containing at least 3 carbon atoms.  The adducts are surface-active and may be used in detergent compositions (see Group III).  The adducts may be prepared by reacting the corresponding acetylenic tertiary carbinols and/or glycols in the presence of a basic catalyst, with sufficient ethylene oxide to form an adduct containing at least 3 ethylene oxide units.  The preferred catalysts are tertiary aliphatic amines; less basic catalysts such as dimethyl-aniline may be used; alkali metal hydroxides are preferably used only to catalyse further reaction with ethylene oxide of an adduct formed using a weaker catalyst. Reaction temperatures may range from about 50 DEG C. to 160 DEG C.  Raised pressures may be used and solvents may be present.  The adducts containing 30-60 ethylene oxide units are solid.  Examples describe the preparation of adducts from (1) 2 : 4 : 7 : 9-tetramethyl-5-decyne-4 : 7-diol, (3) 7 : 10-dimethyl-8-hexadecyne-7 : 10-diol alone or (4) in admixture with 3-methyl-1-nonyn-3-ol, (5) 4 : 7-dimethyl-5-decyne-4 : 7-diol, (6) 2 : 5-diphenyl-3-hexyne-2 : 5-diol, (7) 3-methyl-1-nonyn-3-ol, (8)1-ethynyl cyclohexanol, the adducts containing about 4 to 30 oxyethylene units.  In Examples (1)-(7) the catalyst is triethylamine.  In example 8 caustic soda is used or alternatively a lower adduct is formed using triethylamine and then reacted with more ethylene oxide using caustic soda as catalyst.  The acetylenic carbinols and diols may be prepared from the appropriate ketone and an alkali metal acetylide in liquid ammonia or calcium carbide and KOH, or acetylene and KOH; a mixture of glycol and carbinol is formed which may be separated by distillation.  Specification 802,798 is referred to.