Patent GB-1077997-A (GB)
Title: A process for the preparation of sulphur-containing derivatives of polymerization products of tetrahydrofuran
Inventor: RENNER JOHANN ALBRECHT
IPC: C08G65/334
Filed: 1964-05-29
Abstract: Sulphur-containing tetrahydrofuran polymers are obtained by reacting at least one tetrahydrofuran compound of the formula Cl-[(CH2)4-O]m-Z wherein m is 2-70 when Z is hydrogen, an organic acyl radical, or an "inorganic oxyacid anion" (see below), or m is 1-70 when Z is [-(CH2)4-Cl], with an alkali metal sulphide or an alkaline earth metal sulphide or with an organic mercapto compound, and, if desired, further reacting the product with an alkali metal sulphide or an alkaline earth metal sulphide or with an organic mercapto compound. The tetrahydrofuran compounds (I) are obtained by polymerizing tetrahydrofuran using acid chlorides as polymerization catalyst. They may have a M.W. of 500-2000 and may be (a) Cl-[(CH2)4-O]m1-Q (II) where Q is an organic acyl radical or an "inorganic oxyacid anion" (i.e. a radical obtained by the removal of an OH group from an inorganic oxyacid) and m1 is 2-70; or (b) the corresponding hydrolysed product:-Cl-[(CH2)4-O]m1-H (III) or (c) derivatives of the formula <FORM:1077997/C3/1> wherein m11 is 1-70.  If compounds (II), (III) or (IV) are reacted with an organic mercapto compound which contains a reactive group, then products containing terminal active groups are obtained.  Suitable alkali metal- or alkaline-earth metal sulphides are Na2S, K2S, CaS, BaS, Li2S and MgS. Suitable organic mercapto compounds which may contain reactive-OH, -NH2, or -COOH groups are mercaptoethanol, thioglycollic acid, thioethanolamine, hydroxy-propylmercaptans, thioglycerol, thiolactic acid, thiohydracrylic acid, methylaminoethyl - mercaptan, butanolthiols, mercaptobutyric acids, aminobutane - thiols, aminopentanethiols, mercaptovaleric acids, mercaptocaproic acids and thiophenol derivatives. Specified products which may be obtained by this process are compounds of the formula <FORM:1077997/C3/2> wherein X represents OH, -S(CH2)qOH, -S(CH2)qNH2 or -S(CH2)rCOOH and Y represents a -(CH2)-qOH, -(CH2)qNH2, -(CH2)rCOOH or -[(CH2)4-O]m1-H, n is 1-70, m1 is 2-70, p is 1-10, q is 2-6 and r is 1-5, and wherein X cannot be basic when Y is acid and vice versa.  Examples are given for the production of compounds (V).ALSO:Sulphur-containing tetrahydrofuran polymers are obtained by reacting at least one tetrahydrofuran compound of the formula Cl-[(CH2)4-O]m-Z (I) wherein m is 2-70 when Z is hydrogen, an organic acyl radical, or an "inorganic oxyacid anion" (see below), or m is 1-70 when Z is [-(CH2)4-Cl], with an alkali metal sulphide or an alkaline earth metal sulphide or with an organic mercapto compound, and, if desired, further reacting the product with an alkali metal sulphide or an alkaline earth metal sulphide or with an organic mercapto compound. The tetrahydrofuran compounds (I) are obtained by polymerizing tetrahydrofuran using acid chlorides as polymerization catalyst. They may have a M.W. of 500-2000 and may be (a) Cl-[(CH2)4-O]m1-Q (II) where Q is an organic acyl radical or an "in-organic oxyacid anion" (i.e. a radical obtained by the removal of an OH group from an inorganic oxyacid) and m1 is 2-70; or (b) the corresponding hydrolysed product Cl-[(CH2)4-O]m1H (III) or (c) derivatives of the formula Cl[(CH2)4-O]m11-(CH2)4-Cl (IV) wherein m11 is 1-70.  If compounds (II), (III) or (IV) are reacted with an organic mercapto compound which contains a reactive group, then products containing terminal active groups are obtained.  Suitable alkali metal- or alkaline earth metals sulphides are Na2S, K2S, CaS, BaS, Li2S and MgS. Suitable organic mercapto compounds which may contain reactive -OH, -NH2, or -COOH groups are mercaptoethanol, thioglycollic acid, thioethanolamine, hydroxy-propylmercaptans, thioglycerol, thiolactic acid, thiohydracrylic acid, methylaminoethyl - mercaptan, butanolthiols, mercaptobutyric acids, aminobutane-thiols, aminopentanethiols, mercaptovaleric acids, mercaptocaproic acids and thiophenol derivatives. Specified products which may be obtaine by this process are compounds of the formula <FORM:1077997/C2/1> wherein X represents OH, -S(CH2)qOH, -S(CH2)qNH2 or -S(CH2)rCOOH and Y represents a -(CH2)-qOH, -(CH2)qNH2, -(CH2)rCOOH or -[(CH2)4-O]m1-H, n is 1-70, m1 is 2-70, p is 1-10, q is 2-6 and r is 1-5, and wherein X cannot be basic when Y is acid and vice versa.  Examples are given for the production of compounds (V).