Abstract: A. A novel class of azo compounds R-N.dbd.N-R.sub.1 where R and/or R.sub.1 are groups containing an acylating function, e.g., acyl chloride, chloroformate or anhydride.Example: Cis-4,4'-Azobis-(4-cyanovaleryl chloride).B. a novel class of azo containing polymers(R'--N.dbd.N--C(R.sub.2)(R.sub.2 ') --R.sub.2 "--Y).sub.m --E--(Z).sub.nwherein R' is t-aliphatic, formed by reacting a polymer having at least one group reactive with an acyl group and a compound as in "A" containing only one acylating function. Example: the reaction product of 4-t-butylazo-4-cyanovaleryl chloride and hydroxyl terminated polybutadiene liquid resin.C. a novel class of azo containing polymersZ(E--Y--R.sub.2 "--C(R.sub.2)(R.sub.2 ')--N.dbd.N--C(R.sub.2)(R.sub.2 ')--R.sub.2 "--Y).sub.m' --E--Z,formed by the reaction of a compound as in "A" having two acylating functions with (1) a monomer having two acyl-reactive groups and a monomer having two acylating functions, or (2) a polymer having at least one acyl-reactive group.D.

Abstract: Tertiary-aliphatic alpha-peroxyazo compounds represented by the structure ##STR1## processes for preparing these compounds by reacting ##STR2## with salts or salt solutions ofHOOH (III),(r").sub.3 cooh (iv), ##STR3## and the use of these novel compounds as polymerization initiators for vinyl monomers and as curing agents for resins. For example, 2-t-butylazo-2-(t-butylperoxy)-propane is prepared by reacting the potassium salt of t-butyl-hydroperoxide with 2-t-butylazo-2-chloropropane; and the product is used to cure unsaturated polyester resin at room temperature and to polymerize vinyl chloride at 20.degree.-30.degree. C.

Abstract: A process for preparing a block polymer by first forming a polymer having azo functions by reacting vinyl polymer and a polyazo compound under conditions so that one of the azo functions rupture leaving the other azo function in tact; then, vinyl monomer is reacted with the polymer to produce the block copolymer. The polyazo compounds must contain at least one alkyl or aryl thio or oxa group alpha to at least one of the azo groups in the connecting chain between the azo groups to be useful as the sequential generator of free radicals.

Abstract: Secondary-aliphatic .alpha.-substituted azoalkanes, such as 1-isopropylazo-1-azidocyclohexane, and processes using such azoalkanes as polymerization initiators for vinyl monomers and as curing agents for resins.

Abstract: New aliphatic azo compounds containing an .alpha.-hydroperoxy group and the alkali metal and alkaline earth metal salts thereof as represented by the general structure ##STR1## processes for preparing I where M is H and R is t-aliphatic by reacting t-aliphatic azo compounds having an .alpha.-halo substituent with about an equimolar amount of sodium or hydrogen peroxide; processes for converting I where M is H to its alkali or alkaline earth metal salt by reaction with aqueous solutions of the corresponding base or with calcium or sodium hydride; and the use of these novel compounds as polymerization initiators for vinyl monomers and as curing agents for resins. For example, 2-t-butylazo-2-hydroperoxy-4-methylpentane is prepared from sodium peroxide and 2-t-butylazo-2-chloro-4-methylpentane and used to polymerize vinyl chloride and to cure unsaturated polyester resin.

Abstract: Unsymmetrical azo compounds (R").sub.3 C--N.dbd.N--R' where (R").sub.3 C-- is tert.-aliphatic and R' is --C(R.sub.1)(R.sub.2)(Z) or ##STR1## e.g., 1-t-butylazo-1-chlorocyclohexane, their use as vinyl polymerization initiators and polyester resin curing agents, and methods for preparing same from t-aliphatic hydrazones and t-aliphatic .alpha.-halo-substituted azoalkanes.

Abstract: Secondary-aliphatic .alpha.-substituted azoalkanes of the formula ##STR1## where n is 1 or 2, R' and R" are hydrocarbo, R.sub.1 and R.sub.2 are hydrocarbo or heterocyclic or joined to form a cyclic hydrocarbon group and X is selected from Cl, Br, CN, OH, N.sub.3, SCN and from radicals containing carbon and oxygen, nitrogen or sulfur, for example, 1-isopropylazo-1-azidocyclohexane, and 2-isopropylazo-2-(methoxycarbonyloxy)butane. These azoalkanes are useful as polymerization initiators for vinyl monomers and as curing agents for resins.

Abstract: New aliphatic azo compounds containing an .alpha.-hydroperoxy group and the alkali metal and alkaline earth metal salts thereof as represented by the general structure ##STR1## processes for preparing I where M is H and R is t-aliphatic by reacting t-aliphatic azo compounds having an .alpha.-halo substituent with about an equimolar amount of sodium or hydrogen peroxide; processes for converting I where M is H to its alkali or alkaline earth metal salt by reaction with aqueous solutions of the corresponding base or with calcium or sodium hydride; and the use of these novel compounds as polymerization initiators for vinyl monomers and as curing agents for resins. For example, 2-t-butylazo-2-hydroperoxy-4-methylpentane is prepared from sodium peroxide and 2-t-butylazo-2-chloro-4-methylpentane and used to polymerize vinyl chloride and to cure unsaturated polyester resin.

Abstract: Primary-aliphatic-.alpha.-hydroxyazo-alkanes having the structure: ##STR1## wherein R is hydrogen or a hydrocarbon radical containing 1 to 18 carbon atoms;R.sup.1 is the same as R except R.sup.1 is not hydrogen;R.sup.2 is the same as R except R.sup.2 is neither hydrogen, aryl, nor alkaryl;R.sup.1 and R.sup.2 can together form an alkylene diradical;R, r.sup.1 and R.sup.2 may be optionally substituted with the same or different groups.The compounds of the invention are more stable than the corresponding tertiary aliphatic-alpha-hydroxyazoalkanes. The compounds of the invention are useful as foaming agents for polyester resins and initiators for free radical polymerization of vinyl monomers.

Abstract: Unsymmetrical hydrazo compounds; ##STR1## where (R").sub.3 C-- is a tert-alkyl or tert-aralkyl radical and R.sub.3 and R.sub.4 are hydrogen, lower aliphatic, cycloaliphatic, or an alkylene biradical. Example: ##STR2## These compounds are useful intermediates for preparing the corresponding azo compounds.A process for preparing 1-(R").sub.3 C-- semicarbazide by reacting a urea with t-alkylhydrazine or its acid salt in aqueous medium at 50.degree.-100.degree. C. Example: Urea and t-butylhydrazine HCl were refluxed in water for 4 hours.

Abstract: Unsymmetrical azo compounds (R").sub.3 C--N=N--R' where (R").sub.3 C-- is tert.-aliphatic and R' is --C(R.sub.1)(R.sub.2)(Z) or ##STR1## e.g., 1-t-butylazo-1-chlorocyclohexane, their use as vinyl polymerization initiators and polyester resin curing agents, and methods for preparing same from t-aliphatic hydrazones and t-aliphatic .alpha.-halo-substituted azoalkanes.

Abstract: Amidazo compounds, (R").sub.3 C--N=N--C(=O)--N(R.sub.3)(R.sub.4), where (R").sub.3 C-- is t-alkyl or t-aralkyl, such as t-butylazoformamide, which are useful as polyester resin curing agents and the like.

Abstract: Polyazo compounds containing at least one alkyl or aryl thia or oxa group alpha to at least one of the azo groups in the connecting chain between the azo groups, such as 4-t-butylazo-4-methyl-3-thiapentyl 4-t-butylazo-4-cyanovalerate, which are useful for the sequential generation of free radicals, especially in the preparation of block and graft copolymers.

Abstract: A new class of compounds: R--W--R' were R and R' are identical oxy radicals containing peroxide functions such as dialkyl or diaralkyl peroxide, peroxyketal, peroxyester, or monoperoxycarbonate, and W is a carbonyl group, or carbonyl containing group, or an alkylidene or aralkylidene group, or a phosphorus containing group.ExamplesDi[1,3-dimethyl-3-(t-butylperoxy)butyl]carbonate;Di[1,3-dimethyl-3-(n-butoxycarbonylperoxy)butyl]carbonate;2,2-Bis[3,3-di(t-butylperoxy)butoxy]propane;Di[1,3-dimethyl-3-(t-butylperoxy)butyl]ethyl phosphate.They are free radical affording compounds useful in crosslinking of polyolefins and unsaturated polymers, and for the polymerization of vinyl monomers and diolefinic monomers.

Abstract: A new class of compounds: R-W-R' where R and R' are identical oxy radicals containing peroxide functions such as dialkyl or diaralkyl peroxide, proxyketal, peroxyester, or monoperoxycarbonate, and W is a carbonyl group, or carbonyl containing group, or an alkylidene or aralkylidene group, or a phosphorous containing group.Examples:Di[1,3-dimethyl-3-(t-butylperoxy)butyl]carbonate;Di[1,3-dimethyl-3-(n-butoxycarbonylperoxy)butyl]carbonate;2,2-Bis[3,3-di(t-butylperoxy)butyoxy]propane;Di[1,3-dimethyl3-(t-butylperoxy)butyl]ethyl phosphate.They are free radical affording compounds useful in crosslinking of polyolefins and unsaturated polymers, and for the polymerization of vinyl monomers and diolefinic monomers.

Abstract: Novel t-aliphatic .alpha.-(sulfo) azo compounds: ##EQU1## and the use of compounds I as polymerization initiators for vinyl monomers and as curing agents for resins. For example, 2-t-butylazo-2-thiophenoxy-4-methylpentane, prepared by reacting a solution of thiophenol and sodium hydroxide in methanol with 2-t-butylazo-2-chloro-4-methylpentane at 10.degree. - 15.degree.C., is used to cure an unsaturated polyester-styrene resin at 115.degree.C. and to polymerize styrene at 115.degree.C.

Abstract: Novel symmetrical bis(unsymmetrical t-alkyl and t-aralkyl azo) compounds of the general formula I:r -- n = n -- r.sub.12 -- n = n -- r' (i)where R = R' = (R").sub.3 C--, e.g., 1,2-ethylene bis(4-t-butylazo-4-cyanovalerate); and the use of I for sequential generation of free radicals, e.g. styrene monomer and 1,2-ethylene bis(4-t-butylazo-4-cyanovalerate) are reacted to obtain polystyrene containing attached azo groups which in turn is reacted with methyl methacrylate monomer to obtain a block copolymer of polystyrene and poly(methyl methacrylate).

Abstract: A process for making N-monochloro or bromo monosubstituted urea where a urea RNH--CO--NH.sub.2 is suspended in liquid water at 0.degree.C-60.degree.C and reacted with free chlorine or free bromine, at least 2 g. atoms per mole of urea, preferably in the presence of an acid acceptor such as zinc oxide; R may be alkyl having 3 carbon atoms, cycloalkyl, aralkyl, alkoxycarbonyl, aryloxycarbonyl or acyl.New compounds of the formula R.sub.d --NX--CO--NX'H where X and X' are different and are (1) chloro or bromo and (2) hydrogen and R.sub.d is alkyl or cycloalkyl, 3-15 carbon atoms, or R.sub.1 C(O)--, where R.sub.1 is aliphatic, cycloaliphatic, aryl, alkoxy or aryloxy, each of not more than 10 carbon atoms and when X is H, X' is Cl or Br and R.sub.d is alkyl or cycloalkyl and when X is Cl or Br, X' is H and R.sub.d is R.sub.1 C(O)--.

Abstract: Novel symmetrical bis(unsymmetrical t-alkyl and t-aralykl azo) compounds of the general formula I:R -- N = N -- R.sub.12 -- N = N -- R' (I)wherein R = R' = (R").sub.3 C--, e.g., 1,2-ethylene bis(4-t-butylazo-4-cyanovalerate); and the use of I for sequential generation of free radicals, e.g. styrene monomer and 1,2-ethylene bis(4-t-butylazo-4-cyanovalerate) are reacted to obtain polystyrene containing attached azo groups which in turn is reacted with methyl methacrylate monomer to obtain a block copolymer of polystyrene and poly(methyl methacrylate).

Abstract: Unsymmetrical azo compounds: ##EQU1## where (R").sub.3 C-- is tertiary-aliphatic and Z is cyano or a derivative thereof, e.g., 2-t-butylazo-2-cyanopropane; processes for preparing such azo compounds by (a) adding hydrocyanic acid to a preformed hydrazone, ##EQU2## of a ketone to form a hydrazo compound, and oxidizing the hydrazo compound; or (b) oxidizing the hydrazo compound formed by the reaction of a t-aliphatic hydrazine with hydrogen or alkali metal cyanide in water.