Abstract: This invention relates to novel peroxide blends which are liquid at 25.degree. C. and lower, their method of preparation and their use in curing peroxide crosslinkable polymers.The blend is a mixture of the meta isomers or the meta and para isomers of the compounds of Formulae I, II and III and optionally Formula IV (all as defined herein) in such proportions that the composition provides a liquid mixture at 25.degree. C. or below which has a high crosslinking efficiency for polymeric materials.

Abstract: Cellular polymeric solids are made by mixing an acidulous or acidic polymerizable medium that is polymerizable and/or cross-linkable by a free radical mechanism (e.g. an unsaturated polyester) with an effective amount of two or more acid sensitive mono- or poly-azo compounds containing the group: ##STR1## wherein Y is an acid sensitive group (e.g.

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: A process for preparing an alpha-hydroxyazoalkane of the formula ##STR1## wherein A is aryl or (R).sub.3 C and R, R.sub.1 and R.sub.2 are hydrogen, monovalent aromatic or monovalent aliphatic radicals with the provisos that (i) only one of R.sub.1 and R.sub.2 may be (a) hydrogen or (b) aromatic and (ii) no more than one R is aromatic by reacting the corresponding .alpha.-hydroperoxyazoalkane with a mild reducing agent in a non-acidic medium.

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: Shaped cellular structures formed from media which are polymerizable and/or cross-linkable by free radical initiation to either a thermoplastic or thermosetting solid, process for production of such structures and the composition therefor. Process comprises preparation of composition by mixing an acid sensitive azo compound with an acidulous or acidic polymerizable medium, after which the composition is permitted to foam into a cellular structure of the desired shape.

Abstract: Azoalkanes of the formula ##STR1## WHERE Z is isocyanate or isothiocyanate or derivatives thereof, such as 1-t-butylazo-1-isothiocyanatocyclohexane, which are useful as foaming agents for polyester resins and as free radical initiators for vinyl monomers.

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: Shaped cellular structures formed from media which are polmerizable and/or cross-linkable by free radical initiation to either a thermoplastic or thermosetting solid, process for production of such structures and the composition therefor. Process comprises preparation of composition by mixing an acid sensitive azo compound with an acidulous or acidic polymerizable medium, after which the composition is permitted to foam into a cellular structure of the desired shape.

Abstract: A process for preparing an alpha-hydroxyazoalkane of the formula ##EQU1## wherein R is hydrogen, aliphatic, cycloaliphatic or aromatic and R.sub.1 and R.sub.2 are monovalent aliphatic radicals and R.sub.2 can also be aromatic with the proviso that no more than one R is hydrogen or aromatic by oxidizing a hydrazone of the formula ##EQU2## with a non-acidic, aqueous mild oxidizing solution. Generally, the mild oxidizing agent comprises an aqueous solution of a hypohalite or an alkali metal or alkaline earth metal, preferably sodium hypochlorite. The mole ratio of oxidizing agent to hydrazone should be at least 1:1 to ensure complete oxidation, and preferably one uses a 5% to 15% molar excess of the oxidizing agent.

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.