Fire-retardant phosphorus-sulphur additives and polymer systems containing said additives

FIELD: chemistry.

SUBSTANCE: present invention relates to compounds of formulae:

or ,

which are suitable for obtaining foamed polymers, where X denotes O; T denotes S; X' denotes O or S, n - valence A ≤ 2, R² denotes H or alkyl, R³ denotes a hydrocarbon, and A denotes: alkylene, optionally substituted with an ester, ether or amide; an unsaturated hydrocarbon; an alicyclic group; diphenylmethyl; an aromatic group; , where R⁷ denotes H, a hydrocarbon and p=6-n; , where R⁵ denotes an alkyl group, as in compounds and , or a polymer residue, where the phosphorus-sulphur compound contains 5-50 wt % sulphur.

EFFECT: novel compounds which are effective fire-retardant additives for foamed polymers.

6 cl, 38 ex

This application takes priority from provisional patent application U.S. No. 60/876787, filed December 12, 2006.

The present invention relates to flame-retardant additives for organic polymers and, in particular, phosphoric-sulfuric flame retardant additives.

Flame retardants are commonly added to polymeric products used in construction, automotive industry, electronic industry, layered electrical materials, wires and cables, of textile materials and in other applications. Flame retardants increase the limiting oxygen index (LOI) of polymer systems, resulting in products made from such polymer systems that can withstand the standard tests for Flammability. As flame-retardant additives for organic polymers can be applied to various brominated compounds with low molecular weight (<~1500 g/mol). Many of these compounds such as hexabromocyclododecane and polybrominated diphenyl ethers, are a matter of public concern, which may lead to restrictions on their use and encourages the search for replacements for them.

Various phosphorus compounds used as flame-retardant additives. They include organic phosphates, phosphonates and phosphoramide, some of the s of which is described in U.S. patent No. 4070336 and 4086205, and in "The Chemistry and Use of Flame Retardants (fire retardant Chemistry tools and their application), J.W. Lyons, Chapter 2:Chemistry of Fire Retardants Based on Phosphorous(Chemistry fire resistant means on the basis of phosphorus) p. 29-74 (1987). Other commercially available fire-retardant additive is 2,2'-oxybis[5,5-dimethyl-1,3,2-dioxaphosphinan-2,2'-disulfide], which has the structure:

These connections provide moderate resistance to fire and is usually less effective than hexabromocyclododecane or other brominated flame retardants.

It is desirable to provide an alternative flame retardants for organic polymers and, in particular, for foamed polymers. Fire retardant additive should be able to improve LOI polymer system, when it is included in the polymer at a reasonably low levels. Similarly flame-retardant additive should be able to give a good fire properties of polymer system, again when it is present at a reasonably low level. Because in many cases the flame retardant additive of the most traditionally added to the melt of the organic polymer or (as an alternative or Supplement), it is present on subsequent technological operations with the melt, flame retardant additive should be thermally stable at the temperature of molten polymer. This is refers to the range at 150°C and higher, and often above 220°C. The preferred flame retardant, low toxicity.

The present invention in one aspect is a polymer composition comprising a combustible polymer, which is laced with an effective amount of phosphoric-sulfuric additive represented by the structure I:

in which X denotes oxygen or sulfur, T means a covalent bond, oxygen, sulfur, or-NR⁴-where R⁴means hydrogen, alkyl, inertly substituted alkyl or the group P(X)[(X)'_mR]₂provided that at least one of X and T stands for sulfur, each X' independently denotes oxygen or sulfur, each m is independently zero or 1, when X' is oxygen and a is zero, 1 or 2 when X' is sulfur, n is at least 1 and preferably at least 2, each R independently denotes unsubstituted or inertly substituted hydrocarbonous group, or the R groups together form an unsubstituted or inertly substituted divalent organic group, and a represents an organic linking group.

Compounds according to structure (I) often demonstrate very useful and unexpected combination of properties, including in many cases a very low toxicity to mammals and excellent hydrolytic and thermal stability. Their thermostability allows vkliuchati in high temperature polymer materials and manufacturing operations. Unexpectedly, it was found that many of these materials give exceptional fire-retardant efficiency, when they are added to many polymers and polymer foam structures, especially foamy materials polyvinyl aromatic types.

In some embodiments, the implementation of the phosphorus-sulfur additive is represented by the structure II or III:

where R, X, T, A and n are as described above, again provided that at least one of X and T means sulfur.

In other embodiments, the implementation of the phosphorus-sulfur additive is represented by structure IV:

where X, X', T, n and A are as described above, each R²independently means hydrogen, alkyl or inertly substituted alkyl, and R³means a covalent bond or a divalent linking group. In structure IV every R²preferably means hydrogen and R³preferably, means alkilinity diradical having no hydrogens on the carbon atoms connected directly with neighboring groups (R²)₂C. R³more preferably, means (dialkyl)methylene, and most preferably, (dimethyl)methylene.

In other embodiments, the implementation of the phosphorus-sulfur additive is represented by the structure V:

where X, X', A and n are as defined above.

In other respects the present invention means a phosphorus-sulfur compounds. In some embodiments, the implementation of the phosphorus-sulfur compound represented by structure III. In other embodiments, the phosphorous-sulfur compound is represented by structure IV or structure V. In other embodiments, the implementation of the phosphorus-sulfur compound represented by the structures I or II, where T denotes oxygen, sulfur or-NR⁴-where R⁴means hydrogen, alkyl or inertly substituted alkyl, and A means

(1) an organic polymer;

(2) an organic group that is associated with link-T - through the benzyl carbon, including organic group represented by the structure VI

where R⁷means H, hydrocarbon or inert substituent and p is 6-n;

(3) organic group associated with the link-T - through acrylic or methacrylic group, such as represented by structure VII

where R⁸means-CH₃or-H and A²means organic linking group;

(4) the residue of ester diol or dibasic acid (such as an ester of maleic acid or an ester of fumaric acid), having non-aromatic carbon-carbon unsaturation after adding FOS is Horno-sulfuric group to the carbon-carbon double bond of this complex ester;

(5) the remainder of the fatty acid or its ether complex (including the triglyceride fatty acids)in which the fatty acid has at least one carbon-carbon unsaturated centre after adding phosphoric-sulfuric groups such carbon-carbon unsaturated centre, or

(6) an aromatic group associated with the link-T - through aromatic carbon atom.

Phosphorus-sulfur additive is characterized by the fact that it has at least one phosphorus-sulfur group, which contains a phosphorus atom bound to at least two and preferably at least three atoms of sulfur, oxygen or nitrogen, provided that at least one of these atoms is sulfur atom. This group may contain a single atom of sulfur, including fragments of the following types (structure VIII):

Phosphorus-sulfur group may contain two atoms of sulfur associated with the phosphorus atom, including fragments of the following types (structure IX):

Phosphorus-sulfur group may contain 3 or 4 atoms of sulfur associated with the phosphorus atom, as shown in the structure X:

In addition, phosphorus-sulfur group includes fragments, in which the phosphorus atom is directly linked to carbon atom (group a and/or group R, as is isano above), as shown in the structure XI:

Thus, some useful types of suitable non-halogenated phosphorus-sulfur additives can be represented by structure II and III:

where R, X, T, A and n are as described above and at least one of X and T means sulfur. In structures II and III, preferably, T denotes oxygen or sulfur, most preferably sulfur. X is preferably sulfur, and n preferably is at least 2.

In structures I, II or III group R may be, for example, unsubstituted or inertly substituted aliphatic, cycloaliphatic or aromatic groups.

In this application "inert" the Deputy is the one which does not create undesirable deterioration of the flame retardant properties of the additive. The compound containing inert Deputy, called "inertly substituted". Inert Deputy may be, for example, a group containing oxygen, such as a simple ether, ester, carbonyl, hydroxyl, carboxylic acid or oxiana group, etc. Inert Deputy may be a group containing nitrogen, such as primary, secondary or tertiary amino group, aminogroup, amide group, or the nitro-group. Inert Deputy may contain other heteroatoms such as sulfur, phosphorus, credit the deposits (as in Milanovich or siloxane groups), etc. Preferably, the inert Deputy is not a halogen and does not contain halogen.

Gidrolabilna group, for the purposes of the present invention, is a group that, with the exception of inert substituents, contains only atoms of hydrogen and carbon. Gidrolabilna group can be aliphatic, alicyclic, aromatic, or some combination of two or more of these types.

R-groups in structures I, II or III are preferably unsubstituted or inertly substituted lower alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl and the like, More preferably, two R groups together form a divalent organic radical that completes a ring structure link(X')_m-P-(X')_m-, -O-P-O - or-S-P-O -, respectively, as shown, for example, in the above structure IV. Particularly preferred phosphoric-sulfuric additive is a compound represented by the structure XII:

where X, n, R², R³and A are as described above (preferably, X is sulfur). In structures IV and XII of the group R²preferably represent hydrogen or lower alkyl and, more preferably, hydrogen. R³preferably, means hydrocarbonous group with a straight or branched chain-O - or a covalent bond. More preferred groups R³are gidrolabilna groups that are pairwise disubstituted on the carbon atom or carbon atoms that are linked with groups of R²C. R³most preferably, means methylene, substituted two alkilani, as in the case when R³means (dimethyl)methylene.

Particularly preferred phosphoric-sulfuric additive is represented by a structure XIII:

where X, n and A are as indicated above. Preferably, X is sulfur.

Another type phosphoric-sulfuric additive is represented by the structure V:

in which each X', T and X preferably denotes sulfur and A and n are as defined above.

Group A in structures I, II, III, IV, V, XII and XIII means organic binder group. Organic binding group can have many different possible structures. Organic linking group covalently linked to the link-T- (structures I-V and XIII) or atom-S- (structure XII). Link-T - or-S - may be associated with a carbon atom or heteroatom organic bridging group a, but, preferably, it is connected with the carbon atom. This carbon atom, preferably a primary or secondary atom ug is erode (i.e. associated with one or two other carbon atoms), but less preferably, it is a tertiary carbon atom (i.e. one atom linked to three other carbon atoms).

One type of organic linking group And is unsubstituted or inertly substituted gidrolabilna group. Organic binding group And can contain any number of carbon atoms, although preferably a molecular weight in the calculation of the phosphorus-sulfur group does not exceed about 2000 Da, more preferably, not greater than about 1500 Da and especially it is less than 1000 Da. Phosphorus-sulfur additive may contain from 5 to 50% or more sulfur by weight, and when a represents an organic polymer, phosphoric-sulfuric flame retardant additive preferably contains from 5 to 30% sulfur by weight. Organic binding group may be aliphatic (linear or branched), alicyclic, aromatic, or some combination of these types. Valence organic linking group a is equal to n. In each of structures I-V, XII and XIII n, preferably is at least 2.

Organic linking group And may be linear or branched, substituted or unsubstituted alkilinity radical having a valence equal to n. In Allenova the organic radical can contain any number of carbon atoms. An example of the additive, and eUSA group a, which is substituted (in this case, simple ester groups) alkilinity radical represented by structure XIV:

Organic binding group may be unsaturated hidrocarburos group. In this case, it is preferably associated with a link-T - each phosphoric-sulfuric group via allyl or benzyl carbon atom. Examples of compounds in which the phosphorus-sulfur group is associated with allylic carbon represented by the structures of the XV and XVI, where X, R, R²and R³are as defined above.

In the structures of the XV and XVI of the group R²preferably represent hydrogen or lower alkyl and, more preferably, hydrogen, and the group R³are gidrolabilna groups that are pairwise disubstituted on the carbon atom or carbon atoms that are linked with groups of R²C, preferably, methylene, substituted two alkilani, especially (dimethyl)methylene.

Another type of binder group And for structures I-V, XII and XIII, which is associated with link-T - or-S- (if possible) through the benzyl carbon atom, the above structure VI. Specific examples of the phosphorus-sulfur supplements containing this type of group As shown in the following structures XVII-XIII:

For phosphorus-sulfur group may also direct coupling of aromatic ring group A.

Another type of organic binder group And in structures I-V, XII and XIII is the rest of the compounds having acrylate or methacrylate groups, after adding phosphoric-sulfuric source material for the carbon-carbon double bond of acrylate or methacrylate groups. In this case, the linking group a may be represented by the above structure VII. A specific type of phosphoric-sulfuric flame retardant additives of this type is the reaction product of ester acrylate polyol as one connection with 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol.

Another another type of organic binder group And in structures I-V, XII and XIII is the residue of an unsaturated fatty acid or a complex ester of such an acid (including, it should be noted that, triglyceride such fatty acids, in which at least some part of the component fatty acids contain carbon-carbon unsaturation, and this balance means what is left after adding phosphoric-sulfuric source material for the carbon-carbon double bond of a fatty acid or a complex ester. Examples of such triglycerides are what I vegetable oil, such as soy, canola, olive or corn oil.

Another another type of organic binder group And in structures I-V, XII and XIII, after adding phosphoric-sulfuric group on the carbon-carbon double bond, a is the residue of maleic or fumaric complex ester or ether formed from another diol or dibasic acids having non-aromatic carbon-carbon unsaturation. A specific type of phosphoric-sulfuric flame retardant additives of this type is the reaction product maleic double complex ester with 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol.

Other organic binding group And may contain heteroatoms, including oxygen, phosphorus, sulfur, nitrogen, etc. an Example of a linking group containing phosphorus and oxygen, phosphine is a fragment represented by the structure XXIV:

where each R⁵means alkyl or inertly substituted divalent alkyl, preferably ethylene or methylene. Among the organic linking groups containing heteroatoms, are heterocyclic compounds containing a heteroatom in the ring structure. Heterocyclic compounds can be aliphatic or aromatic. Especially interesting heterocyclic aromatic compounds. An example of such heterocyclics the CSOs aromatic compounds is pospisilova or triazine structure:

which may be substituted phosphoric-sulfuric group at any ring carbon or ring at all the carbon.

Some phosphorus-sulfur additive according to the present invention include those of any of structures I-V, XII or XIII, in which the organic binder group And is an organic polymer. Polymeric organic binder group And associated with side phosphorus-sulfur groups are preferred variant implementation of the present invention. Many organic polymers can serve as a cohesive group And provided that the organic polymer used for the formation of organic linking group has a functional group capable of reacting with the formation of links with link-T - or-S- (if possible) phosphoric-sulfuric group.

The polymer or copolymer, which forms the group And may have a mass-average molecular weight of from about 500 to 300,000 or more. However, those that have smaller mass-average molecular weight, such as 1000-20000, especially 2000-10000, exhibit a tendency to a better dispersion in many polymers, especially styrene homopolymers and copolymers, and may be more effective in providing flame retardant properties.

Suitable tee is an organic polymer, applicable to the formation of organic linking group a, contains or can be modified to contain aliphatic carbon-carbon unsaturation capable of reacting with the formation of the connection with phosphoric-sulfuric group. Examples of organic polymers containing aliphatic carbon-carbon unsaturation include homopolymers of a conjugated diene, such as butadiene, isoprene or cyclopentadiene, or copolymers of two or more conjugated dienes or of at least one conjugated diene and at least one other copolymerizable monomer. Examples of the latter type include copolymers of butadiene or isoprene and a vinyl aromatic monomer such as styrene. Another example of an organic polymer containing aliphatic carbon-carbon unsaturation, is a polymer or copolymer of a monomer having two ethylene-unsaturated groups with different reactivity, such as allylacetate, alismataceae etc. More of these reactive groups can be polymerized to a greater extent (mostly), which leads to the formation of a polymer having ethylene unsaturation in the side groups. Another example of the organic polymer having aliphatic carbon-carbon unsaturation, is a complex p is liefer unsaturated aliphatic dibasic acid, such as maleic acid or fumaric acid (or the corresponding dual esters or anhydrides).

For the introduction of aliphatic unsaturation in organic polymer can be modified in many ways, and such modified polymers can be used for the formation of organic bridging group A. the Traditional way to introduce unsaturation is the reaction of the reactive group in the organic polymer with an unsaturated compound containing ethylene unsaturation and jointly reactive group that reacts with a reactive group in the organic polymer with the formation of the connection. For example, acrylic, acrylate, methacrylic and methacrylate compounds may react with reactive groups such as hydroxyl, ester, primary or secondary amino group and the like, for the introduction of acrylate or methacrylate functions in an organic polymer.

Other organic polymers which can be used for the formation of organic binder group And contain other types of reactive centers, through which the polymer can be associated with a link-T - or atom-S - phosphoric-sulfuric group. Examples of such groups include epoxy groups, and halogen substituents (in particular chlorine or bromine).

For about the education organic linking group, And you can apply many different epoxy resins. Examples of these resins include diglycidyl ethers, polyhydric phenol compounds such as resorcinol, catechin, hydroquinone, bisphenol, bisphenol a, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-Penilaian), bisphenol F, bisphenol K, tetramethylbiphenyl, diglycidyl ethers of aliphatic glycols and polyether glycols such as diglycidyl ethers, C_2-24-alkalophile and poly(ethylene oxide)or poly(propylene oxide)glycols; polyglycidyl ethers of phenol-formaldehyde Novolac resins, phenol-formaldehyde resins, substituted alkilani (epoxy Novolac resin), phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, Dicyclopentadiene-phenol resins, Dicyclopentadiene-substituted phenol resins, etc.

Organic polymers applicable to the formation of organic binder group and replaced by halogen include, for example, polymers and copolymers of halogenated monomers such as vinyl chloride, vinylidenechloride, vinylbenzoic etc. In the alternative, the halogen group can be introduced in a pre-obtained polymer in a variety of ways. It is noted that the polymers of vinylbenzoate form a phosphorus-sulfur additive, in which the phosphorus-sulfur group (one or more) associated with the benzyl carbon atom

Especially interesting organic polymer binder group And is (after adding phosphoric-sulfuric group to the carbon-carbon double bond of the polymer) residue of a polymer or copolymer of a conjugated diene and especially polymer or copolymer of butadiene or isoprene with at least one vinyl aromatic monomer, such as styrene. The copolymers can be statistical or block types. Especially interesting block types are diblock copolymers and triblock copolymers, which contain a Central polybutadiene block and polystyrene end blocks. Diblock copolymers few more preferable than triblock types, when applied to the formation of organic binder group And, in particular, when used with polyvinyl aromatic materials such as polystyrene. Before the introduction of the phosphorus-sulfur groups, the copolymer contains at least 10% by weight of polymerized butadiene. Butadiene is polymerized with the formation of two types of repeating units. One type, called herein the term "1,2-butadiene units", takes the form

and thereby introduces into the polymer of unsaturated side groups. The second type, called herein the term "1,4-butadiene units", takes the form-CH₂-CH=CH-CH and introduces unsaturation in the main chain of the polymer. The butadiene/vinyl aromatic polymer used as an organic linking group, And preferably contains at least a certain number of 1,2-butadiene units before adding phosphoric-sulfuric group. At least 10%, preferably at least 15% and, more preferably, at least 20% and even more preferably at least 25% of the butadiene units in the butadiene/vinyl aromatic polymer is 1,2-butadiene units before adding phosphoric-sulfuric group. 1,2-butadiene units can be at least 50%, at least 55%, at least 60% or less least 70% of the butadiene units in the butadiene/vinyl aromatic copolymer before adding phosphoric-sulfuric group. The proportion of 1,2-butadiene units may exceed 85% or even exceed 90% of the butadiene units in the original copolymer. Methods of obtaining the butadiene/vinyl aromatic polymers with controlled content of 1,2-butadiene is described in the publication J. F. Henderson and M. Szwarc inJournal of Polymer Science(D, Macromolecular Review), Volume 3, page 317 (1968), Y. Tanaka, Y. Takeuchi, M. Kobayashi and H. Tadokoro inJ. Polym. Sci. A-2, 9, 43-57 (1971), J. Zymonas, E. R. Santee and H. James Harwood inMacromolecules, 6, 129-133 (1973) and H. Ashitaka et al., inJ. Polym. Sci. Polym. Chem.21, 1853-1860 (1983).

Polymers of one or more conjugated dienes can be, for example, the chickpeas to bromirovanii, for example, N-bromosuccinimide, which gives allele brominated polymers. Such allele brominated polymers can lead to binding groups And in which the group And is associated with link-T - or-S - via allylic carbon atoms.

Phosphorus-sulfur additive in most cases can be obtained directly by applying a simple chemical methods. Phosphorus-sulfur raw materials are easy to obtain, bringing alcohol into contact with P₂S₅which is easily available as lubricants and raw material for the production of biocides. Alcohol has the structure POH, where R is as defined in structure I above. Get the source phosphorus-sulfur material has a structure XXV as follows.

where X and R are as defined above. Diatomic alcohols having the form HO-C(R²)₂-R³-C(R²)₂0H (where R²and R³are as defined with regard to structure IV above), can react with P₂S₅with the formation of cyclic phosphoric-sulfuric starting material having the structure XXVI:

where X, X', R²and R³are as defined above. Compounds of this type can be obtained using the methods described in Chauhan, H. P. S.; Bhasin, C. P.; Srivastava, G.; Mehrotra, R. , "Synthesis and characterization of 2-mercapto-2-thioxo-1,3,2-dioxaphospholanes and dioxaphosphorinanes" Synthesis and characterization of 2-mercapto-2-thioxo-1,3,2-dioxaphospholane and dioxaphosphorinanes),Phosphorus and Sulfur and the Related Elements(Phosphorus and sulfur and the related elements) (1983), 15(1), 99-104 and Edmundson, "Cyclic Organophosphorus Compounds-Ill, Some Sterically Hindered Pyrophosphates" (Cyclic organophosphorus compounds. III. Some steric employed pyrophosphates),Tetrahedron,1965, 2379-2387. Particularly preferred phosphorus-sulfur-source material is:

where X is the same as defined above, and, preferably, means sulfur.

Phosphoric-sulfuric starting compound can be converted into the corresponding amine salt by mixing with primary, secondary or preferably a tertiary amine compound, and the resulting amine salt can react with an organic halide, forming phosphoric-sulfuric fire retardant substance. The sequence of reactions is traditionally carried out in a solvent for the starting materials may, at room temperature, at a slightly lower temperature or at a somewhat elevated temperature below the temperature of decomposition of the original materials. A suitable temperature is from 10 to 100°C. the Reaction can be schematically illustrate idealized reaction scheme XXVII

where each R¹³independently means hydrogen, hydrocarbon or inertly substituted hydrocarbon, X represents halogen, preferably chlorine or bromine and R, n, A and X are as defined above.

Phosphoric-sulfuric starting compound can also be obtained by direct reaction with electrophiles, such as ortho-dissimilatory, 1,4-dibromo-2-butene, without the initial receipt of the ammonium salt, as described Kaboudin, B.; Norouzi, H.,Synthesis,2004, 12, 2035-2039.

Reagent AX"_nmay be, for example, alkane or alkene, substituted by one or more, preferably two or more, preferably, 2 to 4 halogen atoms, which most preferably is chlorine or bromine. Examples of such substituted alkanes and alkenes include 1,4-butandiol, 1,4-butadiene, 1,2-ethylene, 1,2-ethylenedibromide, 1,2-propylaniline, 1,2-Propylenediamine, 1,4-dibromo-2-butene, 1,4-dichloro-2-butene, etc. Instead reagent AX"_nmay be an aromatic compound, substituted with one or more haloidalkyls groups, especially bromeilles or chloromethylene groups and optionally other substituents in the ring. Examples of such aromatic compounds include benzylchloride, o -, m - or p-celldepleted, o-, m - or p-cylindered, 1,2,4,6-Tetra(methyl bromide)benzene, 1,2,4,6-Tetra(chloromethyl)benzene, 1,2,3,4,5,6-hexa(methyl bromide)benzene, 1,23,4,5,6-hexa(chloromethyl)benzene, 1,3,5-Tris(methyl bromide)-2,4,6-trimethylbenzene, 1,3,5-Tris(chloromethyl)-2,4,6-trimethylbenzene, poly(vinylbenzoate), poly(vinylbenzoate) and copolymers of poly(vinylbenzoate) and/or poly(vinylbenzoate) at least one other copolymerization monomer, polymers and copolymers of vinyl chloride and vinylidenechloride etc.

In another method of production of phosphorus-sulfur additive phosphorus-sulfur-source material lead in direct contact with the compound having one or more aliphatic carbon-carbon double bonds, as schematically shown in reaction sequence XXVIII. The reaction can be carried out in a solvent for the starting material and, in any convenient temperature below the temperature of decomposition of the original materials. A suitable temperature is from 0 to 100°C. the Reaction sequence XXVIII is the following:

wheremean compound having a carbon-carbon double bond. The carbon-carbon double bond may be CIS - or TRANS-configuration. Reactions of this type are described, for example, in the work Mehbah et al.,Phosphorous, Sulfur and Silicon and The Related Elements(Phosphorus, sulfur and silicon and related elements) 1992,73,49-56.

The unsaturated compound may contain only one carbon-carbon double bond or can the content is to be two or more such double bonds. If there are multiple double bonds, they can be paired or may not be, but at least one of them is not aromatic. The double bond may be present in non-aromatic ring structure. Examples of suitable olefinic compounds include, for example ethylene, propylene, 1 - or 2-butene, 1 - or 2-penten, higher alpha-olefins, such as 1-hexene and 1-octene, butadiene, isoprene, cyclopentene, cyclopentadiene, Dicyclopentadiene, 1,5,9-dodecatrien, styrene, divinylbenzene, trivinylbenzene, ethylidenenorbornene, norbornene, norbornadiene, vinylcyclohexane, cyclooctadiene, 1,6-octadien, compounds and adducts containing acrylate and/or methacrylate groups, polymers and copolymers of butadiene and/or isoprene (including block copolymers and random copolymers of butadiene with a vinyl aromatic monomer such as styrene), etc.

Phosphorus-sulfur-source material can be brought into contact with oxiranyl compound, such as epoxy resin, as described above, for the production of phosphorous-sulfur flame retardant compound applicable in the present invention. In this case the group-T-H reacts with epoxypropoxy, opening the epoxide ring to form-HE-group (corresponding to the oxygen atom oxiranes ring). This reaction can be carried out in a solvent for the source is the materials at a temperature of from slightly below room temperature up to the decomposition temperature of the source material. A suitable temperature is from 10°C. to 100°C. If desired, this reaction can be catalysed.

Phosphorus-sulfur additive can be used as flame retardants for a variety of combustible polymers. The term "fuel" in this document simply means that the polymer is able to burn. Combustible polymer can be a thermoplastic or thermosetting polymer.

Interesting flammable polymers include polyolefins such as polyethylene (including copolymers of ethylene, such as copolymers of ethylene with α-olefin, polypropylene and the like; polycarbonates and mixtures of polycarbonates, such as a mixture of polycarbonate with a complex polyester, Acrylonitrile-styrene-butadiene resin, styrene-Acrylonitrile resin or polystyrene; polyamides; polyesters; epoxy resins; polyurethanes; polyisocyanurate and vinyl aromatic polymers (including vinyl aromatic homopolymers, vinyl aromatic copolymers, mixtures of one or more vinyl aromatic homopolymers and/or vinyl aromatic copolymers with another polymer, such as poly(phenylisocyanate) resin and vinyl aromatic polymers, modified rubber); vinyl ester resins; thermoplastic or thermosetting vinyl ester resin, and other flammable polymers which can be dissolved or dispersion is activated phosphorus-sulfur additive.

A particularly interesting polymers are polyolefins. Polyolefin polymers are polymers or interpolymer containing the repeating unit obtained by polymerization of α-olefin. Particularly suitable α-olefins have from 2 to about 20 carbon atoms, preferably from 2 to 8 carbon atoms and include ethylene, propylene, 1-butene, 4-methyl-1-penten, 1-hexene, 1-octene and the like, Preferable α-olefin polymers are homopolymers of ethylene or propylene and interpolymers ethylene with C₃-C₈-α-olefin. α-Olefin polymer may also contain, in polymerized form, one or more of other monomers capable of interpolymerization with an α-olefin and containing an aliphatic or cycloaliphatic group. Such monomers include, for example, vinyl acetate, acrylic acid, methacrylic acid, esters of acrylic or methacrylic acid, and acid anhydrides such as maleic anhydride. α-Olefin polymer preferably contains at least 75% by weight, preferably at least 95% by weight of the polymerized α-olefin monomers. More preferably, the α-olefin polymer is an interpolymer polymer of at least 85% by weight of polymerized ethylene and 15% by weight of another α-olefin. Particularly suitable α-olefin polymers on the require-low density polyethylene (LDPE) - the term used in this description to denote polyethylene homopolymers produced in the process of free-radical polymerization under a high pressure. In the present invention can also be used with products such as linear low density polyethylene (LLDPE) and high density polyethylene (HDPE). You can also apply LLDPE polymers having a homogeneous distribution of the comonomers described, for example, in U.S. patent No. 3645992 issued Elston, and in U.S. patent No. 5026798 and 5055438 issued by Canich. Other applicable type of α-olefin polymer is a substantially linear olefin polymer as described in U.S. patent No. 5272236 and 5278272, incorporated herein by reference. Another suitable α-olefin polymer is a homopolymer or interpolymer propylene. Interpolymer propylene can be interpolymers propylene and one or more other monomers, such as other α-olefin, vinyl acetate, methyl acrylate, acrylate, methacrylate, acrylic acid, taconova acid, maleic acid and maleic anhydride.

Another particularly interesting combustible polymer is a vinyl aromatic polymer.

"The vinyl aromatic polymer is an aromatic polymer compound having a polymerized ethylene-unsaturated group attached directly superadmin atom of the aromatic ring. Suitable vinyl aromatic polymers include homopolymers of vinyl aromatic monomers and their copolymers with one or more copolymerizable ethylene-unsaturated compounds (components up to 50% by weight). Vinyl aromatic polymer or copolymer can be used alone or in mixture with other vinyl aromatic polymer or copolymer and/or a polymer of a different type (such as, for example, poly(phenyleneoxy) or poly-1,6-(2,6-dimethylphenoxy) ether. Vinyl aromatic polymer, preferably has a mass-average molecular weight of from 100,000 to 350,000, measured using chromatography on the sizes of the molecules. Suitable vinyl aromatic monomers include unsubstituted materials, such as styrene, divinylbenzene and vinylnaphthalene, as well as connections, substituted for the ethylene-unsaturated group (such as, for example, alpha methylsterol) and/or substituted in the ring. Substituted in the ring vinyl aromatic monomers include compounds that have halogen, alkoxyl, the nitro-group or unsubstituted or substituted alkyl group, directly connected with the carbon atom of the aromatic ring. Examples of such substituted in the ring vinyl aromatic monomers include 2 - or 4-Postira, 2 - or 4-chloresterol, 2 - Il is 4-mitoxantron, 2 - or 4-nitrostyryl, 2 - or 4-methylsterol, atillery and 2,4-dimethylstyrene. Suitable copolymerizate monomers include acrylic acid, methacrylic acid, ethacrylate acid, maleic acid, taconova acid, Acrylonitrile, maleic anhydride, methyl acrylate, acrylate, butyl acrylate, propylacetate, methyl methacrylate, vinyl acetate, vinyl alcohol, certain amides and butadiene. Interesting foamed polymers of any of these types.

Thermoplastic and thermosetting vinyl ester resins are described, for example, Vinyl Ester Polymers”, Encyclopedia of Polymer Science and Engineering, Mark et al., ed., Vol. 17, pp. 393-445 (1989), is also particularly interesting.

Especially interesting combustible polymer is a polymer or copolymer of a vinyl aromatic monomer, such as styrene polymer or copolymer, as described above, the styrene-Acrylonitrile polymer (SAN), polystyrene, modified rubber (such as high impact polystyrene or styrene-Acrylonitrile-butadiene (ABS) resin. Polystyrene is particularly preferred combustible polymer.

Another particularly interesting combustible polymer is statistical, block - or graft-copolymer of butadiene and at least one vinyl aromatic monomer. Among them, preferred block copolymers, particularly preferred diblock or triblock copolymers of butadiene and styrene.

Combustible polymer can be (both before and after the inclusion of phosphoric-sulfuric additives) in the form of finished products of any type, including, without limitation, a film, sheet material, fiber, foam or molded product.

Foam flammable polymers of any of the above types are particularly interesting because they are used in the automotive industry and in construction, where the characteristics of fire safety is especially important. Foam combustible polymer typically has a foam density of from about 0.5 to about 30 pounds per cubic foot (pcf) (8-480 kg/m³), especially from about 0.8 to about 10 pcf (from 12.8 to 160 kg/m³and, most preferably, from about 1 to about 4 pcf (16 to 64 kg/m³). Foam combustible polymer can be produced by any suitable means, including extrusion methods, reactive foaming and foaming granular polymer. Phosphorus-sulfur additive according to the present invention are often suited for the production of extruded foamed polymers, since these compounds in many cases, have sufficient thermal stability, as shown by the test temperature of 5%weight loss, described below, to be entered in the extrusion process of the foam, through which the foam material. Especially preferred is entrusted flammable polymers are extruded polystyrene and foamed granular polystyrene.

Sufficient phosphoric-sulfuric additives used to improve the fuel efficiency of the polymer in one or more standard tests for fire resistance. One such test is the determination of the limiting oxygen index (LOI), which measures the minimum concentration of oxygen in the atmosphere required to maintain combustion of the polymer. LOI traditionally determined according to ASTM D2863. Combustible polymer containing phosphorus-sulfur compound preferably has an LOI of at least 2%, more preferably at least 3%, more than the corresponding value of one combustible polymer. When the combustible polymer is polystyrene, the LOI of a mixture of polystyrene flame retardant additive is at least 20%, more preferably at least 23%, even more preferably at least 25%. Another test is a measurement of time prior to the termination of combustion, known as FP-7, which are determined according to the method described by A. R. Ingram inJ. Appl. Poly. Sci. 1964,8, 2485-2495. This test measures the time required to stop the burning flame, when in certain conditions, the polymer sample is exposed to flame, then the flame source is removed. Usually the values of the FP-7 should be as low as possible. For polystyrene polymer containing flame retardant to avco, described in this document, it is desirable that the value of FP-7 was less than 10 seconds, preferably less than 5 seconds, even more preferably less than 2 seconds. Typically, these results can be obtained when phosphoric-sulfuric flame retardant additive is from 1 to about 15, preferably from 1 to about 6% by weight of the combined combustible polymer.

In many cases it is convenient to mix the phosphorus-sulfur flame retardant additive with the molten combustible polymer, both before and during the other technological operations with the melt (such as extrusion, foaming, molding and so on). Therefore, phosphorus-sulfur flame retardant additive, preferably, is thermally stable at the temperature at which the process of the molten polymer. For many combustible polymers, this temperature is above 150°C, and for many combustible polymers of special interest (such as polystyrene), it is higher than 200°C., or even above 220°C, or even higher.

A useful indicator of thermal stability is the temperature of 5%weight loss, which is measured by thermogravimetric analysis as follows: ~10 mg phosphoric-sulfuric flame retardants analyze using the device model Hi-Res TGA 2950 (TA Instruments) or equivalent device in the flow of nitrogen gas (60 ml/min) at a heating rate of 10 the C/min in the range from room temperature (nominally 25°C.) to 600°C. Monitor the mass loss of the sample during the stage of heating, and the temperature at which the sample loses 5% of its original mass, is designated as the temperature loss 5% weight (5% WLT). This method provides a temperature at which the sample undergoes cumulative mass loss component 5 wt.% from the original sample mass. Phosphorus-sulfur additive, preferably, shows a 5% WLT equal to at least the temperature at which a combustible polymer is subjected to processing in the melt (for mixing with phosphoric-sulfuric flame retardant additive or processing of the mixture in the manufacture of its products, such as foam, extruded part, molded part or the like). When it is used in the processing of the melt with combustible polymer, phosphoric-sulfuric flame retardant additive should have a 5% WLT equal to at least 150°C. Preferably, 5% WLT is at least 200°C., more preferably at least 225°C., even more preferably at least 240°C. and even more preferably at least 250°C, especially when the combustible polymer is polystyrene.

Phosphorus-sulfur additive can be mixed with a combustible polymer, and applying other methods, such as mixing in a solution of combustible polymer, adding in the process of suspension polymerization is whether emulsion polymerization or in other ways. Thermostability of phosphoric-sulfuric additives is less important if the combustible polymer is processed in the melt in the presence of phosphoric-sulfuric supplements, because in such cases, the phosphorus-sulfur additive is usually not subjected to such high temperatures during process operations.

The polymer mixture according to the present invention may include other additives, such as other flame retardants, heat stabilizers, stabilizers, increasing the stability to ultraviolet light, the seed substances, antioxidants, foaming agents, fillers, cross-linking or implanted substances, sinks acid and coloring tools.

Polymer mixtures containing phosphoric-sulfuric flame retardant additive according to the present invention, can be processed in the melt or in solution to produce a wide range of products. Interesting foamed (cellular or expanded products, because they are used in various fields of construction and automotive industry, in which fire safety is especially important. Foamed (expanded) vinyl aromatic polymers and butadiene polymers and copolymers, as described above, are particularly interesting. According to the present invention can also be produced neechee the s polymers.

The following examples are provided to illustrate the present invention but not to limit its scope. All parts and percentages are given by weight, unless otherwise specified.

Example 1

To a stirred solution of 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (10.0 g, 50 mmol) in toluene (70 ml) was added triethylamine (5.0 g, 50 mmol) to form salts of ammonium. The mixture was heated to 45°C. To the mixture was added 1,4-dibromo-2-ene (5.34 g, 25 mmol) and the mixture was heated at the boil under reflux for 1 hour. Then the solution was washed with saturated aqueous sodium bicarbonate solution (50 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure, obtaining a white solid. The crude product was dispersible in ethanol (40 ml) and filtered, obtaining 8.7 g (80%) of a white solid substance, 2,2'-[2-butene-1,4-diylbis(methylthio)]bis[5,5-dimethyl-1,3,2-dioxaphosphinan]-2,2'-disulfide having the structure:

Thermostability of 2,2'-[2-butene-1,4-diylbis(methylthio)]bis[5,5-dimethyl-1,3,2-dioxaphosphinan]-2,2'-disulfide were evaluated by thermogravimetric analysis as described above. In this test, the sample showed a 5% WLT at 241°C. Proton and³¹P NMR of this sample showed the following peaks:

¹H NMR(300 MHz, CDCl₃) δ: of 5.82 (m, 2H), 4,17 (m, 4H), 3,95 (who, 4H), 3,62 (m, 4H), 1,24 (s, 6H), of 0.93 (s, 6H).

³¹P NMR (CDCl₃vs. H₃PO₄) δ: 89,23.

The portion of the sample was mixed in the melt with polystyrene resin at a mass ratio of 4:96. Hardened mixed melts crushed laboratory crusher Wiley with a 3-mm sieve. Aliquots of powdered mixtures on 25-27 g stamped under pressure in a plate dimension of 100 mm × 100 mm × 1.5 mm, using hydraulic flat press Pasadena (model BL444-C-6M2-DX2357), who worked with the temperature set at 180°C, the duration of the applied pressure equal to 5 min, and applied pressure equal to 25,000 pounds per square inch (psi) (172 MPa). A molded plate was cut into strips to determine the limiting oxygen index (LOI) and FP-7. LOI was evaluated according to ASTM D 2863, and he was found equal to 26.5 per cent. FP-7 were evaluated as described above; this value was found equal to 1.9 C.

10% (by weight) concentrate, based on the weight of the concentrate, phosphoric-sulfuric additive in polystyrene was obtained by mixing 2,2'-[2-butene-1,4-diylbis(methylthio)]bis[5,5-dimethyl-1,3,2-dioxaphosphinan]-2,2'-disulfide and polystyrene. The mixture was compoundable in the melt with polystyrene using conical twin-screw extruder Haake RHEOCORD™ 90, provided with a twisting head. The extruder had three temperature zones, working with temperatures set at 135°C, 170°C and 180°C; temperature is RA nozzle head was set at 180°C. The extruded material was cooled in a water bath and cut into pellets with a length of approximately 5 mm, These granules were converted into foam, consistently using a 25 mm single screw extruder with three heating zones, a compartment for mixing with foaming agent, the Department for cooling and adjustable to 1.5-mm slit nozzle. Three heating zone operated at temperatures that are installed on 115°C, 150°C and 180°C, the mixing zone operated at a temperature set at 200°C. carbon Dioxide (4.5 parts by weight per 100 parts by weight of the combined weight of the pelletized concentrate and additional granulated polystyrene) was administered in the Department of mixing with the blowing agent, applying two different syringe pump RUSKA™ (Chandler Engineering Co.). Pellets of concentrate and pellets of additional polystyrene were mixed in dry form from 0.05 wt.%, calculated on the dry weight of the mixture of barium stearate used as a screw lubrication. The ratio of pellets of concentrate and pellets of additional polystyrene was chosen so that the final concentration of flame retardant additives was 4.2 wt.%. The dry mixture was added to the hopper of the extruder and injected at a speed of 2.3 kg/h In the mixing Department kept the pressure above 1500 psi (10.4 MPa) to obtain a homogeneous lane is mixed polymer gel and foam with a uniform cross-section. Refrigerators lowered the temperature of the expanded onto a gel to 120-130°C. the nozzle Orifice regulated in such a way as to maintain a back pressure of at least 1000 psi (6,9 MPa). Expanded onto the gel expanded at the nozzle exit with the formation of polystyrene foam with a bulk density of about 2.5 pcf (~40 kg/m³). LOI for this foam was 24.7%, and FP-7 was 4.9 C.

Example 2

A mixture of N,N-diethylethanamine, 5,5-dimethyl-1,3,2-dioxaphosphinan-2-tilt-2-oxide (7.5 g, 27 mmol) and 1,4-dibromobutane (2,84 g, 13,2 mmol) was dispersible in 50 ml of ethanol and boiled under reflux for 5 hours. The reaction mixture was cooled and concentrated under reduced pressure. The obtained residue was dissolved in methylene chloride (100 ml), washed with water (40 ml), dried and concentrated, obtaining of 3.60 g (66%) of white solid, 2,2'-[2-butene-1,4-diylbis(methylthio)]bis[5,5-dimethyl-1,3,2-dioxaphosphinan]-2,2'-dioxide having the structure:

The 5% WLT for this material was 255°C. the Plates are made from a mixture of 4% of the product in 96% of polystyrene, had LOI, equal to 22%, and the value of the FP-7, equal to 5.7 C.

Example 3

To a mixed solution of ammonium salt of o,O-diethyl ether complex dithiophosphoric acid (15,8 g, 78 mmol) in ethanol (130 ml) at 80°C portions) was added 1,4-dibromo-2-butene (of 7.55 g, 35 mmol). The resulting mixture was about what was lagali, was diluted with water (150 ml) and was extracted with methylene chloride (3 × 100 ml). The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, obtaining 15 g (99%) O,O'-diethyl ether complex S-[4-(diethoxy-thiophosphorylated)-but-2-enyl]dithiophosphoric acid, having the structure:

Example 4

To a stirred solution of 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (8.0 g, 40 mmol) in toluene (70 ml) was added triethylamine (4.0 g, 40 mmol). The mixture was heated to 45°C. To the mixture was added o-celldepleted (3.51 g, 20 mmol) and then the mixture was heated at the boil under reflux for 1 hour. The solution was washed with saturated aqueous sodium bicarbonate solution (50 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure, obtaining a white solid. The crude product was dispersible in ethanol (40 ml) and filtered, obtaining of 7.8 g (78%) of white solid, 2,2'-[1,2-phenylenebis(methylthio)]bis[5,5-dimethyl-1,3,2-dioxaphosphinan]-2,2'-disulfide having the structure:

The 5% WLT for this material was 240°C. the Proton,¹³C and³¹P NMR of this sample showed the following peaks:

¹H NMR (CDCl₃) δ: 7,40 (m, 2H), 7,25 (m, 2H), 4,32 (d, J=12 Hz, 4H), 4,11 (m, 4H), 3,88 (m, 4H), 1,24 (who, 6H), 0,86 (s, 6H).

¹³C NMR (CDCl₃) δ: 135,22, 135,12, 131,20, 128,76, 77,75, 77,64, 34,57, 34,54, 32,72, 32,64, 22,34, 22,14.

³¹P NMR (CDCl₃) δ: 87,49.

Plate made from a mixture of 3% of the product in 97% of polystyrene, had LOI, equal to 23%, and the value of the FP-7, equal to 3.5 C. Polystyrene foam, obtained from the same mixture, demonstrates LOI equal to 23.3%, and the value of the FP-7, 5.3 C.

Example 5

A mixture of N,N-diethylethanamine, 5,5-dimethyl-1,3,2-dioxaphosphinan-2-tilt-2-oxide (6.2 g, 22 mmol) and o-celldepleted (1,94 g, 11 mmol) was dispersible in 50 ml of ethanol and boiled under reflux for 5 hours. The reaction mixture was cooled and concentrated under reduced pressure. The obtained residue was dissolved in methylene chloride (100 ml), washed with water (40 ml), dried and concentrated, gaining 3.6 g (70%) of white solid, 2,2'-[1,2-phenylenebis(methylthio)]bis[5,5-dimethyl-1,3,2-dioxaphosphinan]-2,2'-dioxide having the structure:

The 5% WLT for this material is 247°C. Plates are made from a mixture of 2.5% of the product in 97.5% of polystyrene, had LOI equal to 21.5 percent, and the value of the FP-7, equal to 11.4 C.

Example 6

Salt of o,O-diethyldithiophosphate ammonium (14,13 g, 69,50 mmol) was weighed in chemical beaker and then was dissolved in ethanol (130 ml). Then the beaker was placed in a hot water bath (80°C) and included mixing. When content with the akan reached 80°C, portions were added α,α'-dichloro-about-xylene (5.53 g, 31,59 mmol). The reaction was stirred at 80°C for 3 hours, after which the reaction beaker was accumulated precipitated ammonium chloride. The contents of the beaker were poured into a separate funnel and was added deionized water to dissolve the ammonium chloride. For the extraction of the product, S,S'-(1,2-phenylenedimethylene)-O,O',O'-tetraethylorthosilicate, from water-ethanol phase was used methylene chloride (3 times). The separated organic phase was dried over anhydrous MgS₄. Methylene chloride was filtered from MgS₄and evaporated in a rotary evaporator leaving an oil. The oil is then placed in a vacuum for several hours to remove the remaining ethanol. After standing oil for several days in the flask was formed crystals S,S'-(1,2-phenylenedimethylene)-O,O',O'-tetraethylorthosilicate. These crystals were separated; it was found that they had a melting point of at 33-34,5°C. the Product had a 5% WLT at 225°C. the Idealized reaction scheme is as follows:

Example 7

To a stirred solution of 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (9,70 g, 48 mmol) in toluene (110 ml) was added triethylamine (4,80 g, 48 mmol). The mixture was heated to 45°C. To the mixture was added 1,2,4,6-Tetra(methyl bromide)benzene (5.0 g, 11 mmol) and the mixture was naked evali boiling under reflux for 14 hours. Then the toluene solution was filtered and the precipitate was dispersively in a saturated aqueous solution of sodium bicarbonate (100 ml). The precipitate was filtered and dried, obtaining white solid, 2,2',2",2'"-[1,2,4,6-fineliner(methylthio)]Tetra[5,5-dimethyl-1,3,2-dioxaphosphinan]-2,2',2",2"'-sulfide. Yield 9.4 g (93%). Product structure is as follows:

The 5% WLT for this material is 281°C. Plates are made from a mixture of 2.8% of the product in 97,2% polystyrene, had LOI equal to 24.3 per cent, and the value of the FP-7 5.6 C.

Example 8

To a stirred solution of 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (8,19 g, 41 mmol) in toluene (110 ml) was added triethylamine (4,2 g, 41 mmol). The mixture was heated to 45°C. To the mixture was added 1,3,5-Tris(methyl bromide)-2,4,6-trimethylbenzene (5.0 g, 13 mmol) and the mixture was heated at the boil under reflux for 14 hours. Then the solution was diluted with methylene chloride (150 ml), washed with saturated aqueous sodium bicarbonate (100 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure, obtaining a white solid. The crude product is recrystallized from acetonitrile, receiving 8.0 g (85%) of a white solid substance, 2,2',2"-[2,4,6-trimethyl-1,3,5-finelines(methylthio)]Tris[5,5-dimethyl-1,3,2-dioxaphosphinan]-2,2',2"-disulfide. Product of the t has the following structure:

The 5% WLT for this material is 283°C. Plates are made from a mixture of 3.1% of product in 96.9% of the polystyrene had a LOI equal to 24.2%, and the value of the FP-7, equal to 2.8 C. Polystyrene foam (density of 2.54 pcf, ~40 kg/m³), obtained from the same mixture, showed LOI, equal to 27%, and the value of the FP-7, equal to 1.1 C.

Example 9

Epoxy Novolac resin with a declared M_nequal to 570, containing approximately 3.6 epoxy units per molecule, (10.4 g) was dissolved in 50 ml of toluene under stirring. To this solution was added 11.2 g of 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphinan-2-sulfide, together with an additional 40 ml of toluene. The mixture was stirred in nitrogen atmosphere. After 30 minutes, was added 50 ml of methylene chloride with the formation of a homogeneous mixture. After stirring for 18 hours at room temperature the product was obtained by precipitation in 600 ml of hexane. The product was dried overnight in a vacuum drying Cabinet at 70°C. the Idealized reaction scheme is as follows:

5% WLT for this material is 239°C.

Example 10

Unsaturated complex polyester was obtained from cyclohexanedimethanol (a mixture of 1,4 - and 1,3-isomers, 50/50), diethylmaleate and isophthalic acid. The molar ratio of maleate/isophthalate was 48:52, srednemirov the molecular weight unsaturated complex polyester (according to gel chromatography, relative to polystyrene) was equal 2620, and its glass transition temperature (T_g) was 20°C. the Unsaturated complex polyester (30.0 g) and anhydrous pyridine (4 ml) was dissolved in 100 ml of methylene chloride and to the solution was added terephthaloylchloride (4.5 g). After stirring under nitrogen atmosphere for 1 hour was added methanol (5 ml). The polymer solution was washed with 100 ml of 1.0 n HCl and the product was isolated by precipitation in methanol (1 l). The product was dried overnight in a vacuum drying Cabinet at 50°C. the Obtained unsaturated complex polyester (15.0 g) and 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphinan-2-sulfide (8.0 g, 40 mmol) was dissolved in 20 ml of 1,2-dichloroethane and the solution was boiled under reflux for 19 hours. The solution was diluted by adding 75 ml of 1,2-dichloroethane and the product was isolated by precipitation in 500 ml of methanol. The product was dried overnight in a vacuum drying Cabinet at 50°C. the mass-average molecular weight of the product was $ 5620. It T_gwas 50°C. Is 5% WLT of this product amounted to 276°C. the Idealized structure of the repeating units of this polymer is as follows:

Plate made from a mixture of 19% of the product in 81% of polystyrene, had LOI equal to 24.3 per cent, and the value of the FP-7, equal to 1.3.

Example 11

In a 500-ml three-neck round bottom flask equipped with a stirrer, a reverse cold what linecom, the supply of nitrogen and addition funnel, was added 38,18 g (of € 0.195 mol) of 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphinan-2-sulfide and 60 ml of toluene, forming a white suspension. Then the flask was heated to 85°C, forming a solution. Then the hot solution is added dropwise within 40 minutes was added styrene-butadiene-styrene (SBS) triblock copolymer (10 g, 0,097 mol)dissolved in 80 ml of toluene at room temperature. SBS copolymer used in this example contained a Central polybutadiene block having an average of 53-unit link, of which approximately 22% of 1,4-butadiene units and 78% were 1,2-butadiene units. On average, polystyrene end blocks were long 23-24 unit link. Then the reaction was stirred under nitrogen atmosphere for 68 hours at 85°C. After the reaction solution was cooled, diluted with 200 ml of toluene and washed twice in water CON and once with water. Then the polymer solution was besieged in methanol and was dried for 5 hours in a vacuum drying Cabinet at 40°C. the Polymer was re-dissolved in 200 ml of toluene, washed twice with water, dried over MgS₄the second time was besieged in 2 l of methanol and dried overnight in a vacuum drying Cabinet at 40°C. was Collected 19,36 g of white powder of the polymer (yield 67,12%). The idealized reaction scheme is as follows:

FR the config NMR in CDCl ₃showed that 5% of the aliphatic double bonds of the original polymer has not responded. Analysis by gel chromatography in THF versus polystyrene standards showed that there was a binding of a small amount of polymer, because the product has M_nequal 128560, and M_wequal 147330.

The 5% WLT of this product was 242°C. Plates are made from a mixture of 3.6% 96.4% polystyrene, had LOI equal to 24.2%, and the value of the FP-7, equal to 4.2 C.

Example 12

Phosphorus-sulfur group was introduced in SB diblock copolymer by a method similar to that described in Example 11. In a 500-ml three-neck round-bottom flask equipped with stirrer, reflux condenser with a flow of nitrogen and addition funnel, was added 27,85 g (0.14 mol) of 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphinan-2-sulfide and 45 ml of toluene (white suspension). The reaction mixture was immersed in an oil bath set at 85°C, and 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphinan-2-sulfide was dissolved in toluene. Then the hot solution was added dropwise over 35 minutes styrene-butadiene diblock copolymer (10 g polymer, 0.07 mol polybutadiene block), dissolved in 80 ml of toluene at room temperature. The reaction was allowed to warm and the mixture was stirred in nitrogen atmosphere for 70 hours. The reaction solution was cooled, Rabaul what if 200 ml of toluene and washed twice in water CON and once with water. The polymer was besieged in 2 l of methanol and dried overnight in vacuum at 70°C. the Polymer was re-dissolved in 250 ml of toluene, dried over MgS₄, was filtered, was besieged in 2 l of methanol and dried overnight in a vacuum drying Cabinet at 70°C. was Collected 18,13 g of white powder of the polymer (yield 76%).

SB diblock copolymer of this example has a polybutadiene block with an average length of 38 Monomeric units. About 29% of the butadiene units are 1,4-units. The polystyrene block has a length of approximately 62 units. The product presents idealized structure, which does not reflect the 1,2 - and 1,4-butadiene in the product:

Temperature 5% WLT for this product is 260°C. the Plates are made from a mixture of 8.4% of product in 91.6% of polystyrene, had LOI equal to 25%, and the value of the FP-7, equal to 1.3 C.

Example 13

In a 500-ml three-neck round-bottom flask equipped with stirrer, reflux condenser with a flow of nitrogen and addition funnel, was added received 19.82 g (0.10 mol) of 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphinan-2-sulfide and 45 ml of toluene with the formation of a white suspension. To this suspension was added triethylamine (10,12 g, 0.10 mol) and the suspension was heated to 45°C. to form a solution. Then the hot solution was added dropwise poly(vinylbenzoate) (15 g, 0,098 mol)dissolved in 80 ml of toluene at room is temperature. After completion of the addition polymer, the reaction mixture was heated at the boil under reflux for 100 minutes. The reaction solution was cooled, diluted with 100 ml of chloroform and washed four times with 300 ml of water. Then the polymer solution was dried over MgS₄was filtered , concentrated and precipitated in 2 l of methanol. The obtained white powder polymer was collected by filtration and dried overnight in a vacuum drying Cabinet at 70°C, getting to 27.2 g of the product. The idealized reaction scheme is as follows:

The product had M_nequal 51859, M_wequal 120880, and PDI equal 2,33, measured by means of gel chromatography in THF against polystyrene standards. The 5% WLT was 292°C. the Plates are made from a mixture of 3.8% product 96,2% polystyrene, had LOI, equal to 22%, and the value of the FP-7, equal to 3.8.

Example 14

In a 500-ml three-neck round-bottom flask equipped with stirrer, reflux condenser with a flow of nitrogen and addition funnel, was added 41,82 g (0.21 mol) of 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphinan-2-sulfide and 60 ml of toluene with the formation of a white suspension. The suspension was heated to 85°C. to form a solution. Then the hot solution was added dropwise within 40 minutes styrene-butadiene-styrene (SBS) triblock copolymer (10 g, 0,105 mol), dissolve the built in 80 ml of toluene at room temperature. 10% of the butadiene units of this polymer were 1,2-butadiene units, and 90% were 1,4-butadiene units. The reaction mixture was stirred in nitrogen atmosphere for 71 hours at 85°C. Then the reaction solution was cooled, diluted with 400 ml of toluene and washed twice in water CON and once with water. Thereafter, the polymer solution was dried over MgS₄besieged in 2 l of methanol and dried overnight in a vacuum drying Cabinet at 40°C. the Polymer product (23 g) was dissolved in 1 l of tetrahydrofuran (THF), receiving a turbid white solution, which was filtered through a 0,45 µm filter HVHP air pressure 10-20 psi (0.7 to 1.4 bar). Clean filtrate polymer was besieged for the second time in 2 l of methanol. White polymer product was collected by filtration and dried overnight in a vacuum drying Cabinet at 40°C. was Collected to 13.4 g of white powder of the polymer (yield of 43.5%). The idealized reaction scheme is as follows:

Proton NMR in CDCl₃showed that 11.7% of the aliphatic carbon-carbon double bonds in the original polymer remained unreacted. Analysis by gel chromatography in THF against polystyrene standards showed that there was a binding of a small amount of polymer. The product had M_nequal 124860, M_wequal 137030, and a polydispersity equal to 1,097 Is 5% WLT for this product amounted to 244°C. Plate made from a mixture of 3.6% 96.4% polystyrene, had LOI equal to 22.3%, and the value of the FP-7, equal to 4.2 C.

Example 15

In a 250 ml three-neck round-bottom flask equipped with stirrer, reflux condenser with a flow of nitrogen and addition funnel, was added at 8.36 g (0,042 mol) of 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphinan-2-sulfide, 3 g of styrene-butadiene-styrene (SBS) triblock-copolymer (0,021 mol polybutadiene block) and 40 ml of toluene with the formation of a white suspension. The reaction mixture was immersed in an oil bath set at 110°C, and all solids were dissolved in toluene. The reaction mixture was allowed to warm up and then it was stirred in nitrogen atmosphere for 69 hours. The reaction solution was cooled to 40°C. and diluted with 50 ml of toluene. Directly in the crude solution was added triethylamine (2,98 ml 0,021 mol) and the reaction was allowed to mix in the atmosphere of nitrogen at 40°C for 1 hour, during which the formed precipitate. The crude mixture was passed through a layer of silica and the filtrate polymer was concentrated in a rotary evaporator. Then the polymer solution was besieged in 1 l of methanol and dried overnight in vacuum at 70°C. was Collected 5,78 g of white powder of the polymer (yield 80.5 per cent).

The idealized reaction scheme is as follows:

The 5% WLT for this material was 248°C. Plates are made from a mixture of 7.8% of the product in 92.2% of polystyrene, had LOI equal to 24.5%, and the value of the FP-7 0.9, C.

Example 16

To mix the solution by triethylammonium salt of 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (18,77 g, 63 mmol) in 150 ml of pyridine was added trichlorotriazine (3.50 g, 18 mmol). The mixture was heated to 105°C for 2 hours. The obtained dark-yellow solution was diluted with methylene chloride (300 ml), washed with water (1 l), dilute HCl solution (1 M, 250 ml) and saturated aqueous sodium bicarbonate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, obtaining a light yellow solid. The crude material was first purified, dispersive in warm acetonitrile and cooling in an ice bath, followed by filtration, obtaining a pale yellow solid. Recrystallization from methanol gave of 3.96 g (yield 33%) of white product, Tris[2-mutilatio-(5,5-dimethyl-1,3,2-dioxaphosphinan-2-thioxo)phosphine oxide, which is represented by the structure:

The 5% WLT product was 243°C. Plates are made from a mixture of 2.7% 97.3% polystyrene, had LOI, equal to 22.8%, and the value of the FP-7, equal to 4.4 C.

Example 17

A mixture of cyanuric chloride (1.84 g, 10 the mole) and ammonium salt of 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (7,10 g, 33 mmol) in 75 ml of acetonitrile was heated under reflux for 4 hours. The reaction mixture was cooled and concentrated under reduced pressure. The obtained solid substance was diluted in 150 ml of methylene chloride and washed with aqueous saturated sodium bicarbonate solution (100 ml). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, obtaining a yellow solid. This material was purified by dissolving in methylene chloride (100 ml), filtering through silica gel and then removing the solvent under reduced pressure, getting 4,60 g (67%) of white solid, 2,2',2"-[s-triazine-2,4,6-Tris(thio)]Tris[(5,5-dimethyl-1,3,2-dioxaphosphinan)-2,2',2"-sulfide], having the structure:

The 5% WLT product was 249°C. Plates are made from a mixture of 2.7% 97.3% polystyrene, had LOI, equal to 23.8%, and the value of the FP-7 is 4 C.

Example 18

Sulfur (3,52 g, 110 mmol) was added in portions to a solution of N-benzyl-N-5,5-dimethyl-1,3,2-dioxaphosphinan-2-yl)-5,5-dimethyl-1,3,2-dioxaphosphinan-2-amine (10.2 g, 27 mmol) and the mixture was allowed to mix overnight. The reaction mixture was concentrated under reduced pressure. The residue was dispersible in chloroform (100 ml), filtered and the filtrate was stored in a freezer over night. The cold reaction mixture is again f is literaly and the filtrate was concentrated, getting a white solid. Recrystallization of this solid in ethanol gave to 4.81 g (40%) of a white solid, N-benzyl-N-(5,5-dimethyl-2-sulphido-1,3,2-dioxaphosphinan-2-yl)-5,5-dimethyl-1,3,2-dioxaphosphinan-2-amine-2-sulfide having the structure:

The 5% WLT for this material was 202°C. Plates are made from a mixture of 4.8% of the product in 95.2 percent of polystyrene, had LOI equal to 23, and the value of the FP-7, equal to 1.1 C.

Example 19

A mixture of neopentyl glycol (13.8 g, 132 mmol) andabout-xmliterator (24,7 g, 66 mmol) was dispersible in chlorobenzene (250 ml)containing pyridine (1 ml), and heated to 115°C for 10 hours. An aliquot was examined by³¹P NMR and found that the mixture still contained the original materials. The reaction mixture was heated and stirred in the next 15 hours. The reaction mixture was concentrated under reduced pressure, getting sticky solid brown color. This solid was dissolved in 120 ml of a mixture of ethyl acetate hexane (1:1) and was chromatographically on silica gel, receiving a yellowish-brown solid (20.5 g). This solid was washed with a mixture of ethyl acetate hexane (1:3, 50 ml)to give 7 g of a light grey solid. Other 2 g of material was obtained by concentrating the filtrate and washing the material with a mixture atilas the Tata with hexane. The combined output was 32% [1,2-phenylenebis(methylene)]bis[5,5-dimethyl[1,3,2]dioxaphosphinan]2,2'-disulfide having the structure:

The 5% WLT for this material amounted to 284°C. Plates are made from a mixture of 5.1% of the product in 94.9% of polystyrene, had LOI, equal to 22.8%, and the value of the FP-7, equal to 1.2 C.

Example 20

A mixture of 1,4-dibromobutane (2,42 g, 11 mmol) and ammonium salt of 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (6.50 g, 30 mmol) in 50 ml of ethanol was boiled under reflux for 4 hours. Then the reaction mixture was cooled, diluted with 100 ml of chloroform and washed with aqueous saturated sodium bicarbonate solution (100 ml). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, getting 4.71 g (93%) of white solid, 2,2'-[1,4-Rutilus(methylthio)]bis[5,5-dimethyl-1,3,2-dioxaphosphinan]-2,2'-disulfide. The product has the following structure:

The 5% WLT for this material was 244°C. Plates are made from a mixture of 2.9% of the product in 97.1% of polystyrene, had LOI equal to 22.6, and the value of the FP-7, equal to 7.1 C.

Example 21

Bicyclo[2,2,1]2,5-heptadien (0,92 g, 10 mmol) was added to a stirred solution of 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (4.0 g, 20 mmol) in 40 ml of toluene. The result of this was copy thermal reaction, povysheva the temperature of the reaction mixture to 56°C with the formation of a white precipitate. The reaction mixture was additionally heated to 70°C. for one hour and then it was allowed to cool to room temperature. Filtration of this mixture gave 4.5 g of the product, 2,2'-[bicyclo[2,2,1]heptane-2,5-diylbis(thio)]bis[5,5-dimethyl-1,3,2-dioxaphosphinan]-2,2'-disulfide. Using LC/MS of this compound was characterized as bis-adduct having the structure:

The 5% WLT for this material was 264°C. Plates are made from a mixture of 3% of the product in 97% of polystyrene, had LOI, equal to 23%, and the value of the FP-7, equal to 3.9 C.

Example 22

A mixture of triacrylate pentaerythritol and tetraacrylate pentaerythritol having an average acrylate functionality, equal to 3.4, and an equivalent weight equal to 89,34 g/equivalent, was added together with 100 ml of methylene chloride in a 500-ml odnogolosy round-bottom flask equipped with a magnetic stirrer and a flow of nitrogen. Added 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (10,96 g, by 0.055 mol) and the resulting homogeneous solution was allowed to mix within 48 hours. Addition was added 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (1.0 g, of 0.005 mol) and the mixture was allowed to mix within the next 48 hours. At this point, the NMR analysis showed that reacted 93% acre is atnah groups. The solvent was removed from the reaction mixture in a rotary evaporator heated to 80°C. the Remaining material was placed in a vacuum drying oven for ~16 hours at 80°C. was Obtained of 13.6 g (output selected substances were 85%) transparent, colorless, like water, the vitreous material. The idealized reaction scheme (with the formation of four-membered adduct) is represented as follows:

The 5% WLT for this material was 274°C. Plates are made from a mixture of 3.5% of the product in 96.5% of polystyrene, had LOI equal to 23.3%, and the value of the FP-7, equal to 3.5 C.

Example 23

In a 250 ml three-neck round bottom flask was added diethylmaleate (0.1 mol, and 17.2 g). Under stirring was added 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (0.1 mol, of 19.8 g) and the resulting mixture was heated for 2 hours at 100°C. the Idealized reaction scheme is as follows:

The 5% WLT for this product was 218°C. Plates are made from a mixture of 4,6% of the product in 95.4% of polystyrene, had LOI equal to 23.2%, and the value of the FP-7, equal to 0.2 c.

Example 24

Mix a solution of 1,9-decadiene (5.0 g, 36,1 mmol) and 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (14,33 g of 72.3 mmol) in toluene (75 ml) was heated to 80°C for 6 hours.³¹P-NMR analysis of an aliquot showed prisutstvie the original thiol, as well as mono - and bis-adducts. The mixture was concentrated to half its volume and heated in the next 6 hours at 80°C. the Mixture was diluted with methylene chloride, was extracted with aqueous saturated sodium bicarbonate, dried over anhydrous magnesium sulfate and concentrated under reduced pressure, obtaining oil, which slowly hardened, giving 18.5 g (96%) 2,2'-[Dean-2,9-diylbis(thio)]bis(5,5-dimethyl-1,3,2-dioxaphosphinan)-2,2'-disulfide. The product had the following structure:

The 5% WLT for this product amounted to 239°C. Plates are made from a mixture of 6.3% of product in 93.7% of polystyrene, had LOI equal to 24.3 per cent, and the value of the FP-7, equal to 2.6 c.

Example 25

5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (8.0 g, is 40.4 mmol) was dissolved in toluene (100 ml). Was added triethylamine (3.8 g, is 40.4 mmol) and the mixture was allowed to mix for 10 minutes. Then added bromodiphenylmethane (10.5 g, 42,4 mmol) and the reaction mixture was heated up to 80°C for 2 hours. HPLC analysis of an aliquot showed that most of the original bromide compounds recycled. The reaction mixture was diluted with methylene chloride (100 ml) and washed with aqueous saturated sodium bicarbonate solution (100 ml). The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, obtaining a white solid prophetic the STV. The crude material was recrystallized from toluene. The yield of 2-[(diphenylmethyl)thio]-5,5-dimethyl-1,3,2-dioxaphosphinan-2-sulfide was 13.2 g (95%). This compound had the following structure:

The 5% WLT for this product was 238°C. Plates are made from a mixture of 8.3% 91,7% polystyrene, had LOI, equal to 26%, and the value of the FP-7 is equal to 0.4 c.

Example 26

N,N-Diethylethanamine-6H-dibenz[c,e][1,2]oxaphosphorin-6-mercapto-6-oxide (8.0 g, is 22.9 mmol) was dissolved in methylene chloride (75 ml)containing 1,4-dibromo-2-ene (2,45 g, 11.5 mmol)and the resulting mixture is boiled under reflux. After 3 hours boiling under reflux, most of the source material was recycled. The reaction mixture was washed with saturated aqueous sodium bicarbonate solution (100 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure, obtaining 4.6 g(73%) 6,6'-[(2E)-but-2-EN-1,4-diylbis(thio)]bis(6Hdibenz[c,e][1,2]oxaphosphorin-6,6'-dioxide as a white solid with the following structure:

The 5% WLT for this product was 270°C. the Plates are made from a mixture of 6.4% of the product in 93.6% of polystyrene, had LOI equal to 24.8 per cent, and the value of the FP-7 1 c.

Example 27

To a stirred solution of 1,4-bis[Dimity is[2-(5-norbornene-2-yl)ethyl]silyl]benzene (5.0 g, 11.5 mmol) in 40 ml of toluene was added 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (4,56 g, 23 mmol). The mixture was heated up to 80°C for 6 hours. Then a transparent reaction mixture was washed with an aqueous solution of sodium bicarbonate (100 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure, obtaining oil, which slowly hardened, turning into a white solid (9.2 grams, 96%). The structure of the product, 2,2'-{1,4-phenylenebis[(dimethylsilane)ethane-2,1-delbello[2,2,1]heptane-6,2-dirty]}bis(5,5-dimethyl-1,3,2-dioxaphosphinan)-2,2'-disulfide, was as follows:

The 5% WLT for this product was 285°C. the Plates are made from a mixture of 4.9% of the product in 95.1% of polystyrene, had LOI, 21.7%, and the value of the FP-7, equal to 4.4 c.

Example 28

To a stirred solution of 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (of 2.06 g, 10 mmol) in toluene (40 ml) was added triethylamine (0.10 g, 10 mmol). The mixture was heated to 45°C. and was added 5,5-dimethyl-2[(4-chloromethylene)methyl]-1,3,2-dioxaphospholane-2-oxide (3.00 g, 10 mmol). Then the mixture was heated to 90°C for 4 hours. The solution was washed with saturated aqueous sodium bicarbonate solution (50 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure, obtaining white solid, 4.3 g (92%). The product, 2-({4-[(5,5-dimethyl-2-oxido-1,3,2-di is capastrano-2-yl)methyl]benzyl}thio)-5,5-dimethyl-1,3,2-dioxaphosphinan-2-sulfide, had the following structure:

The 5% WLT for this material was 257°C. Plates are made from a mixture of 4.8% of the product in 95.2 percent of polystyrene, had LOI, 21.7%, and the value of the FP-7, equal to 2.9 C.

Example 29

To a stirred suspension of 6N-dibenz[c,e][1,2]oxaphosphorin-6-oxide (10 g, and 46.3 mmol) in 100 ml of toluene was added drop wise addition of triethylamine (4.68 g, and 46.3 mmol). Then in small portions was added sulfur (1.48 g, and 46.3 mmol). The reaction mixture was allowed to mix at 45°C for 1 hour. To the reaction mixture was added o-celldepleted (of 4.05 g of 23.1 mmol) and then the reaction mixture was heated to 90°C for 5 hours. The reaction mixture was cooled and concentrated under reduced pressure and the residue was diluted with methylene chloride (120 ml). Methylenchloride the solution was washed with an aqueous solution of sodium bicarbonate (1×100 ml), dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, obtaining a white solid. The product was further purified by filtering through silica gel with methylene chloride and ethyl acetate (8:2) as eluent, getting 8,2 g(59%) 6,6'-[1,2-phenylenebis(mutilatio)]bis(6N-dibenz[c,e][1,2]oxaphosphorin)-6,6'-dioxide, in the form of a white solid with the following structure:

The 5% WLT for this m the material was 262°C. Plate made from a mixture of 7% of the product in 93% of polystyrene, had LOI equal 24,8, and the value of the FP-7, equal to 3.2 C.

Example 30

To a stirred suspension of 6N-dibenz[c,e][1,2]oxaphosphorin-6-oxide (10 g, and 46.3 mmol) in 100 ml of toluene was added drop wise addition of triethylamine (4.68 g, and 46.3 mmol), then in small portions was added sulfur (1.48 g, and 46.3 mmol). The reaction mixture was allowed to mix at 45°C for 1 hour. To the reaction mixture was added 1,3,5-Tris(methyl bromide)-2,4,6-trimethylbenzene (6,09 g of 15.3 mmol), after which the mixture was heated to 90°C for 5 hours. The reaction mixture was cooled and then concentrated under reduced pressure and the residue was diluted with methylene chloride (120 ml). Methylenchloride the solution was washed with an aqueous solution of sodium bicarbonate (100 ml), dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure, obtaining of 13.1 g (95%) product, 6,6',6"-[(2,4,6-trimethylbenzene-1,3,5-triyl)Tris(mutilatio)]Tris(6N-dibenzo-[c,e] [1,2]oxaphosphorin)-6,6',6"-trioxide, in the form of a light grey solid. Assume the following structure:

The 5% WLT for this material was 219°C. Plates are made from a mixture of 6.2% of the product in 93.8% of polystyrene, had LOI equal to 24.8 per cent, and the value of the FP-7 0.1 C.

Example 31

Tetraethylenepentaamine (6,03 g, 20.3 mm is l) (obtained by the method according Nougier, R. M. and Mchich J.,Org. Chem.1985, 50, 3296-3298. "Alkylation of Pentaerythritol and Trimethylolpropane, Two Very Hydrophilic Polyols, by Phase-Transfer Catalysis" - "Alkylation of pentaerythritol and trimethylolpropane, two very hydrophilic polyols by phase transfer catalysis") and 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (of 19.91 g, 100,6 mmol) was added in a 250 ml round bottom flask under nitrogen atmosphere. The reaction mixture was heated for 48 hours, after which NMR analysis showed complete conversion of the allyl groups of the starting material. The product was dissolved in a mixture of 50 ml of methylene chloride and 50 ml of ether and was extracted successively with 50 ml of saturated NaHCO₃, dithionites (25 ml, 10% aq.) and 20 ml of NaHCO₃. After each extraction the resulting emulsion was destroyed by addition of 20 ml of a saturated solution of NaCl in each extraction. The aqueous layer was decantation and the organic phase was dried over anhydrous MgS₄. Then the solution was filtered through a layer of silicon dioxide (3,1 × 7.5 cm) and washed with 50 ml of methylene chloride. Evaporation in a rotary evaporator and drying in vacuum gave 22 g of the crude product as a clear oil.¹H and³¹P NMR characterized the product as a mixture of diastereomers. The reaction can be schematically represented as follows:

The 5% WLT for this product was 241°C. Plates are made from a mixture of 4,6% of the product is 95.4 percent polystyrene, had LOI, equal to 23.5%, and the value of the FP-7, equal to 2.0 C.

Example 32

In a 500-ml three-neck round-bottom flask equipped with stirrer, reflux condenser with a flow of nitrogen and addition funnel, was added 76,96 g (0,388 mol) of 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphinan-2-sulfide, 7 g (0,129 mol) of polybutadiene homopolymer dissolved in 60 ml of toluene and 140 ml of toluene. Polybutadiene polymer contained 20% of 1,4-butadiene units and 80% of 1,2-butadiene units. The reaction mixture was immersed in an oil bath set at 85°C, and all solids were dissolved in toluene. The reaction mixture was allowed to warm up and mixed in a nitrogen atmosphere for 75 hours. Then the reaction solution was cooled to 40°C. the crude solution was added triethylamine (37,35 ml, 0,268 mol) and then the reaction mixture was allowed to mix in the atmosphere of nitrogen at 40°C for 1 hour. Formed a white precipitate. The toluene was removed from the crude mixture in a rotary evaporator. THF (200 ml) was added directly to the white sticky solid substance and the mixture was allowed to mix at room temperature over night. White solid was filtered from solution of THF and the filtrate was besieged in 5 l of methanol. A white precipitate of polymer was dried overnight in vacuum at 70°C, re-dissolved in 100 ml of THF and re-wasp is given in 2 l of methanol. The polymer was collected by filtration and dried overnight in a vacuum oven at 65°C. was Collected 26,85 g of white powder of the polymer (yield 82%).

¹H NMR in CDCl₃showed that 8.8% of the original carbon-carbon double bonds remained unreacted: δ 5,46 (vinyl), 5,18 (vinyl), 4,25 (2H, neopentyl), of 3.97 (2H, neopentyl), 3,76 (1H), 3,50 (1H), 1,78 (-CH₂- main circuit)and 1.51 (-CH₂- the main circuit), 1,25 (3H, -CH₃), of 0.97 (3H, -CH₃).³¹P NMR (CDCl₃):, 90,95 ppm

The idealized reaction scheme is as follows:

The 5% WLT for this product was 252°C. Plates are made from a mixture of 4,6% of the product in 95.4% of polystyrene, had LOI, equal to 23%, and the value of the FP-7, equal to 2.3 C.

Example 33

To mix the solution hexacis(methyl bromide)benzene (2.0 g, 3.2 mmol) and 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (3,9 g of 19.8 mmol) in toluene (100 ml) was added triethylamine (2.0 g, to 19.8 mmol). The mixture was heated at the boil under reflux for 6 hours and then cooled and filtered. The precipitate was dissolved in methylene chloride (100 ml) and washed with saturated aqueous sodium bicarbonate (2×100 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure, obtaining 2,2',2",2'",2"",2'""-[benzene-1,2,3,4,5,6-hexalectris(mutilatio)]hexacis(5,5-dim the Teal-1,3,2-dioxaphosphinan)-2,2',2",2'",2"",2"'"-execulive in the form of a white solid substances (4,2 g, 99%). Assume the following structure of product:

The 5% WLT for this material amounted to 262°C. Plates are made from a mixture of 5.3% of the product in 94.7% of polystyrene, had LOI equal to 24.3 per cent, and the value of the FP-7, equal to 1.4 C.

Example 34

Unsaturated complex polyester was obtained from cyclohexanedimethanol (a mixture of 1,4 - and 1,3-isomers, 50/50) and dimethylfumarate. The mass-average molecular weight unsaturated complex polyester (according to gel chromatography relative to polystyrene) was $ 16400, and its glass transition temperature (T_g) was 16°C. the Unsaturated complex polyester (10.0 g) and anhydrous pyridine (2 ml) was dissolved in 30 ml of methylene chloride and to the solution was added acetic anhydride (3.0 g). After stirring under nitrogen atmosphere for 24 hours, the polymer solution was washed with 30 ml water and the product was isolated by precipitation in methanol (250 ml). The product was dried for 5 hours in a vacuum drying Cabinet at 70°C. the Obtained unsaturated complex polyester (5.0 g) and 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphinan-2-sulfide (4.4 g, 22 mmol) was dissolved in 10 ml of 1,2-dichloroethane and the solution was boiled under reflux for 23 hours. The solution was diluted by adding 70 ml of 1,2-dichloroethane, and the solution was washed with 30 ml of water containing 1.0 g of sodium bicarbonate. The product was isolated by precipitation in 500 ml of methanol. Prod the CT was dried overnight in a vacuum drying Cabinet at 50°C. The mass-average molecular weight of the product was equal to 8800. It T_gwas 45°C. Is 5% WLT for this product amounted to 271°C. the Idealized structure of the repeating units of this polymer is as follows:

Plate made from a mixture of 10% in 90% of polystyrene, had LOI equal to 25.0%, and the value of the FP-7, equal to 0.6 C.

Example 35

Allyl simple ester m-crisologo of novolak obtained fromm-crisologo of novolak (mass-average molecular weight of 1,600) and allylbromide.m-Crazyby novolak (9.80 g) was dissolved in 70 ml of N,N-dimethylformamide (DMF) and to the solution was added sodium hydride (2.5 g) for 30 minutes. Then to this mixture was added (within 30 minutes) allylbromide (14.9 g). After stirring under nitrogen atmosphere overnight, the reaction mixture was filtered, diluted with 70 ml of toluene and washed with 70 ml of water. The resulting polymer solution was concentrated and dried overnight in a vacuum drying Cabinet at 60°C, receiving 13,0 g allyl simple etherm-crisologo of novolak with mass-average molecular weight equal to 1650. Allyl simple broadcastm-crisologo of novolak (8.0 g) and 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphinan-2-sulfide (14.8 g, 75 mmol) was dissolved in 10 ml of toluene and heated for 18 hours at 100°C. the resulting mixture is abbasli in 70 ml of toluene and then washed with 50 ml water, containing 4 g of sodium bicarbonate. The product was isolated, viparita toluene, and was further dried overnight in a vacuum drying Cabinet at 70°C. the mass-average molecular weight of the product was $ 3100. It T_gwas 450°C. Is 5% WLT for this product amounted to 277°C. the Idealized structure of the repeating units of the polymer are as follows:

Plate made from a mixture of 9.4% of product in 90.6% of polystyrene, had LOI equal to 24.8 per cent, and the value of the FP-7, equal to 0.2 C.

Example 36

N,N'-methylenebisacrylamide (7.0 g, 0.045 mol) in 70 ml of tetrahydrofuran (THF) were added in a 250 ml three-neck round bottom flask, equipped with magnetic stirrer with flow of nitrogen. Added 5,5-dimethyl-2-thioxo-[1,3,2]dioxaphosphinan-2-thiol (18.0 g, 0,091 mol) and the mixture was allowed to mix for 24 hours. The product was isolated, viparita THF and then precrystallization of 300 ml of toluene. The resulting product was a white crystalline solid with melting point at 65°C. the Idealized structure has the following form:

The 5% WLT for this material was 220°C. the Plates are made from a mixture of 6.9% of the product in 93.1% of polystyrene, had LOI equal to 24.5%, and the value of the FP-7, equal to 0.8 C.

Example 37

Triethyl is min (2,02 g, 20 mmol) was added to a stirred solution of 1,3-bis(CHLOROTHALONIL)benzene (3,27 g, 10 mmol) and 5,5-dimethyl-1,3,2-dioxaphosphinan-2-thiol (of 3.96 g, 20 mmol) in toluene (70 ml). The mixture was heated at the boil under reflux for 3 hours. The reaction mixture was cooled and washed with an aqueous solution of sodium bicarbonate (100 ml), dried and concentrated, obtaining 2,2'-{1,3-phenylenebis[(phenylmethylene)thio]}bis(5,5-dimethyl-1,3,2-dioxaphosphinan)-2,2'-disulfide in the form of a white solid. The product yield was 4.8 g (74%). The product had the following structure:

The 5% WLT for this material was 259°C. Plates are made from a mixture of 8.1% product 91,9% polystyrene, had LOI equal to 25.8%, and the value of the FP-7 1 C.

Example 38

To a suspension 2,4,8,10-tetraoxa-3,9-diphosphatase[5.5]undecane-3,9-disulfide (3 g, 11.5 mmol) in methylene chloride (50 ml) was added triethylamine (2,33 g, 23 mmol), and then portions was added sulfur (0.74 g, 23 mmol). The mixture was allowed to mix for 1 hour at 40°C. was Added bromodiphenylmethane (5.7 g, 23 mmol) and the mixture was heated to 45°C for 4 hours. The reaction mixture was washed with saturated sodium bicarbonate solution, dried over anhydrous MgS₄and concentrated under reduced pressure, getting 5,42 g (72%) of product as a white solid. The product had the trail of the General structure:

The 5% WLT for this material was 240°C. the Plates are made from a mixture of 8.2% of the product in 91.8% of the polystyrene had a LOI equal to 26.7%, and the value of the FP-7, equal to 1.4 c.

1. Phosphorus-sulfur compound represented by any of structures:

or

where X means oxygen, T denotes sulfur, each X' independently denotes oxygen or sulfur, n is the valence of a and equal to at least 2, each R²means hydrogen or lower alkyl, R³means linear or branched hydrocarbon group, and a represents
a) linear or branched alkylen, possibly substituted ester groups, ether groups or amide groups;
b) unsaturated hydrocarbon group;
c) alicyclic group;
d) diphenylmethyl;

where R⁷means hydrogen or a hydrocarbon group and p is equal to 6-n,

where each R⁵means alkyl,
h) an aromatic group associated with the atom T through an atom of the benzyl;
i) a combination of aliphatic, alicyclic and aromatic groups, as in compounds

or (j) the remainder of the organic polymer formed from a polymer with srednevekovoi molecular weight of from 500 to 300,000, defined the group, consisting of homopolymer of a conjugated diene, a copolymer of two or more conjugated dienes, a copolymer of a conjugated diene and styrene, monomer, polymer or copolymer having two ethylene-unsaturated groups, a complex polyester unsaturated aliphatic dibasic acid, dipyridamole simple ester of polyhydric phenol compounds or aliphatic glycols, polyglycerols simple ether of phenol-formaldehyde Novolac resins, phenol-formaldehyde resins, epoxy Novolac resins, phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, Dicyclopentadiene-phenol resins, Dicyclopentadiene-substituted phenol resins, vinyl chloride polymers and copolymers, vinylidene chloride vinylbenzoate, where phosphorus-the sulfur compound contains from 5 to 50 wt.% of sulfur.

2. Phosphoric-sulfuric compound according to claim 1, in which the group a is associated with the atom T via allyl or benzyl carbon atom.

3. Phosphoric-sulfuric compound according to claim 2, which is a 2,2',2",2"'-[1,2,4,6-fineliner(methylthio)]Tetra[5,5-dimethyl-1,3,2-dioxaphosphinan]-2,2',2",2"'-sulfide, 2,2',2"-[2,4,6-trimethyl-1,3,5-finelines(methylthio)]Tris[5,5-dimethyl-1,3,2-dioxaphosphinan]-2,2',2"-disulfide, or 2,2'-{1,3-phenylenebis[(phenylmethylene)thio]}bis(5,5-dimethyl-1,3,2-dioxaphosphinan)-2,2'-disulfide.

4. Phosphorous-sulfur compound is about to claim 1, in which group And mean a polymer of styrene, a polymer of butadiene, a copolymer of styrene and butadiene, the remainder of the epoxy resin, unsaturated residue of a complex of the polyester or the residue of a polymer or copolymer vinylbenzoate.

5. Phosphoric-sulfuric compound according to claim 1, which is 2,2',2"-[s-triazine-2,4,6-Tris(thio)]Tris[(5,5-dimethyl-1,3,2-dioxaphosphinan)-2,2',2"-sulfide].

6. A method of obtaining a polymer foam, comprising the formation of a molten mixture of combustible thermoplastic or thermosetting polymer, at least one blowing means and phosphorus-sulphur compounds according to any one of claims 1 to 5 under pressure, and then extruding the molten mixture through a nozzle into a region of reduced pressure so that the molten mixture expands and cools, forming a foamed polymer.