TW200918590A - Phosphorus-sulfur FR additives and polymer systems containing same - Google Patents

Abstract

Certain phosphorus-sulfur compounds are effective in reducing the LOI of combustible organic polymers and in providing better FR characteristics to the polymers as determined by other standardized tests. The phosphorus-sulfur compounds are sulfur-bridged, metal-bridged or in the form of salts such a ammonium, sulfonium or phosphonium salts.

Description

。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The present invention relates to flame retardant additives for organic polymers and in particular to phosphorus-sulfur flame retardant additives. L Prior Art 3 Background of the Invention 10 Flame retardant additives are typically added to polymer products for use in construction and other applications. Flame retardant additives increase the oxygen limited index (LOI) of polymer systems, allowing articles made from these polymer systems to pass standard fire tests. Various low molecular weight (<~1500 g/mole) brominated compounds are useful as flame retardant additives for organic polymers. Many of these flame retardant additives, such as the six desert cyclopentadecane, are under pressure and are subject to public pressure, thus limiting their use. Accordingly, there are motives to find alternatives to them. Various phosphorus compounds have been used as flame retardant additives. It includes the organophosphates, phosphonates and phosphoniumamines, some of which are described in U.S. Patent Nos. 4,070,336 and 4,086,205. Another commercially available flame retardant additive is 20 2,2'-oxybis[5,5-dimethyl-1,3,2-dioxaphosphane] 2,2'-disulfide, It has the following structure:

These compounds tend to provide general flame retardancy and are therefore generally not as effective as 5,018,590, such as hexazone or other brominated FR additives. Alternative flame retardant additives for organic polymers and especially for foamable polymers are preferred. The flame retardant additive should provide the LOI of the polymer system when incorporated into the polymer at a suitably low level. Likewise, the flame retardant additive should provide good fire extinguishing properties to the polymer system when present in a suitably small amount of 5. In many cases, since the flame retardant additive is preferably added to the melt of the organic polymer, or (or otherwise) is present in subsequent melt processing operations, the temperature of the molten polymer is typically 150. The flame retardant additive should have thermal stability in the range of °C or higher, and usually at a temperature of at least 200 ° C or above 220 ° C. The flame retardant additive preferably has low toxicity. SUMMARY OF THE INVENTION In one aspect, the present invention is a polymer composition comprising a combustible polymer in which a 15 -sulfur additive represented by the following structure I has been mixed:

Wherein each X is independently oxygen or sulfur, each m is independently zero or 1, p is 1 or 2, and each R is independently an unsubstituted or inertly substituted hydrocarbon group or any R^XV-P-PV-R structure R The groups together may form an unsubstituted or inert 20 substituted divalent organic group. In certain embodiments, the invention is also a polymer composition comprising a flammable polymer to which a wall-sulfur additive represented by the following structure 200918590 II has been mixed.

Wherein each X is independently oxygen or sulfur, each m is independently zero or 1, Μ represents a metal atom which may have 5 hydration of bound water, η is a number from 1 to 4, and each R is independently unsubstituted or The inertly substituted hydrocarbyl group or the R group of any R-(X)mP-(X)mR structure together may form an unsubstituted or inertly substituted divalent organic group. In Structure II, the bond shown between the metal atom and the sulfur atom may have more or less ionic characteristics depending mainly on the choice of the metal. Further, 10 in some cases, the metal ruthenium atom may be hydrated, in which case water molecules may be interposed between the metal atom and the sulfur atoms. In the illustrated idealized structure, hydration water may be omitted for clarity, but for the purposes of the present invention, such structures are understood to include hydrated analogs.

In certain embodiments, the invention is also a polymer composition comprising a flammable additive to which a sulphur-sulfur additive represented by the following structure III 15 has been mixed:

200918590 wherein each X is independently oxygen or sulfur, each m is independently zero or 1, 1 is an integer of 1 or higher, when 1 is 1, q is zero, and when 1 is an integer of 2 or higher, q is 1, Z represents a cationic group, and each R independently is an unsubstituted or inertly substituted hydrocarbon group or any R group of the R-lXh-P-iXU-R structure may together form an unsubstituted 5 or an inert substitution The valence is an organic group and A is an organic bonding group. The invention is also a phosphorus-sulfur compound represented by structure II or structure III. The polymer compositions of the present invention contain certain phosphorus-sulfur additives. The first phosphorus-sulfur additive is a sulfur bridged compound represented by the following structure (I):

10 wherein each X is independently oxygen or sulfur, each m is independently zero or 1, p is 1 or 2, and each R is independently an unsubstituted or inertly substituted hydrocarbon group or any R-(X)mP-(X)mR The R groups of the structure together may form an unsubstituted or inertly substituted divalent organic group. Certain sulfur bridged phosphorus-sulfur additives include such additives represented by the following structures IV and V 15 :

Wherein R and p are as defined above. In structures I, IV and V, the R groups may be, for example, an unsubstituted or inertly substituted aliphatic, cycloaliphatic or aromatic group. 200918590 In the present application, an "inert" substituent is a substituent that does not undesirably interfere with the flame retardant properties of the compound. A compound containing only an inert substituent is said to have "inert substitution". The 'oxime substituent may be, for example, an oxygen-containing group such as _, vinegar, a group, a thiol group, an epoxide group, and an epoxy group. a group etc. 5 The inert substituent may be a nitrogen-containing group such as a first, second or third amine group, an imido group, a phosphonium group or a nitro group. The inert substituent may contain other heteroatoms such as Sulfur, phosphorus, antimony (such as decane or decyloxy), etc. The inert substituent on the phosphorus-sulfur additive is preferably not _. In addition to the inert substituents shown in detail, for the purposes of the present invention, a hydrocarbon 10 group Is a group containing only hydrogen and a carbon atom. The nicotyl group may be an aliphatic, alicyclic, aromatic group or some combination of two or more of these types. The glare in structures IV and V is preferably not a low-cracking group substituted or inertly substituted, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, second-butyl, etc. In certain embodiments, any thiol group of the R-(H(X)mR structure

The group can form a divalent organic group, as shown, for example, in the structure of the following structure, which can form a ring structure with the m_p(x)m_ bond:

And wherein each R2 is independently a hydrogen, an alkyl group or an emotionally substituted sclerosing group, each of r3 is independently a covalent bond or a 2 divalent linking group, and P is as defined above. In the structure VH, 'each R is preferably hydrogen' and r3 is preferably an alkyl group which is directly bonded to the carbon atom (group) of the {200918590 group and which does not contain hydrogen. R3 is more preferably a dialkylmethylene group and most preferably a dimethylmethylene group (propylene group). More particularly preferred sulfur bridged phosphorus-sulfur additives include the additives shown in structures VIII and IX below:

VIII

5 where p is as defined above. Other suitable types of sulfur bridged phosphorus-sulfur additives are illustrated by the following structures X and XI:

Where p is as defined above. 10 Another type of phosphorus-sulfur additive is the type of metal bridge represented by the following structure II:

Wherein each X is independently oxygen or sulfur, each m is independently zero or 1, Μ represents a metal atom which can have hydration of bound water, η is a number from 1 to 4, and each R 15 is independently unsubstituted or The inertly substituted hydrocarbyl group or the R group of any R-(X)mP-(X)mR structure together may form an unsubstituted or inertly substituted divalent organic 10 200918590 group.

Certain metal bridged phosphorus-sulfur additives include additives represented by the following structures XII and XIII:

Wherein R, η and Μ are as defined for structure II, and in structures XII and XIII, the R groups are preferably as defined by the previous structures IV and V, and in some embodiments, any R-(X) The R groups of the mP-(X)mR structure together may form a divalent organic group, as shown, for example, in the structures XIV and XV below, the divalent organic group and the -(Xh-P^Xh- The bond can form a ring structure:

Wherein R2 and R3 are as defined in the foregoing structures VI and VII, and Μ and η are as defined in the previous structure II. In the structures XIV and XV, each R2 is preferably hydrogen, and R3 is preferably an alkyl group which does not contain hydrogen on the carbon atom (group) directly bonded to the adjacent (R2) 2C group. More preferably, R3 is a dialkylmethylene group and most preferably a dimethylammonium 15 group. More particularly preferred metal-bridged phosphorus-sulfur additives include the additives shown in the following structures XVI and 11 200918590 XVII:

Among them, Μ and η are also as defined in Structure II above. Other suitable types of metal bridged phosphorus-sulfur additives are illustrated by the following structures 5 XVIII and XIX:

Wherein Μ and η are also as defined in the previous structure II. In Structure II and ΧΙΙ-ΧΙΧ, in each case, the metal atom Μ can form a coordinate (coordination) bond with a sulfur atom on each thiophosphate group. Suitable metals include, for example, soil-checking metals such as erroneous mothers; metals such as cerium; Group 4 metals such as titanium and zirconium; Group 15 metals such as lanthanum and cerium; Group 12 metals such as zinc And cadmium; metals of Groups 8, 9 and 10, such as iron, Ming, nickel, niobium and I bar; and Group 11 metals such as copper or silver. Preferred metals include #5, magnesium, zinc, and money. 15 In Structure II and ΧΙΙ-ΧΙΧ, depending on the choice of the metal, the bond between the atomic ruthenium and the sulfur atom of the gold 12 200918590 may have more or less ionic character. Further, in some cases, the metal ruthenium atom may be hydrated, in which case water molecules may be intercalated between the metal atom and the sulfur atoms. For example, when lanthanum is Ca or Mg, the bond tends to be highly ionic, and in some cases, the structure also includes water for hydration. In the structures shown, water for hydration may be omitted for clarity, but for the purposes of the present invention, it is understood that such structures include hydrated analogs.

Furthermore, Structure II and XII-XIX are merely experimental structures and when in solid state, it is not intended to explicitly state any particular crystalline structure of the molecule. The organic-10 phosphorus-sulfur molecular groups can exhibit various geometric or spatial arrangements relative to the metal in a solid state. The third type of phosphorus-sulfur additive is an ion compound represented by the following structure III:

15 wherein each X is independently oxygen or sulfur, each m is independently zero or 1, 1 is an integer of 1 or higher, when 1 is 1, q is zero and when 1 is an integer of 2 or higher, 1 is 1 Z represents a cationic group, and each R independently is an unsubstituted or inertly substituted hydrocarbon group or an R group of any R-(X)mP-(X)mR structure together forms an unsubstituted or inertly substituted divalent organic group. a group, and A is an organic bonding group. 20 Certain ionic phosphorus-sulfur additives include additives from the following structures XX and XXI generation 13 200918590:

Wherein R, Z, A, q and 1 are as defined in the foregoing Structure III. In structures XX and XXI, the R groups are preferably as described in the previous structures IV and V. In certain embodiments 5, two R groups of any R-(X)mP-(X)mR structure may form a divalent organic group, such as, for example, as shown in the following structures XXII and XXIII, The valence organic group may form a ring structure with the -(X)mP-(X)m-bond:

Wherein R 2 and R 3 are as defined in the previous structures VI and VII, and Z, A, q and 1 10 are as defined in the previous structure III, and in the structures XXII and XXIII, each R 2 is preferably hydrogen, and R 3 is more Preferably, the alkyl group is free of hydrogen on the carbon atom (group) directly bonded to the adjacent (R2) 2C group. R3 is more preferably a dialkylmethylene group and most preferably a dimercaptomethylene group. More particularly preferred ionic phosphorus-sulfur additives include the additives shown in the following structures XIV and XV: 14 200918590

N XXIV xxv wherein Z, A, q and 1 are also as defined in Structure III above. Other suitable types of ionic phosphorus-sulfur additives are illustrated by the following structures XXVI and XXVII:

Γ^Ί Ί\ s· -z—i—^ XXVI1 where Z, A, q and 1 are also as defined in Structure III above.

In any of Structures III and XX-XXVII, the value of 1 can range from 1 to a large number. When the A group is an organic polymer as described below, the value of 1 can be 1000 or higher, and can be from 2 to 500, more typically from 2 to 100. 10 When A is a non-organic polymer, 1 is typically from 2 to 8, more typically from 2 to in structures III and XX-XXVII, which may be ammonium, squama, samarium or sulphate (phosphazenium) ) group. In the case where 1 is 1 and q is zero, the ammonium ethyl group may be in any of the following forms: H4N+, H3(R4)N+, 15 H2(R4)2N+ or H(R4)3N+ or (R4)4N+, wherein Each R4 is independently a hydrocarbyl group or a hydrocarbyl group of the inert group 200918590. Preferably, the R4 groups are phenyl, substituted phenyl, benzyl or lower carbon (such as CM leuco). When 1::>1 and (4), the record base can be any of the following: H3N+-A, H2(R4)N+-A, H(R4)2N+-A, or (R)3N-A 'where R4 The definition is as described above. The oxime group can have the following formula: (R4)3S+ (when 1 is !) or (R4)2S+_A (when _). Similarly, when 1 is 1, the squaring group may be in the form of (7) 4) 4^ or when 1 >; [and q may be 1 (RV+-A form 'R4 is also as defined previously. The squamous nitrogen group contains - Or a variety of molecular groups:

10 Suitable niobium nitrogen groups include groups which are represented by the following structures and are also represented: r (J=P(A3)) Plant N(Rs)2 A—N—P+-^N=p(a3) ^_N{r5)2 (N=P(a3)士N(R5)2 (XXIX) =P(A3)2^-N(R5)2 j —'j+*~(N=p(A3))TN (R5)2 Rs (N=p(a3)士n(rs)2

R5 N (XXX) wherein, in each occurrence, each r5 is independently (a) an unsubstituted or inertly substituted alkyl or aryl group, (b) an unsubstituted or inertly substituted alkyl or aryl group, And the other -R5 group on the same nitrogen atom may form a ring 15 structure including the nitrogen atom, (C) an unsubstituted or inertly substituted alkyl or aryl group, which is bonded to the bond to Another R5 group sharing a different nitrogen atom of a phosphorus atom together may form a ring structure including a -NPN- or -NP=N-molecular group, or (d) hydrogen. 16 200918590 Each R is preferably a hydrogen-based group (especially methyl, ethyl, n-decyl or isopropyl), or may form a c2.5 extension group with another -R5-, which is associated with a ruthenium atom - The N-mN_P good molecular group - can form a ring structure. Each a3 is independently -[(4)(A3)]k-NR2' where R is as defined above. Each _ is zero or a positive integer. Preferably, the k values are such that the group contains κ 6 phosphorus atoms. It is noted that the charge on any of the squamous nitrogen groups can be delocalized within the base and is represented by the charge in formulas XXIX and XXX, which may not be present on a particular phosphorus atom. r

The oxime group in the fine and xx-xxvn may be any organic bonding group having a valence equal to i (when 101 is an integer of 2 or higher). It may be a hydrocarbon group which comprises a linear or branched aliphatic, alicyclic, aromatic hydrocarbon group or a mixture of two or more such groups. Aliphatic and alicyclic groups can be saturated or unsaturated. The s-A group may contain an inert substituent as described above. In certain preferred embodiments, the A group is an organic polymer. 15 In most cases, these scale-sulfur additives can be prepared directly using simple chemical methods. The starting material can be easily prepared by using P4S10 which is easily obtained with a lubricant and a raw material for biocide production, in contact with an alcohol or a mercaptan. The alcohol and thiol have the structure ROH and RSH, respectively, wherein R is as defined above for structure I. The reaction product is a thiol compound having the following structure:

R

(X)m

SH

R

(XXXI) where X, R and m are as defined above. The diol of the formula H〇-C(R2)2_R3-C(R2)2〇H (the R and R3 of 17 20 200918590 is defined by the above structure νι&νπ) is reacted with pj(7) to form the following structure. Cyclic starting material:

(XXXII) wherein X, r2 and r3 are as defined above. In the structure XXXII, each r2 is preferably 5 hydrogen and R3 is preferably a dialkylmethylene group, particularly a dimethylmethylene group (propylene group). The reaction product can be prepared by reacting a thiol compound according to the structure XXXI or hydrazine with a mixture of sodium methoxide in a methanolic solution, and reacting it with potassium iodide and iodine in an aqueous solution to prepare a structure. The bridge is connected with phosphorus-sulfur additives. The monosulfide bridge-sulfur additive can be formed by reacting the disulfide bridged compound with a mixture of 10 triphenylphosphine in a solution. The structure 11 and the ruthenium 11_乂1乂 metal bridged phosphorus-sulfur additive can be prepared by directly contacting the hydroxide or salt of the metal with the starting compound of the structure XXXI or XXXII. Such synthesis is described, for example, in C Glidewe U, In〇rganic 15 Chimica Acta, 1977 25 159. Preferably, the reaction is carried out in solution in which the metal hydroxide or salt is soluble in the solvent. The metal, the carbonate, the hydroxide, the oxide and the acetate are generally used. If necessary, the starting compound can be formed into a corresponding salt by mixing with the first, second or third amine compound and then reacting with the β-metal salt. The reaction can be graphically represented by the following reaction scheme: 18 200918590

i \

(XXXIV) 5 wherein X, R, m, n and M are as defined above, X1 is an anion, and each R6 is independently hydrogen, a hydrocarbyl group or an inertly substituted hydrocarbyl group (preferably an alkyl group). In Reaction Scheme XXXII, X1 should not be 02_ or carbonate, and in each of the reaction schemes, X1 is preferably a halide, especially a chloride or a bromide. The structure II and XX-XXIX phosphorus-sulfur additives in which the ethyl group is an ammonium molecular group can be formed in at least two ways. In the first mode, the starting compound of the structure XXXI is reacted with a compound having one or more primary, secondary or tertiary amine groups to form the phosphorus-sulfur additive. In the second mode, the starting compound of structure XXXI is reacted with a compound having one or more ammonium groups to form the sulphur-adding additive. The amine-containing compound which can react with the starting material of the structure XXXI includes, for example, a polyamine such as ethylenediamine (H2NCH2CH2NH2), diethylenetriamine (H2NCH2CH2NHCH2CH2NH2), and other alkylamines and alkyleneamines; Tillage and other cyclic polyamines, and a variety of organic polymers containing amino acids. These organic polymers include polyethers having terminal amine groups, such as poly(propylene oxide) polymers of the first amine group 19 200918590 end group, which include polymers commercially available under the trade name Jeffamine®. A polymer of acrylamide can be used. In addition, a variety of amine-containing polymers can be formed by introducing the amine groups onto previously formed polymers using a variety of methods. For example, ammonia, the first or second amine can be reacted with a functional group on a functionalized polymer such as a polymer or copolymer of ethylene-5 alkenyl chloride, vaporized ethylene or dichloroethylene to form the polymerization. Amino group of matter. The clock compound can be formed from the corresponding amine compound by reaction with an aprotic acid such as hydrochloric acid or sulfuric acid (to form the chloride or ammonium sulfate salt) or by basifying the amine. 10 The structure m and the XX-XXIX phosphorus-sulfur compound wherein Z is a shovel, scale or scale nitrogen can be formed by reacting the starting compound of the structure XXXI with a compound having one nickel, scale or scale nitrogen group. An example of such a method is to use sweat and

Schlientz is described in Inorg. Synth. 1874, 15, 84. A linear polymer having a crosslinked polymer other than that described in the following paragraph can be used to prepare an organic polymer containing a squamous nitrogen group using a method similar to that described in WO 01/90220 A2. In general, the two main methods for attaching a squamous nitrogen group to the organic polymer are (1) attaching a previously formed scaly group to the organic polymer, and (2) attaching to the organic polymer. Construction, scaly nitrogen group:

By reacting an amine-substituted organic polymer with phosphorus pentachemical phosphorus, and then reacting with a compound having the knot hN=P(A2)]X-NR2}3 over L20 = "constructing the polymer, , a squamous nitrogen group. It can form a corresponding scale gas directly in the form of chloride.) The soil is a phosphorus-sulfur compound which can be used as a plurality of flammable poly-p and M. 4. The flammability in the text simply means the polymer. It is flammable under ambient or lower conditions. The related combustible polymers include polyalkylene, Ικ ethylene (which includes ethylene copolymers such as ethylene · "smoke") | propylene, etc. Polycarbonate, and polycarbonate blend, Wei (4), nitrile, stupid, butadiene resin or polyphenylene ruthenium "poly" & amine, polyester 'epoxy Resin, polyurethane, and ethyl t-fragrance (which includes an ethylene-based aromatic homopolymer, an ethylene-based aromatic dimer, or - or a plurality of vinyl aromatic homopolymers) And/or a blend of vinyl f 10 15 20 1 ), and a towel thereof to dissolve or disperse the carbonized carbon: flammable polymer ° '' Ethylene-based aromatic, the polymer is a substance having a polymerizable rare unsaturated group directly bonded to an aromatic ring-shaped aromatic compound, such as a styrene-based aromatic monomer. Including unsubstituted rare unsaturated groups on "~ethylbenzene and ethylene naphthalene; and compounds in the substitution. ^Γ (such as "·methyl styrene"), and 7 or cyclin, alkoxy, or pi, the B-wean aromatic monomer including the singularity of the surface directly bonded to the aromatic ring - ❹ It is not the body of the body ^^4\ monomer. These are substituted by the ring of ethylene, aromatic monooxy acetophenone, 2·=dilute, 2_ or 4_gas stupid, 2_ or 4 _Methyl dimethyl phenyl hydrazine. Dilute, 2 or 4 - methyl styrene and 2,4- phenethyl hydrazine & alkenyl aromatic monomer is stupid, t methyl ψ terpenene, Divinylbenzene and a mixture of them. Any U or shell type foaming polymer is of importance. The polymer burning polymer is a vinyl aromatic mono-hybrid polymer or a total of: or stupid::: :: polymer or copolymer, propylene-polymerized phthalonitrile-butadiene (ABS) resin. Polystyrene is a more flammable polymer of 200918590. Another related combustible polymer is butadiene and a random, embedded, or graft copolymer of at least one vinyl aromatic monomer. Any of the foregoing types of foamable flammable polymers are of particular importance because they are useful in vehicles and construction where fire protection properties are important properties. Foaming The foaming density of the flammable polymer is suitably from about 1 to about 30 dicans per pc (pcf) (16-480 kg/m3), and more preferably from about 1.2 to about i〇pcf (i9.2 to 160 kg). /m 3) and preferably from about 1.2 to about 4 pcf (19.2 to 64 kg/m3). These phosphorus-sulfur flame retardant compounds are suitable for the preparation of extruded polymer foams, as for example The heat stability of the compounds is shown to be suitable for introduction into the foam extrusion process for preparing the foam as shown in the % weight loss temperature test. Sufficient phosphorus-sulfur compounds are used to improve the one or more standards of the combustible polymer. The performance in the fire test. The suitable amount is typically at least 1% by weight or at least 2% by weight or at least 3% by weight based on the weight of the polymer and the phosphorus-sulfur compound. 15 The phosphorus-sulfur compound content It may be as much as 25% by weight or as much as 15% by weight or as much as 10% by weight. One such standard fire test is the Limiting Oxygen Index (LOI) test, which evaluates the lowest of the atmosphere required to maintain the combustion of the polymer. Oxygen content. L01 can be conveniently determined according to ASTM D 2863. The LOI of the combustible poly 20 compound containing the phosphorus-sulfur compound is higher. It is at least 2%, more preferably at least 23% and even more preferably at least 25%. Another fire test is a time-to-extinguish assay (also known as FP-7), which is based on R. Ingranl is determined by the method described in J. Appi·P〇ly. Sci. 1964, 8, 2485-2495. This test measures the flame when a polymer sample is exposed to combustion under specific conditions. The time required for the flame to be extinguished when the 2009 18590 combustion source is removed is then removed. For non-porous polymers, the time to extinguish the flame is less than 10 seconds, preferably less than 5 seconds. In the case of a porous polymer (having a density of l〇pcf or less), the time for extinguishing is less than 15 seconds, preferably less than 10 seconds and more preferably less than 5 seconds. In general, these results are obtained when the 5 composite flammable polymer contains from 1 to about 15, preferably from 1 to about 6% by weight of the phosphorus-sulfur flame retardant additive. Preferably, the phosphorus-sulfur flame retardant additive is incorporated into the molten combustible polymer prior to or during another melt processing operation (such as extrusion, foaming, molding, etc.). Accordingly, the phosphorus-sulfur retardant additive is preferably stable at a temperature at which the molten polymer is processed. This temperature is typically above 150 ° C and is 200 ° C or higher, or even 220 ° C or higher, for many particularly important combustible polymers. A useful indicator of thermal stability is the 5% weight loss temperature, which is determined by thermogravimetric analysis as follows: using a TA Instruments Hi-Res TGA Model 2950 15 or equivalent, at a flow rate of 60 milliliters per minute (ml/min) The gaseous nitrogen and the heating rate of 10 ° C / min were analyzed in the range of room temperature (in nominally 25 ° C) to 600 ° C ~ 10 mg of the sulfur-sulfur flame retardant additive. During this heating step, the mass loss of the sample was monitored and the time at which the sample had lost 5% of its original weight was referred to as the 5% weight loss temperature (5% WLT). The method provides a temperature at which a sample has been subjected to a cumulative weight loss of 5% by weight based on the weight of the initial sample. Preferably, the phosphorus-sulfur flame retardant additive is capable of melt processing the combustible polymer to blend with the phosphorus-sulfur flame retardant additive or processing the blend into an article, such as a foam, extrusion 5% WLT for parts, molded parts, or the like. In combination with many combustible polymers, the phosphorus-sulfur flame retardant additive should have a 5% WLT of at least 150 °C. The 5% WLT is preferably at least 200 ° C, more preferably at least 220 ° C, still more preferably at least 240 ° C, and still more preferably at least 250 ° C. [Embodiment 3] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The polymer blend according to the present invention may include other additives such as other flame retardant additives, flame retardant adjuvants, thermal stabilizers, ultraviolet stabilizers, nucleating agents, and anti- An oxidizing agent, a foaming agent, an acid scavenger, and a coloring agent. The polymer blend containing the phosphorus-sulfur flame retardant additive according to the present invention can be processed by melt or solution to form a variety of products. Foaming (porous) products are important because they can be used in a variety of construction and automotive applications where fire resistance is important. The overall density of the foamable polymer product may be 10pcf or less, more typically from 1.5 to 5 pcf and especially preferably from 1.5 to 3 pcf. The following foaming polymer is particularly important: a copolymer of a vinyl aromatic polymer, a butadiene polyphosphate, and a vinyl aromatic polymer and/or a butadiene polymer as described above, or according to the present invention The invention produces a non-porous polymer. The following examples are provided to illustrate the invention, but not to limit its scope. All parts and percentages are by weight unless otherwise specified. Example 1 20 Add a solution of sodium methoxide in methanol (25% by weight solution, 10 ml, 45 mmol) to 5,5-dimethyl-2-thioketo-1,3,2-di Phosphatidyl-2-thiol (9.0 g, 45 ml) was stirred and stirred for 30 minutes. Concentration under reduced pressure gave a clear solution and the residue was dissolved in water (100 ml). The aqueous solution was added to a solution of potassium iodide and iodine, resulting in precipitation of a tan solid. Filtration and 24 200918590 Recrystallization from ethanol to obtain 6.2 g (70% yield) of 2,2,-disulfide 5,5,5,5,-tetramethyl, such as a pale yellow solid having the following structure Base-2,2,-dialkylthiodiyl-bis-[1,3,2-dioxaphosphorane):

5 5% of the substance WLT is 227 °C. A part of this sample was melt-blended with a polystyrene resin at a weight ratio of 4.2:95.8. Prior to molding, a Wiley laboratory grinder and a 3 mm sieve size milled 5 liter equivalent cured blend were used. Use Pasadena Hydraulic

Platen Press (Model # BL444-C-6M2-DX2357), operating at a freezing point temperature of 180 ° C at a pressure of 5 minutes and a pressure of 25,000 pounds (psi) per square inch (172 MPa), will be 25- A 27 gram portion of the ground melt blend was pressed to form a plaque having a size of 100 mm x 100 mm x 1.5 mm. The molded plaques were cut into strips suitable for the Oxygen Limit Index (LOI) and FP-7 ignitability tests. LOI 15 was evaluated according to ASTM D 2863 and the LOI was found to be 25.7%. The time during which the flame was extinguished on the fp-7 test was evaluated and found to be 0.8 seconds. Example 2 Addition of triphenylphosphine (2.62 g, 1 Torr) to 2,2,-disulfide 5,5,5',5'-tetradecyl-2,2'-dialkylthiodiyl_ Bis-[1,3,2-dioxaphosphol-2-oxane] (3.94 g, 10 mmol) in 25 mL of toluene. The mixture was stirred at room temperature for 4 hours. The resulting turbid solution was filtered and the precipitate was slurried in air (20 mL) and filtered to yield 2.5 g (69%) of 2,2,-disulfide 5,5 as white solid. 5',5'-Tetramethyl 25 200918590 -2,2,-Sulphur diyl m2_二崎碟”

5% of this material has a WLT of 237. (:. A plaque made from a blend of 25% of the product in 97 5% polystyrene (see example!) has (4) (10) and 5 has a flame extinction time of 1 on the FP_7 test. 5 seconds. 10% by weight of the substance in the polystyrene is prepared as follows: blending the 2,2,-disulfide 5,5,5,5,4-tetramethyl-2,2,_ Alkylthio-yl-bis-[1,3,2-dioxaphosphane], polystyrene, and 2% by weight of powdered organotin carboxylate based on the weight of the blend Agent (for example, commercially available THERMCHEKTM 832 from 10 Ferro Coi*poration). The blend is melt blended with polystyrene using a Haake RHEOCORDtm 90 twin screw extruder equipped with a pellet die. Three temperature zones operated at a condensation point temperature of 135 ° C, 17 ° C & 180 C and a mold condensation point temperature of 180 ° C. The extruded filaments were cooled in a water bath and cut to a length of about 5 mm. 15 pellets. Use 25 mm single screw extruder with 3 heating zones, foaming agent mixing parts, chiller parts and adjustable 1.5 mm adjustable slit die in sequence The foam is formed. The three heating zones are operated at a condensation temperature of 115 ° C, 150 ° C and 180 ° C, and the mixing zone is operated at a condensation temperature of 2 ° C. Open the hole to maintain a back pressure of at least 20 1000 psi (6.9 MPa). Use two different RUSKATM (Chandler

Engineering Co.) Injecting carbon dioxide (4.5 parts by weight (pbw) per 100 pbw combined weight of the concentrate and polystyrene granules into the blowing agent mixing part. Concentrating small particles and additional polystyrene small particles Dry blending with 0.05 wt% based on the weight of dry blend 26 200918590 as a screw lake slip agent. The ratio of the selected concentrated pellets to the other polystyrene pellets can be obtained. 4.2% by weight of the final concentration of the flame retardant additive. The dry blend was added to the feed funnel of the extruded formulation and fed at a rate of 2.3 kg per hour (5 kg/hr) per hour. Maintained above 15 〇Opsi (1 〇.4 MPa) to obtain a polymer gel with uniform mixing and promote the formation of a foam having a uniform cross section. The cooler can heat the foamable gel Dropped to 120-130 ° C. The expandable gel swells when it leaves the mold to form an expandable polystyrene foam having an overall density of 10.8 pcf (39.7 kg/m 3 ). The LOI of the body is 24.5%, and it is extinguished on the FP-7 test. The time is 7.5 seconds. Example 3 Adding zinc bromide (2.25 g '1 〇 millimolar) to 5,5-dimercapto-2-thiol-[1,3,2-di-sigma 2-merol (4.0 g '20 mmol) in a solution of 7 ml of 15 benzene in benzene and heating the mixture to 85 ° C for 4 hours. As the reaction progresses, the clear reaction mixture becomes White and turbid. Cool the 5 hr reaction mixture and filter to give 2.9 3 g of a white solid with the following ideal structure (ignoring any hydration water):

2〇 This material has a melting temperature of 246 ° C and a 5% WLT of 258 ° C. Proton NMR and 31 P NMR spectra were characterized as follows: 'H NMR (THF-d8, δ): 3.98 (d, J = 16 Hz, 4H), 1 〇 2 (s, 6H). 31P NMR (THF-d8, δ): 100.67 (s, l). 27 200918590 The fascia made from a blend of 2.8% of this product in 97.2% polystyrene has an LOI of 20·5 and an extinction time of 13 seconds on the FP-7 test. Example 4 An ammonium salt of 0,0-dinopentyl disulfate (2.87 g, 10 mmol) was added to a solution of zinc bromide (1.13 g, 5 mmol) in 25 ml of ethanol. Stirring the mixture took a night. The reaction mixture was then concentrated under reduced pressure and the residue was crystallised in toluene (75 ml). The filtrate was filtered and concentrated to give 2.85 g (94%) of white solid. Self-burning and recrystallization to obtain bis[0,0-bis(2,2-dimethylpropanyl)phosphinodithiol-S,S with the following idealized structure (ignoring any hydration water) ']-Zinc:

The refining temperature of this material is 220-222 ° C ' and its 5% WLF is 237 ° C. Proton NMR and 31 P NMR spectra showed the following characteristics: NMR (CDCl3, δ): 3.80 (d, J = 6.9 Hz, 8H), 0.97 (s, 36H). 15 31P NMR (CDC13, δ): 98.30. The plaque made from a blend of 3.3% of the product in 96.7% polyethylene had a LOI of 20% and the extinguishing time on the FP-7 test was leap seconds. Example 5 Bismuth triacetate (7-539 g, 25.22 mmol) was added to 2_5,5-dimethyl-2-indole-1,3,2-di. Phosphacyclohexane (15.000 g, 75 67 mmol) 28 20 200918590 In a solution of 150 ml of ethanol to form a yellow precipitate of the wall of the coatable flask. After heating overnight, the precipitate formed a bright yellow slurry which did not require agitation. The reaction mixture was then refluxed for several hours and filtered. The yellow sediment was washed with two portions of ethanol 'two portions of water and two portions of ethanol and dried under suction 5 . The yield of the orange-yellow powder (5,5-dimethyl-2-nonyl-1,3,2-diphosphorane)-ruthenium sulfide was 11.01 g (61.2%). The idealized reaction flow diagram (which ignores any hydration water) is as follows:

The 5% WLT of this material is 259. (: plaques made from a blend of 3% of the product in 97% polyphenylene ene terene have an LOI of 22.5 and a FP-7 value of 3.8. Example 6 in a single neck 250 ml flask 2-Sulphide 2-mercapto-5,5-dimethyl-1,3,2-dioxaphosphane (16.00 g, 80.71 mmol) was slurried in 1 mL of water. Calcium carbonate (4.2 g, 42 mmol) was slowly added and about 5 15 L of ethanol was added to decompose the formed foam. Heating the resulting white slurry takes several days. The water was then removed on a rotary evaporator and heated to about 5 Torr. The white solid was extracted with propylene g and passed through to leave a small amount of white powder on the block. The volatiles were removed from the acetone solution on a rotary evaporator to give a viscous 29 2009 18590 white solid. Water is added to dissolve most of the solid. The resulting mixture was filtered. The aqueous solution was dried on a rotary evaporator to obtain 17.42 g of a white solid product having the following ideal structure (water not showing hydration).

4.1 sec 10 Example 7 The crystalline structure of this material is consistent with the high ionic structure of the water with 7 hydration in which the highest ionic interaction is combined. The 5% WLT of this material is 27 〇 °C. The plaque made from a blend of 2.8% of the product in 97.2% polystyrene had an LOI of 21.3% and the extinguishing time on the FP-7 test was the addition of 2-sulfonyl 2-mercapto-5,5. - Dimercapto-1Λ2-di, phosphonium (15 g, 75.67 mmol) to magnesium hydroxide in a single neck 25 ml flask (2.207 g '37.83 mmol) in 1 mL water The body of the pulp. The mixture was refluxed for several hours. The reaction mixture was passed through to remove insolubles. The water was removed on a rotating 15 hair dryer and heated to about 50 °C. The residue was extracted with acetone, and the volatiles were filtered and evaporated to afford 19 s.

The crystalline structure of this material is consistent with the high ionic structure in which 6 hydration waters are combined with 20 4 Mg ions. 30 200918590 Example 8 In a single-neck 250 ml flask, 2-sulfonated 2-hydrazino-5,5-dimethyl is m-dioxaphosphorane (〗 6.00 g, 80.71 mmol) in 100 ml = Slurry. Carbonate planer (13.281 g, 4 〇 76 mmol) was added slowly, and 5 liters of methanol was added to control foaming. The resulting slurry was agitated at ambient temperature under a stream of nitrogen which reduced the volume of the liquid to about 50 ml. It took a while to transition the formed polymer over the course of the week and extract it several times with water. A small amount (<1 g) of white solid remained on the block and was discarded. Remove water on the rotary evaporator. The white solid formed is soluble in water, DMS, Me〇H, and has a low solubility in acetone. It is insoluble in CH3Cl3, toluene and hexagram. The residue was extracted with methanol and transitioned. The volatiles were removed on a rotary evaporator. The solid was scraped off' polymerized/dissolved in methanol and filtered. The white solid was washed with several small portions of methanol, two W each of 60 ml) of benzene, two portions (6 mM each), and dried under suction to obtain 21 〇 5 g (79 〇%) such as snow white powder. The product. The 15 product has the following idealized structure:

The 5% WLT of this material is 325 °C. Example 9 <7 Adding BlCl3 (1 (Ug, 32" millimolar) to 2-sulfurized 5,5-dimercapto-2-hypocyclohexane (10) 7 g, heart 6 mmol) and triethyl The amine (7 g of '13 liters' 96.2 mmol) was dissolved in 150 ml of ethanol. The yellow sacred object of the wall of the flask. After heating overnight, 31 200918590 the precipitate formed a fresh yellow slurry without agitation. The reaction mixture was then refluxed for several hours and passed through. The yellow precipitate was washed with two portions of ethanol, two portions of water and two additional portions of ethanol and dried under suction. The yield of ruthenium (5,5-dimethyl-2-indolyl-1,3,2-diphosphazene)2-ruthenium sulfide was 12.98 5 g. The idealized reaction flow chart (ignoring the water for hydration) is as follows:

5% of the material is 264 ° 〇 from 3.3% of the product in 96.7% polystyrene blended plaque has a LOI of 22.3% and extinguished on the FP-7 test The time is 6.4 seconds. 10 Example 10 Add tetradecylethylenediamine (1 g, 8.6 mmol) to 5,5-dimercapto-2-thioketo-[1,3,2-dioxaphosphane. 2-thiol (3.41 g, 17.2 mmol) in a stirred slurry of toluene (200 mL). A white solid formed immediately in the flask. The reaction mixture was stirred at room temperature overnight. The solid was filtered on a 15 degree sintered glass filter having a cold water vacuum. The white solid was washed with cold toluene (2 x 25 mL) and dried on the filter for 5 min. The solid was dried in a vacuum oven for 3 hours to give 3.98 g of bis[5,5-dimethyl-1,3,2-di as a white crystalline solid. No. Heteropolyhexene 32 200918590 Alkyl-2-thiol 2-sulfided] ruthenium, osmium, iridium, osmium-tetramethylethane-1,2-diammonium. This material has the following ideal structure:

The material has a melting temperature of 218 ° C and a 5% WLT of 226 ° C. The plaque made from a blend of 1.6% of the product in 98.4% polystyrene had 21.3% L Ο I and the extinction time on the F P - 7 test was 7.1 seconds. Example 11 10 15 A solution of diethylenetriamine (0.1 g, 0.97 mmol) was added dropwise to 2-sulfonyl 2-mercapto-5,5-dimethyl-1,3,2-diphosphazene ( 0.576 g, 2.91 mmoles of a stirred slurry in toluene (50 mL). A white solid formed immediately in the flask. The reaction mixture was warmed to ~40 °C and stirred for 20 min. The reaction mixture was concentrated under reduced pressure and the residue was dried in a vacuum oven for 2 hours to give 0.69 g of as a white crystalline solid (5,5-dimethyl-1,3,2-diphosphonium) Heterocyclohexane-2-thiol 2-sulfided) N-(2-aminoethyl)ethane-1,2-diammonia. This material has the following ideal structure:

The material has a melting temperature of 218 ° C and a 5% WLT of 224 ° C. Example 12 Bis(triphenylphosphine)imide acetate (15.0 g, 25.10 mmol) was suspended in 500 ml of water and then dissolved by heating with heat. The clear solution was filtered from very small amounts of insoluble black matter. Add 2-sulfonate 2-mercapto-5,5- 33 200918590 Dimethyl-1,3,2-dioxaphosphane (4.98 g, 25.1 mmol) in 12 μl of hot water slurry Body and precipitate a large amount of white solid. Stirring the mixture took a night. The reaction mixture was heated to near boiling point on a heating pack to cool it slightly and filtered. The precipitate was washed several times with cold water and then dried on a 5 suction filter under a stream of air. 16.56 g of a white powder having the following idealized structure was obtained:

(C6H5)3PfiP(C6H5)> ^ 5% of the substance WLT is 329. (: The compound is soluble in methanol, gas, acetone and DMSO, but insoluble in water, toluene, and calcined. The non-thioate acid anion is observed by ES-MS of negative 10 and positive ion plates, respectively. [Μ]-=196·99) and the presence of PPN cations ([Μ]+=538·18). Proton, 13C and 31P NMR spectra showed high purity materials. These spectra showed the following features: 4X1^11 (299.99 MHz) , CDC13, vsTMS) δ: 7.66 - 7.72 (m, 6H), 7.43 - 7.55 (m, 24 Η), 4.00 (d, 4H, J 15 = 15.38 Hz), 0.99 (s, 6H). 13C NMR (75.44 MHz, CDC13, vs CDC13) δ: 133.70, 131.78 (1:3:3:3:1 m_ pentet, J = 5.7 Hz, outside 2.7 Hz), 129.39 (1:3) :3:3:1 m-pentagon (pentet), J = 6.7 Hz, outside 2.7 Hz), 126.64 (d d, J = 107.99 Hz, J = 2.01 Hz), 74.17 (d, J = 8.05 Hz), 32.26 (d, J = 5.37 Hz), 20 22.10 〇31P NMR (121.44 MHz, CDC13, vs H3P〇4) δ: 112.49, 21.73.

Hz, CDC13, vs H3P〇4) δ: 21.75. Example 13 34 200918590 2-sulfonated 2-indolyl-5,5-dimethyl-1; 3,2-dihexaphosphorane (6.0 g, 30.27 mmol) & NaHC in 175 ml of water 〇3 (3 gram, 35 7 millimolar) to obtain a turbid solution containing a fine precipitate. A solution of tetraphenyl chloride scale (11.35 g, 30.27 mmol) in 1 mL of water was added. The reaction mixture was heated to boiling and then allowed to cool overnight to obtain a large amount of white precipitate. The mixture was filtered, washed several times with cold water and dried under suction to give a thin crystalline crystals as a white solid and product of powder, 5,5-dimethyl-2-Myl-1,3,2 -One. No. Heterocyclic Hexa Burned _2_sulfurized tetraphenyl scale. This material has the following ideal structure:

The yield was 14.41 g. 5% of this material has a WLT of 303 °C. This compound has good solubility in sterols. It has acceptable solubility in chloroform, acetone and DMSO, but is insoluble in water, toluene, and hexane. NMR spectroscopy showed that the material was obtained in a very high purity. The spectrum shows the following characteristics: H NMR (299.99 MHz, CDCI3, vs TMS) δ: 7.88 7.95 (m of t, 4H, J = 7.6 Hz, J = 2.2 Hz), 7.78 - 7.86 (m of t, 8H, J = 7.3 Hz, J = 3.7 Hz, J = 0.6 Hz), 7.62 - 7.70 (d' d' 8H, J = 13.1 Hz, J = 8.4 Hz, J = 1.5 Hz, J = 1.2 Hz) ' 3.94 ( d, 4H, J = 15.38), 0.96 (s, 6H). 13C NMR (75.44 MHz, CDCI3, vs 20 CDCI3) δ: 135.61 (d, J = 3.35 Hz) ' 134.27 (d, J = 10.73 Hz), 130.69 (d, J = 12.74 Hz), 117.25 (d, J = 89.21 Ηζ), 74·17 (d, J = 7.38 Hz), 32.31 (d, J = 5.37 Hz), 22.16. 31P NMR (121.44MHz, CDCl3, vsH3P〇4) 5: 112.20, 23.6h 35 200918590 Example 14 Combine 2-sulfurized 2-dissolved _5 5 dimethyl _u, 2-di 4 _cyclohexyl _ gram '3G.27 millimoles) and NaHCQ3 (3 GG grams, %) in 175 ml water 7 millimoles) to obtain a turbid solution containing fine sediments. A solution of 5 (32 g, 3 〇 27 mmol) in 1 ml of water was added to obtain a turbid solution. The hydrazine reaction mixture is heated and it takes several hours to produce a slurry. The water was removed under reduced pressure and gently heated on a rotary evaporator. The residue was extracted with 3 mL of hot CHCl3 and filtered. Most of this residue remained undissolved. The undissolved residue was extracted with MeOH and filtered. The combined extracts of 10 were evaporated to dryness on a rotary evaporator to give 9.6 g of white powder. The powder was extracted with a hot mixture of 5 〇/5 MeOH/CHCl3 and filtered. The volatiles were removed from the organic fractions on a rotary evaporator to give 818 g of 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphane-2 as a white powder. Tetramethylammonium sulfide. This material has the following ideal structure: d4 The material begins to decompose at about 220 ° C and its 5% WLT is 232 ° C. The product has good solubility in DMSO, MeOH and water, partial solubility in acetone and chci3, and insoluble in toluene and hexane. Proton, 13C and 31P NMR spectra showed the following properties: 20 lU NMR (299.99 MHz, CDC13, vs TMS) δ: 4.00 (d, 4H, J = 15.38 Hz), 3.50 (s, 12H), 1.03 (s, 6H). NMR: (C. 36 200918590 CDCI3, vs H3PO4) δ: 110.00. I: Simple description of the figure 3 (none) [Explanation of main component symbols] (none)

C 37

Claims (1)

200918590 X. Patent application: L polymer composition containing flammable polymer mixed with dish-sulfur additive: XX represented by the following structure • (X)n RR ^X)m (S) p (X) towel R ι\ wherein each X is independently oxygen or sulfur, each m is independently zero or i, p is _ and each R is independently an unsubstituted or inertly substituted hydrocarbon group or a woman R-TO „P_(x J-like-shaped filaments are substituted for the divalent organic group substituted by the heart. 10 2. The polymer filament of the item (4), which is represented by any one of the following structures; ;\ίΙ -(S)p- '丨丨(S)p IU〇, ,ό 〇, where ρ is 1 or 2' and each _ is unsubstituted or secretly substituted by a ketone or any R (Xh- The ambiguity of the PUR structure - a divalent organic group which can form an unsubstituted or inert substitution. 3. The polymer composition of the first embodiment of the patent application fcU is a representative of any of the following structures. 15 200918590 wherein p is 1 or 2, and each R 2 is independently hydrogen, alkyl or an inertly substituted alkyl group, and each R 3 is independently a covalent bond or a divalent bond group, and p The foregoing patent 4 range of the polymer composition according to item 3, wherein each R2 is hydrogen, and R3 is is directly bonded to an adjacent (112) 2 (in: the carbon atom of the group 10 (group) does not contain hydrogen dehydroabiediyl. 5. The polymer composition of claim 1, wherein the phosphorus-sulfur additive is represented by any one of the following structures; f where p is 1 or 2. 6. The polymer composition of claim 1, wherein the phosphorus-sulfur additive is represented by any one of the following structures; 15 where p is 1 or 2. 7. A polymer composition comprising a combustible polymer to which a scale-sulfur additive represented by the following structure has been mixed: 39 200918590 wherein each X is independently oxygen or sulfur, each m is independently zero or 1, Μ represents a metal atom which can have hydration binding water, η is a number from 1 to 4, and each R is independently unsubstituted Alternatively, an inertly substituted hydrocarbyl group or an R group of any R-(X)mP-(X)mR structure may form an unsubstituted or halo-substituted divalent organic group. 8. The polymer composition of claim 7, wherein the phosphorus-sulfur additive is represented by any one of the following structures: Wherein Μ represents a metal atom which may have a hydration binding water, η is a number from 10 1 to 4, and each R is independently an unsubstituted or inertly substituted hydrocarbon group or any R-(X)mP-(X) The R groups of the mR structure together may form an unsubstituted or inertly substituted divalent organic group. 9. The polymer composition of claim 7, wherein the phosphorus-sulfur additive is represented by any one of the following structures: Wherein Μ represents a metal atom which may have a hydration binding water, η is a number from 1 to 4, each R 2 is independently hydrogen, an alkyl group or an inertly substituted alkyl group, and each R 2 is independently a covalent bond or a divalent bond. a group, and ρ is as described above. 40 200918590 10. The polymer composition of claim 9 wherein each R 2 is hydrogen and R 3 is free of hydrogen on the carbon atom (group) which has been directly bonded to the adjacent (R 2 ) 2 C group. Alkanediyl. 11. The polymer composition of claim 7, wherein the phosphorus-sulfur additive is represented by any one of the following structures; Wherein Μ represents a metal atom which may have a hydration binding water, and η is a number from 1 to 4. 12. The polymer composition of claim 7, wherein the phosphorus-sulfur addition additive is represented by any one of the following structures; Wherein Μ represents a metal atom which may have hydration combined water and η is a number from 1 to 4. 13. A polymer composition comprising a combustible polymer in which a 15 sulphur-sulfur additive represented by the following structure has been mixed: 41 200918590 Wherein each X is independently oxygen or sulfur, each m is independently zero or 1, 1 is an integer of 1 or higher, when 1 is 1, q is zero, and when 1 is an integer of 2 or higher, q 1, Z represents a cationic group, and each R is independently unsubstituted or inertly substituted for 5 generations of a hydrocarbon group or an R group of any R-(X)mP-(X)mR structure may form an unsubstituted or inert substitution. a divalent organic group, and A is an organic group. 14. The polymer composition of claim 13, wherein the phosphorus-sulfur additive is represented by any one of the following structures: Wherein 1 is an integer of 1 or more, when 1 is 1, q is zero, and when 1 is 2 or more, q is 1, and Z represents a cationic group, and each R is independently unsubstituted or inertly substituted. The hydrocarbyl group or the R group of any R-(X)mP-(X)mR structure together may form an unsubstituted or inertly substituted divalent organic group, and A 15 is an organic group. 15. The polymer composition of claim 13 wherein the phosphorus-sulfur 42 200918590 Wherein 1 is an integer of 1 or more, when 1 is 1, q is zero, and when 1 is 2 or more, q is 1, Z represents a cationic group, and each R 2 is independently hydrogen, alkyl or inert In the substituted alkyl group, each R3 is independently a covalent bond or a divalent bonding group, and A is an organic group. 16. The polymer composition of claim 15 wherein each R2 is hydrogen and R3 is free of hydrogen on the carbon atom (group) which has been directly bonded to the adjacent (112) 2 (: group) The polymer composition of claim 13, wherein the phosphorus-sulfur additive is represented by any one of the following structures. Wherein 1 is an integer of 1 or more, when 1 is 1, q is zero and when 1 is 2 or more, q is 1, Z represents a cationic group, and A is an organic group. 15 18. The polymer composition of claim 13, wherein the phosphorus-sulfur additive is represented by any one of the following structures: 43 200918590 In Wherein 1 is an integer of 1 or more, when 1 is 1, q is zero and when 1 is 2 or more, q is 1, Z represents a cationic group, and A is an organic group. 19. The polymer composition according to any one of claims 1 to 18, wherein the combustible polymer is polystyrene. 20. The polymer composition of claim 19, wherein the polymer composition is foamable. 21. A phosphorus-sulfur compound, represented by the following structure: 10 wherein each X is independently oxygen or sulfur, each m is independently zero or 1, Μ represents a metal atom which can have hydration binding water, η is a number from 1 to 4, and each R is independently unsubstituted or The inertly substituted hydrocarbyl group or the R group of any R-(X)mP-(X)mR structure together may form an unsubstituted or inertly substituted divalent organic group. 44 200918590 22. A phosphorus-sulfur compound as claimed in claim 21, which is represented by any of the following structures Wherein Μ represents a metal atom which may have a hydration binding water, η is a number from 5 to 1 and each R is independently an unsubstituted or inertly substituted hydrocarbon group or an R group of any RJXVP-eV-R structure. Together, an unsubstituted or inertly substituted divalent organic group can be formed. 23_ A phosphorus-sulfur compound as claimed in claim 21, which is represented by any one of the following structures Wherein Μ represents a metal atom which may have a hydration binding water, η is a number from 1 to 4, each R 2 is independently hydrogen, an alkyl group or an inertly substituted alkyl group, and each R 2 is independently a covalent bond or a divalent bond. a group, and ρ is as described above. 24. The phosphorus-sulfur compound of claim 23, wherein each R2 is 15 hydrogen and R3 is hydrogen free on the carbon atom (group) which has been directly bonded to the adjacent (R2) 2C group. Alkanediyl. 45 20091859ο • A phosphorus-sulfur compound as claimed in claim 21 of the patent scope, which is represented by any of the following structures The middle one represents a metal atom which can have water for hydration and η is a number from 1 to 4. 26. A phosphorus-sulfur compound as claimed in claim 21, which is represented by any of the following structures Wherein Μ represents a metal atom which may have hydration combined water and η is a number from 1 to 4. 27. A phosphorus-sulfur compound, represented by the following structure: Wherein each X is independently oxygen or sulfur, each m is independently zero or 1, 1 is an integer of 1 or more, when 1 is 1, q is zero, and when 1 is an integer of 2 or higher, 46 200918590 q is 1, Z represents a cationic group, and each R independently is an unsubstituted or inertly substituted hydrocarbon group or an R group of any R-(X)mP-(X)mR structure may form an unsubstituted or inert substitution. a divalent organic group, and A is an organic group. 5 28. A phosphorus-sulfur compound as claimed in claim 27, which is represented by any of the following structures: Wherein 1 is an integer of 1 or more, when 1 is 1, q is zero, and when 1 is 2 or more, q is 1, and Z represents a cationic group, and each R is independently unsubstituted 1 or The inertly substituted hydrocarbyl group or the R group of any R-(X)mP-(X)mR structure together may form an unsubstituted or inertly substituted divalent organic group, and A is an organic group. 29_ A phosphorus-sulfur compound as claimed in claim 27, which is represented by any one of the following structures: Wherein 1 is an integer of 1 or more, when 1 is 1, q is zero, and when 1 is 2 or 47 200918590 is greater, q is 1, Z represents a cationic group, and each R 2 is independently hydrogen, alkyl Or an inertly substituted alkyl group, each of which is independently a covalent bond or a divalent bond group, and A is an organic group. 5: The phosphorus-sulfur compound of claim 29, wherein each R 2 is hydrogen, and R 3 is not bonded to the carbon atom (group) adjacent to (112) 2 (: group) Hydrogen alkanediyl. 31. A phosphorus-sulfur compound as claimed in claim 27, which is produced by any of the following structures: 10 wherein 1 is an integer of 1 or more, when 1 is 1, q is zero and when 1 is 2 or more, q is 1, Z represents a cationic group, and A is an organic group. 32. A phosphorus-sulfur compound as claimed in claim 27, which is represented by any one of the following structures: I A, Wherein 1 is an integer of 1 or more, when 1 is 1, q is zero and when 1 is 2 or more, q is 1, Z represents a cationic group, and A is an organic group. 48 200918590 VII. Designated representative map: (1) The representative representative of the case is: (). (None) (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: R (X)m ^(X)m (X)m R R