DE2224163A1 - New bis (2,3-dibromopropyl) phosphonates, process for their preparation and their uses - Google Patents

Description

IICHT5ANWÄITE ^

IF. JUR. DIFL.-CHEM. WALTER BEIL

ALFRCO! LOcivt: MEÄ ^{Ka / G}

Dfi. JU ¹ S. ? '.'":. ^r .-] '.- A. H ₁ -J. WOLFF

DR. ^ ..-. ".- .., 0.3,1 !. 17th May 1972

4aa r IiA t \ ;:. F !. '«f Λί · Λ iUAIN - HÖCHST

Our no. 17 859

Stauffer Chemical Company 'New York ,, N.Y., V.St.A.

New bis (2,3-dibromopropyl) phosphonates, process for their preparation and their uses

The present invention relates to the bis (2,3-dibromopropyl) phosphonates the general formula

¹¹ ^ ~ OCH ₉ CHBrCH ₉ Br XP

¹ OCH ₂ CHBrCH ₂ Br

in which X is a phenyl radical or a Y-CHp radical, where Y is a chlorine or bromine atom, and processes for their preparation. The new compounds according to the invention are:

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222A163

Bis (2,3-dibromopropyl) chloromethylphosphonate, ' Bis (2,3-dibromopropyl) bromomethylphosphonate and Bis (2,3-dibromopropyl) phenyl phosphonate.

It has been found that the new compounds have numerous otherwise flammable substrates such as urethane foams and the so-called polyester resins, which are produced by the reaction of dibasic acids and dibasic acids Alcohols are obtained to impart excellent flame retardant properties. Of those listed above Compound is the bis (2,3-dibromopropyl) chloromethylphosphonate because of the simplicity and low cost of manufacture, as well as the results obtained therefrom Use as a flame retardant for synthetic resins and foams are preferably used. It it should be noted that the use of the term "halogen" in this disclosure applies to both chlorine and bromine atoms relates. It is also apparent to those skilled in the art that the phenyl radical in the bis (2,3-dibromopropyl) phenylphosphonate may optionally be substituted by one or more non-interfering radicals, i.e. by radicals the presence of which does not affect the use of the compound as a fire retardant additive. Such non-disturbing ones Residues include halogen atoms, nitro, alkyl, hydroxyalkyl, sulfonate, carboxyl and hydroxyl radicals.

The compounds of the invention can be prepared in two different ways. These manufacturing routes are represented by the following equations:

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222A163

Path No. 1

If

X-PCl ₂ +
O

11

X-P

Path No. 2

2HOCH ₂ CHBrCH ₂ Br

OCHoCHBrCHoBr

OCH ₂ CHBrCH ₂ Br

2HCl

X-PCl ₂ +

0 π

X-P,

Il

X-P

2HOCH ₂ CH = CH ₂ -

.0CH ₂ CH = CH ₂

"OCH ₂ CH = CH ₂

2Br

-OCH ₂ CHBrCH ₂ Br

₂ CHBrCH ₂ Br

2HCl

where X has the meaning given above.

In carrying out the process of Equation No. 1 above, a halomethylphosphonic acid dichloride is used or a phenylphosphonic acid dichloride in twice the amount, on a molar basis, of 2,3-dibromopropanol

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implemented. This reaction takes place in an organic solvent solution in the presence of a catalytically effective amount of a Lewis acid. The selected solvent should have a boiling point of at least about 60 ° C and can consist of benzene, chloroform, tetrachloroethane, preferably carbon tetrachloride. Suitable Lewis acid catalysts include aluminum trichloride, magnesium chloride and preferably titanium tetrachloride. In most cases the catalyst should be present in the system at a concentration of about 0.1-1.0 % based on the total weight of both reactants, ie, based on the weight of the halomethyl or phenylphosphonic acid dichloride and the 2,3-dibromopropanol .

For carrying out the reaction, the, the two reactants and the selected catalyst-containing organic solvent solution at a temperature of about 40 - heated 100 ⁰ C, preferably at about 80 ° C to the first equivalent to develop the hydrogen chloride that occur as a byproduct. The solution is then refluxed at the boiling point of the solvent to evolve the second equivalent of hydrogen chloride. The reaction times required to evolve each equivalent of hydrogen chloride are about the same, with the total reaction time being about 2 to 24 hours, depending on the amounts of reactants used. This process is preferred to the process according to route no. 2 because the compounds according to the invention are obtained in higher yield and because it is more economical.

When performing the method according to the above

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Equation No. 2 listed is first the diallyl phosphonate as an intermediate according to a known Reaction produced in which phenylphosphonic acid dichloride or a halomethylphosphonic acid dichloride, e.g. chloromethylphosphonic acid dichloride, a double amount, on a mole basis, allyl alcohol and triethylamine is added. This reaction is carried out at a temperature of 0 to 5 ° C. The triethylammonium chloride obtained as a by-product is then removed by dissolving in water and washing with aqueous sodium bicarbonate. the organic layer is then separated and dried with a desiccant such as magnesium sulfate. After removing of the solvent by distillation is the diallyl halomethyl or diallyl phenyl phosphonate from the reaction mixture obtained. It can then be purified by further distillation.

The intermediate diallyl halomethyl or diallyl phenyl phosphonate thus prepared is then in a solvent consisting of a chlorinated hydrocarbon such as methylene chloride, chloroform or tetrachloroethane, preferably dissolved in carbon tetrachloride. This solution wid then slowly mixed with a solution of bromine in a chlorinated hydrocarbon solvent, again preferably carbon tetrachloride is used. The bromine should be used in an amount that is up to Mole basis equal to twice the amount of the diallyl halomethyl or diallyl phenyl phosphonate intermediate. The reaction is slightly exothermic. After the reaction is over, the organic layer is dried, filtered and removing the solvent under vacuum, wherein the

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desired bis (2,3-dibromopropyl) halomethyl or phenyl phosphonate is obtained. That made by either of the two manufacturing methods described above Bis (2,3-dibromopropyl) halogen or phenyl phosphonate a mixture of crystalline and liquid optical isomers,

At this point it should be noted that the preparation of a compound that is close to the phosphonates according to the invention is related, namely bis (2,3-dibromopropyl) aziridinylphos-

phonate, i.e. CH "

(CH ₉ Br-CHBrCH ₅ O) ₀ PN ' \ ^d

0 ^CH 2

is also currently being considered. This compound is made by reacting ethyleneimine and 2,3-dibromopropylphosphonyl chloride produced with triethylamine as a catalyst, with triethylamine hydrochloride also being a by-product is obtained.

As mentioned above, the novel compounds prepared by the process of the present invention impart excellent properties flame retardant properties when used with a number of polymeric substrates usually very are easily flammable, are intimately mixed. It has been found that these compounds are particularly suitable for Manufacture of flame-retardant polyester resins are suitable. This group of resins generally includes the products that by heating a mixture of glycols, e.g. propylene or diethylene glycol, unsaturated dibasic acids or anhydrides, e.g. fumaric acid or anhydrides, e.g. fumaric or maleic anhydrides, and optionally

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a saturated dibasic acid or an anhydride * e.g. isophthalic, phthalic, chlorendic, tetrabromophthalic and tetrachlorophthalic acid and their anhydrides, which are used for Control the reaction and modify the properties of the product obtained. The liquid polyester thus obtained is then usually mixed with a reactive monomer, e.g. Styrene, diallyl phthalate, diallyl isophthalate or triallyl cyanurate added and to catalyze the final Copolymerization is a peroxide catalyst, e.g. benzoyl peroxide, introduced. These polyesters, or unsaturated polyesters as they are often called, are curable and are widely used in reinforced plastics and for embedding electrical components. The new Compounds according to the invention are therefore particularly suitable for these unsaturated polyester resins, which are, for example, with glass fiber mats, Glass fabrics, woven glass fiber strands, chopped roving, paper, asbestos, textiles and the like are reinforced to impart excellent flame retardancy.

The bis (2,3-dibromopropyl) halomethyl- or phenylphosphonate can also be used as a flame retardant for urethane resins that are rigid, flexible or foamed can be used. These polymers are usually made by reacting an isocyanate such as toluene diisocyanate or diphenylmethane-4-l | 'diisocyanate with a second Reagent consisting of a polyol with 2 or more hydroxyl groups. In the present description the term "isocyanate material" includes all polyisocyanate or urethane compounds containing two or more unreacted -NGO residues. The most popular

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Urethane resins are made by reacting toluene diisocyanate made with a polyether or polyester polyol. Typical polyesters are the reaction products of adipic acid and / or phthalic anhydride and ethylene glycol. Other polyols that can be used instead of the polyester are polyethers such as polyoxypropylene diols and polyoxypropylene triols, castor oil, methylglucoside polyether polyols and Drying oils and the like.

This is what sets urethane foams apart from others cellular plastics that the chemical reactions causing the foaming at the same time as the polymer-forming reactions Reactions proceed. As with the urethane resins, the polymeric component of the urethane foams is carried through Reaction of a polyol with an isocyanate produced. If the isocyanate is used in an amount greater than that which reacts with the polyol is used and if water is present, the excess isocyanate reacts with the Water forms carbon dioxide, which foams the mixture, urethane foams can be flexible or rigid and have open or closed cells, depending largely on the polyol used. Networked Foams are rigid or semi-rigid. Sometimes auxiliary propellants or foaming agents are also used, such as the different ones Halocarbons, especially in rigid foams, are used. Others often in urethane foams incorporated ingredients are catalysts that control the rate of the reaction and a surface active ingredient Means to stabilize the rising foam and to regulate the cell size.

20 9 8 48/1 246

Urethane foams are manufactured using three general processes:

the prepolymer process, the sini prepolymer process and the one-shot process. In the prepolymer process a polyol is reacted with an isocyanate to produce a compound that is stored and subsequently mixed with water, a catalyst and in some cases with a foam stabilizer. In the semi-prepolymer process there is 20 pounds of the polyol previously reacted with all of the isocyanate, and this product is later reacted with one containing the remaining ingredients Main loading implemented. In the one-step process, an isocyanate, a polyol and a catalyst are used introduced into separate streams leading to a mixer attachment from which the mixed ingredients are removed and be brought into a form.

Regardless of the manufacturing process, polyurethane foams can be found increasing use in a wide variety of applications, such as household furnishings, aircraft construction, inserts for mattresses and upholstery, lining materials or jacket materials and sleeping bags, soundproof walls, for insulation against heat loss, for rescue facilities, fishnet floats, foam rubber articles, air filters, packaging material and for bone surgery.

Other polymeric substrates with which the invention New compounds that can be mixed to obtain flame-retardant mixtures include: Polymers of Nitriles of ethylenically unsaturated acids such as polymeth-

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acrylonitrile, polyacrylonitrile, and the copolymers of methacrylonitrile or acrylonitrile with a small amount of one or more vinyl monomers such as the lower alkyl acrylates and methacrylates, styrene and ct-methylstyrene;

Polymers of methyl methacrylate such as polymethyl methacrylate, and the copolymers of methyl methacrylate with small Amounts of one or more α, Α-ethylenically unsaturated Monomers that can be polymerized with these, such as the C-J-Cq-alkyl, cycloalkyl and bicycloalkyl esters of acrylic acid, and the Cg-Cg alkyl, cycloalkyl and bicycloalkyl esters of methacrylic acid such as ethyl acrylate and methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, norbornyl acrylate, and cyclohexyl acrylate, vinyl aryl compounds such as e.g. ce-methylstyrene and styrene, and a, ß-ethylenic nitriles unsaturated carboxylic acids such as acrylonitrile and methacrylonitrile;

Acrylonitrile-butadiene-styrene resins, usually called "ABS" resins, which are usually made from a mixture of a styrene-acrylonitrile copolymer with a ratio of 60 to 80: 40 to 20, and about 10 to 40 wt. it of an acrylonitrile-butadiene copolymer with a ratio of 5 to ¹ IO: 95 to 60 or of a mixture of a styrene-acrylonitrile copolymer in a ratio of 60 to 80: 40 to 20 and about 10 to 40 parts by weight 5 ? a graft copolymer of the latter on polybutadiene;

Poly (ce-olefins) such as polypropylene and polyethylene and copolymers one or more »-olefins such as ethylene or propylene with a small amount of one or more ethylenically unsaturated monomers such as 4-methylpentene-1, butene-1,

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Norbornene and its derivatives, cyclopentadiene, cyclopentene, Cyclobutene, vinyl acetate, the C ^ -C ^ -alkyl acrylate and Methacrylate esters and mixtures of homo- and copolymers the cc-olefins and other types of thermoplastic Polymers;

Polymers of styrene such as polystyrene, poly (a-methylstyrene) and poly (tert-butylstyrene) and copolymers of styrene, Ot-methylstyrene or tert-butylstyrene with a small Amount of one or more ethylenically unsaturated comonomers, such as nitriles of ethylenically unsaturated carboxylic acids such as acrylonitrile and methacrylonitrile, C 1 -C 4 alkyl esters of acrylic and methacrylic acids such as methyl methacrylate and 2-ethylhexyl acrylate, and graft copolymers of Styrene, tert-butylstyrene or α-methylstyrene with polybutadiene and other hydrocarbon elastomers;

Cellulose resins such as cellulose esters and mixed esters such as cellulose nitrate, cellulose acetate butyrate, cellulose acetate propionate and cellulose ethers such as ethyl cellulose;

Polyamide resins, ie the resins which are produced by the condensation of di- or polyamines with di- or polybasic acids or by the polymerization of lactams or amino acids. Typical polyamides are nylon H ₃ which is made from pyrrolidone, nylon 6 which is obtained by polycondensation of caprolactam, nylon 66 which is obtained by condensation of hexamethylenediamine with adipic acid, nylon 610 which is obtained by condensation of hexamethylenediamine with sebacic acid, nylon 7, which is a polymer of ethylaminoheptanoate, nylon 9 »which is made from 9-aminononanoic acid, and nylon 11 which is made from 11-aminoundecanoic acid;

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Polycarbonate resins, i.e. the resins produced by the reaction of a difunctional alcohol or phenol, such as bisphenol A and phosgene or an alkyl or aryl carbonate;

Polyacetal resins, that is, the resins obtained by anionic polymerization of formaldehyde to form a linear molecule of the -0-CH ₂ -O-CHp-O-CH _{2 type} ;

Polyphenylen_oxidharze produced by oxidative polymerisation of 2,6-dimethylphenol in the presence of a copper amine complex catalyst getting produced;

Polysulfone resins, i.e. the resins with an SOp bond, those by the reaction of sulfur dioxide with olefins such as 1-butene or, preferably, by the reaction of bisphenol A. obtained with 4,4'-dichlorodiphenylsulfone;

the acrylate-styrene-acrylonitrile resins, usually called "ASA" resins, which consist of copolymers which contain a larger amount of a C2-Cg-alkyl acrylate ester, based on about 65-95 % by weight, based on the latter , a styrene-acrylonitrile cojrfpolymer in a ratio of 70 to 80 to 30 to 20 is grafted, and

the methacrylate-butadiene-styrene resins, usually "MBS" resins called, which contains a smaller amount of a methyl methacrylate-styrene-acrylonitrile terpolymer, that is grafted onto and / or mixed with polybutadiene or a copolymer of butadiene, and minor amounts of comonomers such as styrene and acrylonitrile.

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It has been found in all cases that the new fiction, contemporary Compounds with polymeric substrates form mixtures, which are characterized by their excellent flame retardancy Characteristic features and the ease of the mixture. The term "fire retardant" or "flame retardant" refers to in the present disclosure to the special property of a material that has a certain degree of it Resistance to ignition and "burning" confers. So a fire retardant or flame retardant fabric is a Substance that has low flammability and flame spread having.

The actual mixing of the bis (2,3-dibromopropyDhalogenmethyl- and phenylphosphonates with the selected polymeric substrate, i.e. with one or more of the polymers listed above can be made by any conventional method which results in an intimate mixture the additional compound or compounds with the bulk of the substrate polymer leads. So it can be incorporated into the reaction product that is used for curing or polymerizing of the polymer is used, or it can be blended with a previously prepared polymer.

As for the proportions, it depends. applied amount of the compound according to the invention with a polymer substrate, depending on the degree of fire retardancy desired for the resulting mixture specific physical properties that are sought, as well as other technical and economic properties Considerations that are familiar to the person skilled in the art. However, in order to get a substance that is self-extinguishing, it is

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an effective amount generally desired, one or more of these novel compounds to be used, sufficient to provide the resulting mixture has a phosphorus content of at least about 1 wt - to give.%. Depending on the various above-mentioned Paktoren the novel compounds of the invention may DIE, mixtures containing about 5 to 30 wt -.% Of one or more of these bis (2,3 ~ dibromopropyl) halogenmei \ tyl- or -phenylphosphonate included.

The mixtures obtained can also contain stabilizers, plasticizers, fillers, pigments, dyes, tanning agents, Decorative additives such as reflective metal foils or flakes and other embedded solids such as fiberglass, Textile fibers, asbestos, paper and the like, provided that they have the flame retardant properties ^ n do not affect these products. These mixtures can also contain other flame retardants such as antimony compounds, chlorinated paraffins, perchlorinated alicyclic compounds, bromine containing organic compounds, halogenated alkyl phosphates or phosphonates, alkyl phosphates (alkyl acid phosphates) and small amounts of phosphoric acid.

The new mixtures according to the invention, the mixtures of one of the aforementioned polymers and one or contain several of the new compounds according to the invention, can be used for all purposes known to the person skilled in the art of coating, Forming, adhesive impregnation, laminate and foam production may be used where it is desired to impart a fire retardant property to the final product. These fire retardant mixtures can therefore be used as

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coating agents, impregnating agents, fillers, laminating agents (laminants), adhesives and the like for substrates such as wood, paper, metals, textiles based on natural and synthetic fibers or mixtures thereof, synthetic polymer films such as those based on of polyolefins, regenerated cellulose, i.e. cellophane, polyvinyl chloride, polyester and the like, leather, natural and synthetic rubbers, fiberboard and plastics produced by addition or condensation polymerization processes can be used.

With regard to the use of bis (2,3-dibromopropyl) chloromethy lphosphonate s as a faQ. that because the chloromethyl group is bonded directly to the P = O group, the chlorine atom in the chloromethyl group is highly reactive. Because of its high degree of reactivity, the chlorine atom can make cellulosic fabric and readily alkylate other cellulosic substrates, resulting in their permanent incorporation into the cellulosic substrate results, which significantly improves the durability of the resulting fire-retardant finish.

The following examples serve to illustrate the invention. In the following examples, unless otherwise stated, all parts are by weight.

example 1

This example illustrates the preparation of bis (2,3-dibromopropyl) chloromethyl phosphonate by reacting 2,3-dibromopropanol with chloromethylphosphonic acid dichloride.

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A three-necked flask equipped with a water cooler, a thermometer and gas inlet and gas outlet devices was filled with 176 »3 g (0.81 mol) 2,3-dibromopropanol, 66.5 g (0.40 mol) chloromethylphosphonic acid dichloride, 200 ml carbon tetrachloride and 0, 10 ml of a charged titanium chloride catalyst, the reactants were initially for one hour at 40 C and then for two hours at 80 ⁰ C heated. During this time, an equivalent of HCl developed, which was removed from the reaction vessel and placed in a water container. In the course of a further 4 hours of heating at 80 ° C., the second equivalent of HCl evolved. After cooling, the light yellow liquid obtained was washed with two portions, a total of 400 ml, of a 20% strength by weight aqueous NaHCO .. solution and then with 400 ml of water. Thereafter, the organic layer was separated and dried over anhydrous magnesium sulfate. After filtering off the desiccant, the carbon tetrachloride was removed in vacuo, leaving a milky white liquid (213.5 g, 97 % yield)

received whose refractive index "25 _{Λ cCnc,,}

'λ ■ "- 1.5625 and their

Acid number = 2.80 mg KOH / g of the sample. The IR analysis showed only a trace of residual 2,3-dibromopropanol and is consistent with the assumed structure of the product.

After standing at room temperature for a few days, the white liquid began to crystallize extensively. Since each dibromopropyl radical includes a chiral carbon atom, it is believed that the crystalline portion of the product of one of the optical isomers of bis (2,3-dibromopropyl) chloromethylphosphonate, most likely

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is the meso modification. . Accordingly, constitute, the liquid part of the product is probably the dl-racemic modification of that phosphonate The crystalline isomers was recrystallized from isopropanol to give white needles were obtained, which had a melting point of 68-69 ⁰ C; NMR, ie nuclear magnetic resonance, (CCL ^) γ 5 »9 5.3 (6h, multiplet, PCH ₂ + POGH ₂ ) and τ 6.5-6.0 (6H, multiplet, CH ₂ BrCHBr);
Analysis:

Calculated: C 15.82 H 2.26 P 5.80 % found: C 15.85 H 2.09 P 5.93 %.

In a repetition of the manufacturing process described above Bis (2,3-clibromoprpyl) bromomethylphosphonate was produced, the chloromethylphosphonic acid dichloride was replaced by an equivalent amount of bromomethylphosphonic acid dichloride.

Example 2

This example illustrates the preparation of bis (2 _s 3 ° dibromopropyl) chloromethylphosphonate by the reaction of bromine nifc diallylchloromethylphosphonate

The Diallylchlormethylphosphonat if ur-de initially prepared by · in that (g 85 _s 0 · 8 mol) 250 ml of benzene, "T-riäthylamin and 48.7 g (0.8 mol + 5 1) gave allyl alcohol in a reaction vessel. The contents of the vessel were stirred and then abgekühlt- to 0 C. Thereafter, 67 g (0.4 mol) ChlormethylphosplionsäurediChlorid over a period of 75 minutes slowly added _s while maintaining the temperature in the range of 0 ^ 5 C was "The he = · Holding slurry would be in an ice bath for 45 minutes

2098A8 / 1246

touched. This slurry was then treated with 250 ml of ice water to dissolve the triethylamine hydrochloride precipitate. The benzene solution containing the product was washed with 125 ml of a cold 5% by weight aqueous NaHCO 3 solution and then with 125 ml of a cold 5% by weight aqueous NaCl solution, after which it was concentrated by distillation over copper resinate. The product obtained was distilled in an oil bath, 46.0 g (57 % yield) having a boiling point of 86-88 ° C./0.45 mm being obtained; "25 _ _{Λ hf} - _h

14.9 g (0050 mol) of the diallylchloromethylphosphonate thus prepared were dissolved in 100 ml of carbon tetrachloride in a flask. A solution of 16.0 ^ (0.010 mol) of bromine in 50 ml of carbon tetrachloride was then added to the resulting solution. A weakly exothermic reaction was found. After the addition of bromine had ended, the carbon tetrachloride solution was washed with 100 ml of a 5% strength aqueous sodium bicarbonate solution and then with 100 ml of water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The solvent was removed in vacuo. The product (27 »1 g ₉ quantitative yield) showed an IR spectrum and physical constants identical to those of the compound prepared by the method described in Example 1»

Example 3

This example illustrates the use of one of the new compounds according to the invention for the production of flame-retardant polyester resins.

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Table I.

O CD CO

CO

ro

CD

Flame
more inhibiting
additive Polyester-
Resin system With glass
ver
strengthens LOI at Concentrate iof ^ of 15phr 20phr HLT-15 / Evaluation / Glimm-
time (sec. 2 / with conc
trations of 5phr lOphr | l5phr 84 / - Bis (2,3-di-
bromopropyl) -
chloromethyl
phosphonate Hetron 24370
RCI Polylite
31-007 Yes
Yes Ophr 5phr lOphr 26.1 28.1 Ophr 100/68 100/55
48 / - Koplac 1060-5 no 28.4
19.5 33.3 38.0
24.0 24.8 20 / -
0 / - RCI 34-440 Yes 17.7 21 _a 8 100/68 Polymethyl
methacrylate no 36 / - rris- (2,3-di-
j-rompropyl) -
phs | pphat Hetron 24370
RCI Polylite
3Ϊ-ΟΟ7 Yes
Yes 16.9 20.5 25 _S 3 25.3 100/81 24 / - Koplac IO6O-5 no 28.4
19 _S 5 34.3 38.2
23 * 0 22.8 24 _S 3 20 / -
0 / - Polymethyl
methacrylate no 17.7 21 _s 0 16.9 2O ₃ 4

VO

ro ro

CD CO

Hetron 24370 - an unsaturated polyester of chlorendic acid (Hooker Chemical Company), RCI Polylite 31-007 - a non-halogenated unsaturated polyester (Reichold Chemicals, RCI 34-440 - an unsaturated polyester of tetrabromophthalic acid (Reichold Chemicals, Inc.), Koplac 1060- 5 - a non-halogenated unsaturated polyester (Koppers Company, Ina »), phr = parts per 100 parts resin»

The non-glass reinforced samples in Table I above are rods with the dimensions 13 mm 100 mm and were produced by first the appropriate polyester resin and the bis (2,3-dibromopropyl) chloromethyl phosphonate and prepared according to the method of Example 2 intimately mixed a small amount of catalytic benzoyl peroxide. The resulting mixture was then subsequently in tubular forms one hour at 100 ⁰ C and for an additional 18 hours at 135 - hardened I ^{1 0} C IO.

The samples amplified with glass were cut from reinforced sheets, consisting of a mixture of the suitable polyester resin and a suitable amount of bis (2,3 ~ dibromopropyl) chlormethy Iphosphonat and 30- ¹ IO% of glass consisting of 3 layers of glass mat (457> 7 g / m; 1-1 / 2 oz./sq.ft.) arranged in layers between 2 layers of glass fabric (339 »06 g / m; 10 oz./sq.yd.). After the plates had thickened and become established, they were cured at 60 ⁰ C before the test in an oven for 16 hours.

As control samples for this experiment, samples were produced which in one case did not contain a compound according to the invention while others contained an equivalent amount of tris (2,3-dibromopropyl phosphate, a commercially available flame retardant Addition instead of bis (2,3-dibromopropyl) chloromethylphosphonate contained.

The flame retardancy of these polyester resin samples was determined according to the Limiting Oxygen Index (LOI) ASTMD-2863 and the methods of the Hooker Laboratory Test-15 (HLT-15). The 'former Procedure was used by Fenimore and Martin in the

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November 1966 issue of "Modern Plastics" described while the latter method is briefly described in Lyons, Chemistry and Uses of Flame Retardants, Wiley Interscience, 197ο is described. Briefly summarized, the LQI procedure puts flame retardation in a direct relationship to a Measurement of the minimum percentage of oxygen in an oxygen / nitrogen mixture that contains the sample burns; LOI is calculated as follows:

/ O ₀ I.

LOI = ZJ £ - - r 100

So a higher LOI value shows a higher degree of Anti-flame on. The HLT-15 test was carried out in a draft-free room (cabinet) with 20.32 χ 1.27 x 0.318 cm samples which hung vertically from above. A 12.70 cm long Bunsen burner flame with a 3 »81 cm long inner blue cone has been tilted at an angle of 20 ° from vertical so that the blue cone is just that touched the lower end of the sample. Five specimens from each sample were tested according to the following scheme:

Applications Burning time (On Time) Off Time in sec. in sec. 1 VJl 10 2 7th 14th 3 IO 20th 4th 15th 30th 5 25th 50

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A rating of 4 was given each time a sample extinguished during the off time. A score of 0 is given and the attempt ended in a specimen, if it still continued to burn over the given time to come. If all 5 samples pass the applications, a rating of 100 is achieved. The elapsed burning times were then added to produce a further rating, ie the flame time of the sample. Thus, a high rating and a low glow time indicate superior flame retardancy.

The above data in Table I show that the bis (2,3-dibromopropyl) chloromethylphosphonate when used gives excellent results as a flame retardant additive for polyester resins; these results are better than those which were achieved with a commercially available phosphate additive. In addition, the new invention Phosphonate compounds have a degree of hydrolytic stability that is superior to that of was found in these commercially available phosphate ester additives.

Example 4

This example illustrates the preparation of bis (2,3-dibromopropydphenylphosphonate by the reaction of 2,3-dibromopropanol with phenylphosphonic acid dichloride.

In a reaction vessel, the 56.9 g (0.26 mol) of freshly distilled 2,3-dibromopropanol dissolved in 150 ml of carbon tetrachloride and 0.5 g of anhydrous magnesium chloride was added a solution of 25, ¹ I g (0.13 mol ) Phenylphosphonic

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acid dichloride in 50 ml carbon tetrachloride. No reaction was observed at room temperature (approx. 25 C); after heating to Rückflußtemperstur (80 ⁰ C), however, HCl developed at a moderate speed. The IR analysis of equal amounts showed that the reaction was 80 % complete after 4 hours and practically 100% after 20 hours.

The clear, water-pale solution obtained was washed partially with 250 ml of a 5% strength by weight aqueous NaHCO 3 solution and then twice with 250 ml of water. The organic layer was separated and dried over anhydrous magnesium sulfate; the solvent was stripped off in vacuo to give a white liquid (53 g, 73 % yield).
The analysis showed the following:

NMR (CCl ₄ ):

τ 1.8-2.7 (5H, multiplet, phenyl) T 5.3-5.8 (6H, multiplet, CH ₃ BrCHBr) T 6.2 (4H, broad singlet, -CH ₂ O-)

eiuuex ·; :

3090, 3060 and 3040 cm " ¹ I _Phen yl 1580 cm" ¹ )

IR (clean):

3090,3 1580 cm 1252 cm " ¹ (P- * 0)

1160, IO35 and 990 cm " ¹ (POC)

Elemental analysis:

Theoretically found

% P 5.5 5.0

% Br 57.3 60.1

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Example 5

This example explains how to use the / connection of the Example 4 for the production of flame-retardant polyester resin mixtures.

Table II

Plamm Polyester- with glass LOI at Kon lOphr . ,, _ HLT-15 at more inhibiting Resin- ver centrations a conc additive system strengthens from tration of Ophr 5phr Bis (2,3-di- Hetron Yes 21.1 100/114 bromopropyl) - 24370 phenylphos- phonate Koplac no 17.7 1060-5 Tris (2,3-di- Hetron Yes 21.0 100/81 bromopropyl) - 24370 phosphate Koplac no 17.7 1060-5

The test samples of Table II were prepared like those of Table I. The data in Table II show also the excellent results obtained when using bis (2,3-dibromopropyl) phenylphosphonate as a flame retardant Additive for polyester resins were obtained.

Example 6

This example illustrates the use of one of the new compounds according to the invention for producing a flame-retardant one Urethane foam.

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A number of different polyurethane foams was prepared _s by their respective components were mixed in the sequence as they are listed in the table below and each of the obtained mixtures was filled into a 20.32 cm square container.

To carry out the procedure, all ingredients, with the exception of the TDI, i.e. the toluene diisocyanate, were carefully selected mixed together, after which the TDI was introduced, whereby the foaming reaction was initiated. In each case the TDI index of the foams obtained was 108, the latter factor being calculated as follows became:

Equivalents of the -NCO groups

TDI index = ■ - = X

All equivalents of the -OH groups in the polyol, flame retardants, and water

The degree of flame retardancy of the foams obtained was determined by the method specified in ASTM D-1962. This test determines the surface flammability of the foams by using a foam specimen with the dimensions. 15.24 5.08 χ 1.27 cm on a horizontally arranged
Hardware cloth is laid out so that the .1.27 cm dimension is vertical, and a three-inch blue flame ends for 60 seconds
a barrel bunsen burner having a diameter of 0.952 cm, which is provided with a 4.76 cm wide slot attachment, is brought into contact. During this test, the burning rate is measured in cm per minute and it is also observed whether the sample extinguishes by itself and the time it takes

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it needs to go out by itself, or whether it continues burns until it is completely burned. The results of these measurements are also shown below Table listed.

Part (s)

Control foam foam sample fabric No. 1 No. 2

A 3000 molecular weight triol is obtained
by reaction of propylene oxide
and glycerin (Olin Corp., trade name
"Poly G 3O3O") 200.0 200.0 200.0

Bis (2,3-dibromopropyl) chloromethyl

phosphonate 30.0

Tris (2,3-dibromopropyl) phosphate 30.0

Water 8.0 8.0 8.0

A surface-active silicone

(Union Carbide Corp., "L-540") 1.8 1.8 1.8

N-ethyl morpholine (catalyst) 0.4 0.4 0.8

A 67 % solution of dimethyl

aminoethyl ether in dipropylene

glycol (catalyst), (Union

Carbide Corp., "Niax Catalyst

A-I ") 0.35 0.35 0.35

A 50% solution of tin-II

octoate in dioctyl phthalate

(Katlysa <% r), (M & T Div. Of American

Can Co., "Catalyst T-IO") 0.8 0.8 0.8

Methylene chloride (blowing agent) 6.0 6.0 6.0

An 80:20 mixture of 2,4 and

2,6-toluene diisocyanate (TDI) 102.3 102.3 102.3

2098A8 / 12AG

Parts (g) (continued)

Control foam foam sample No. 1 No. 2

ASTM D-I692 - Big Burns - Self - Self -

ter with erasing erasing speed of in 40 sec. in 25 sec. 22.86 cm / after burning after Ver-Min. To burn to a complete burn of only 7,87 cm by 5,59 cm

The above data show that bis (2,3-dibromopropyl) chloromethylphosphonate when used as a flame retardant additive for urethane foams, excellent results supplies; these results are much better than those obtained with tris (2,3-dibromopropyl) phosphate, a commercially available flame retardant additive.

209848/1246

Claims (12)

Patent claims: New bis (2,3 ~ dibromopropyl) phosphonate of the general formula OCH ₂ CHBrCH Br χ - ρ _χ OCH ₂ CHBrCHpBr in which X denotes a phenyl radical or a Y-CH ₂ radical, where Y is a chlorine or bromine atom. 2. Bis (2,3-dibromopropyl) chloromethylphosphonate as a compound according to claim 1. 3. Bis (2,3-dibromopropyl) bromomethylphosphonate as a compound according to claim 1. 4. Bis (2,3-dibromopropyl) phenylphosphonate as a compound according to claim 1. 5. Process for the preparation of the bis (2,3-dibromopropyl) phosphonates according to Claim 1, characterized in that 2,3-Dibromopropanol at elevated temperatures with a Halomethyl or phenylphosphonic acid dichloride converts. 6. Process for the preparation of bis (2,3-dibromopropyl) phosphonates according to Claim 1, characterized in that one bromine with a diallylhalomethyl or phenylphosphonate in a chlorinated hydrocarbon solvent 209848/1246 reacted and the 2,3 ~ dibromopropanol obtained from the The reaction mixture is separated off. 7. A flame retardant mixture containing an intimate mixture of a polymeric substrate and an effective amount a bis (2,3-dibromopropyl) phosphonate according to claim 8. Mixture according to claim 7 »characterized in that the polymeric substrate is a polyester resin. 9. Mixture according to claim 7 »characterized in that the polymeric substrate is a reinforced polyester resin. 10. Mixture according to claim 7 »characterized in that the polymeric substrate is a urethane foam. 11. Mixture according to claim 7, characterized in that the polymeric substrate is a polymethyl methacrylate. 12. Mixture according to claim 7, characterized in that the bis (2,3-dibromopropyl) phosphonate bis (2,3-dibromopropyl) -phenyeiiphO3phonat is. For Stauffer Chemical Company according to · ** 9 · 9 «ιβ · η on" (Dr. H.J. Wolff) Lawyer 209848/1246