DE2211762A1 - Chlorine-containing polyether-polyol copolymers and polyurethanes made therefrom - Google Patents

Description

^^ 5

P α t ο π t α η ν / α I t β 8 Mönchen 2, Bräuhau.stroße 4 / III

Case L-253
12 / 1'0 / ka

IiL Industries, Inc., Hew York, USA

Chlorine-containing polyether-polyol copolymers and products made therefrom

Polyurethanes

The present invention "relates to the manufacture of chlorine-containing polymeric compositions. In particular, it relates to the production of chlorine-containing polyether-polyol polymers and the Manufacture of flame-retardant polyurethanes from these polymers.

There is one in the United States and around the world further and steadily expanding market for polyurethane foams. These materials are used to manufacture a wide variety of Foam structures including insulation, upholstery used in homes, automobiles and for aerospace and many other purposes. Polyurethane foams can generally be converted into rigid foams

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or flexible foams. The flexible foams are widely used in upholstery, seats, mattresses and The like, whereas the rigid foams are mainly used as reinforcement parts in constructions, electrical insulation, and insulation serve for hot water or steam pipes and the like.

In addition, non-foamed polyurethane compositions are used widely used in the form of elastomers, coatings, potting compounds, mimes and synthetic porous materials.

A significant technical part of many known polyurethane compositions, in foamed or non-foamed, flexible or rigid form, is their flammability. These polyurethanes are completely flammable and highly flammable and burn quickly, once they are inflamed. It is very likely that The legislation will mandate that polyurethane foams be used in various fields including homes, automobiles and Aircraft used must be made flame retardant.

Many attempts have been made in the past to use polyurethanes To impart fire resistance and flame retardancy. These known methods largely have the addition of fire-resistant ones Accessories to materials included. Literally millions of dollars spent on add-on material purchases this year issued to impart flame retardancy to polyurethane foams.

Attempts have also been made to create new chemical reagents for making flame retardant polyurethanes. So were halogenated Reagents have been proposed which have been believed to impart flame retardancy to the foams made from them would. For example, polyester-polyol reagents based on "Ohlorendic anhydride" (derivatives of 1,4,5,6,7,7-hexachlorobicyclo- [2,2,1] -5-hepten-2,3-dicarboxylic acid -anhydride) reacted with organic isocyanates to make polyurethane materials.

However, such known proposals are costly because of their cost.

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speed and the unsatisfactory foam products made therefrom have not been entirely satisfactory. Some of them showed from acquaintances Polyurethane foams made from halogen-containing starting materials considerable hydrolytic instability. It was enough to expose such foams to water or even to moist air, to the release of hydrochloric acid from chlorine-containing Effect urethane compositions.

Other types of chlorine-containing foams show good flame resistance, however, they are not commercially viable because of the poor properties of the foam products. This is particularly true towards the pail of flexible foams, where the well-known attempts JPLamm resistance due to the incorporation of a halogen (e.g. chlorine) content in the foam, generally led to the destruction of the flexibility of the foam.

It is therefore constantly after new ways to make polyurethanes flame-retardant Give properties and look for new polyurethane compositions are sought that have these desirable properties.

An important object of the present invention is to provide new flame retardant polyurethane compositions.

Another object of the present invention is to provide polyurethane compositions that are flame retardant and to have good hydrolytic stability and flexible properties.

Another object of the present invention is to provide new chlorine-containing polyether-polyol copolymer compositions used for the production of flame-retardant polyurethanes can be.

A more specific subject matter of a preferred embodiment present invention is the. Creation of flame-retardant, flexible Polyurethane foam compositions. ,

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-A-

Further articles and gate parts of the invention are set out below listed or result from it.

According to the invention, flame-retardant polyurethanes are produced from polyether-polyol copolymers with a molecular weight between about 700 and about 10,000 containing between about 20 and 50 weight percent chlorine, and preferably between about 35 and 50 percent chlorine. That Chlorine is in trichloromethyl groups in these polyether-polyalcohol polymers present, which are attached to the polymer chain.

The invention creates both these new chlorine-containing polyether-polyol compounds as well as the polyurethanes made from them. The polyurethanes are made by reacting those described above chlorine-containing polyether polyols with an organic polyisocyanate manufactured. The polyurethane compositions obtained are not only flame-retardant, but also hydrolytically stable and can be used either as rigid or flexible foams or as unfoamed polyurethane elastomers, coatings, potting compounds, fibers, Films and the like are produced.

According to the invention, a chlorine-containing polyether-polyol polymer is created. This polymeric material has a molecular weight of about 700 to 10,000, preferably about 400 to 6000 and a chlorine content between about 20 and 50 wt.

The chlorine-containing polyether-polyol compositions of the invention are made by copolymerizing certain oxirane monomers on polyhydroxy starting materials or initiators. These polyhydroxy initiators contain from 2 to about 6 hydr

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xyl groups and include "for example ethylene glycol, propylene glycol, Trimethylolpropane, glycerine, trimethylolethane, pentaerythritol , 1,2,4-butanetri oil, 1,2,6-hexanetriol, phenyl-trimethylolT-methane, Mannitol and the like. The use of triol initiators is currently preferred. Trimethylol propane is a "special." preferred initiator for use in the manufacture of flexible, flame-retardant polyurethane foams.

In accordance with the invention, the polyhydroxy initiators are used as a starting point used for polyether polymerization at every functional point of the starting material. Close in this way the polyether-poly-oils according to the invention depending on the number of the hydroxyl groups present in the starting material, two or more polyether chains. Any of these polyether chains ends in a hydroxyl group that gives the final composition its polyol structure.

The polyether chains are made by random copolymerization or block copolymerization of trichloropropylene oxide (TCPO) with a low-1,2-alkylene oxide, based on the functional onellen hydroxyl groups of the starting material produced. Alkylene oxides which polymerize with TCPO to form these polyether chains are represented by the following formula :

CHn - CH -

wherein R is hydrogen, CH, or C ₂ H ₅ .

It is therefore apparent, polyol-copolymer PoIyäther that the polyether chains of the new to the present invention may be copolymers of Eetten TCPO with ethylene oxide, propylene oxide or 1,2-butylene oxide. These copolymer chains are produced by random or block copolymerization of the monomers and the proportions of TCPO and the 1,2-alkylene oxide, e.g. propylene oxide,

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which are present in the copolymer chains can largely can be varied without departing from the scope of the invention. This ratio should be such that the polyether-polyol polymers contain approximately from 20 to 50% by weight of chlorine.

The copolymers of the invention comprise repeating units of chlorine-containing monomers (e.g., TCPO) and repeating units Units of one or more of the 1,2-alkylene oxide monomers described above, randomly or can be arranged in blocks as desired. The number and the arrangement of the repeating units can vary from chain to chain of the copolymer.

The term "copolymer" as used herein is also intended to include mixtures of chlorine-free polyether polyols with the above chlorine-containing ones copolymers described or with chlorine-containing polymers in accordance with the following formula I, wherein η = 0, so that the polymer chains are homopolymeric TCPO- (or the like.) Chains are, include. This blend creates a "copolymer" composition having the desired molecular weight and chlorine content which are characteristic of the composition according to the invention and which are particularly useful for the preparation of refractory flexible foams. The final polyurethane products made from such blends show Structures similar to those of polyurethanes made from the true block or random copolymers of the present invention were manufactured.

The copolymers of the invention thus include trichloromethyl-containing pendant ones Segments and chlorine-free segments that they add to the structure of the final polyurethane. These segments can be sprinkled into each polymer chain, as in the real copolymers, or in separate chains, as in the case of the mixtures.

In accordance with a preferred embodiment of the Invention, the polyether polyols for the production of flame

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adverse polyurethane foams are used. Use for this purpose. Dete polyols should have a chlorine content of at least about $ 30 & and preferably at least about $ 35. For the production Non-foamed polyurethanes, such as potting compounds, are polyols with lower chlorine levels, down to about 20 ^, useful.

As described above, the polyether polyols according to the invention contain repeating units made from! ECPO, however, according to the present invention, other chlorine-containing Compounds of the formula

CH,

CH

(OH ₂ )

CCl,

where y is 0, 1 or 2, take the place of TCPO. Trichlorobutylene Oxide (TCBO) and Trichloropentene Oxide (TCPENO) reagents also provide the appended CCl ^ residues found in the polyether-polyol compositions according to the invention are present.

The new polyether-polyol copolymers created by the present invention have the structural formula I:

(CHo) ν R

I ^y j

, - C - O - [(CI-I ₂ - CH - 0) (CH ₂ - CH - O) _n I _1n [CH ₂ - CH ₂ - Ο} Η

** fit * i tr

CCL

Ri - c - O - [(CH ₂

(O ₂ )

'- CH-

O) (CH-CH-O) J _1n [CH ₂ -CH ₂ -OKH

(X)

"VY

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where q is in each case an integer of at least 1, y is in each case selected from 0.1 or 2, η is in each case 0 or an integer of at least 1, m, η, ρ and q are integers chosen so that the molecular weight of the polymer is from about 700 "to 10,000", ρ is each 0 to about 10, w is an integer from 0 to 4, each R is selected from H, CH _5, or C ₃ H ₅ , each R 'is selected from H. or an organic or substituted organic radical is selected to fill the remaining valences and X

CCl ₃

«JH ₂ ) _y H

R ' ₂ - C _: O - [(CH ₂ - CH - O) _q (CH ₂ - CH - O) _n ) _m [CH ₂ - CH ₂ - 0} _p H.

means.

To explain formula I, it should be stated that y is equal to 0 if one of the monomers used to form the polyether chains the composition used is TCPO. TCPO is that preferred chlorine-containing oxirane monomers and y in formula I is therefore preferably 0.

The value of q in Formula I is an integer of at least 1. This value is for the presence of repeating units of chlorine-containing monomers, e.g. TCPO, in the polymer chains certainly. Thus, if q are 1 and η 1, the chains are equimolar Copolymer chains of TCPO and alkylene oxide monomers with a chain length defined by the value of m. As the copolymers are generally random in nature, it can be seen that the values of η and q need not be the same in any particular polymer chain.

The polymer chains of the compounds according to the invention can be block copolymer chains both how to be random copolymer chains and Formula I contemplates such a structure. So in one

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In the case of a block polymer, the value of m must be 1 or 2 and the values of q and η be sufficiently large to achieve the required molecular weight of the polymer.

The value of η in formula I can be 0 or an integer of at least Be 1. In the first pail, the chlorine-containing polyether chains form TCPO, TGBO, or TCPENO homopolymer chains; whereas in the latter case, when η is 1 or more, the chains have random or block copolymers of TCPO or the like comonomer repeating units of ethylene oxide, propylene oxide or 1,2-butylene oxide Mlden.

In accordance with the invention, when η in the above formula I, η is 0 and the chlorine-containing polymers represented by the formula contain homopolymers TCPO chains (or the like), the polymers are mixed with chlorine-free polyether polyols, to create the copolymers according to the invention. These "copolymer ^!" Chains included. The blended copolymers can comprise blends of chlorine-free ether polyols with the chlorine-containing copolymers described above as well as with the polymers containing homopolymeric TCPO, TCBO, or TCPEUO chains.

Propylene oxide is a preferred comonomer in the preparation of the monomeric chains of the polyether polyols according to the invention and the radical R in formula I is therefore preferably a methyl group, which indicates that the dopolymeric polyether chains TCPO (or the like) propylene oxide copolymer chains.

According to a preferred embodiment of the present invention, the polyether chains are the polyether-polyol copolymers End-capped with ethylene oxide to create primary hydroxyl groups at the ends of the polymer chains. The primary hydroxyl groups

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pen are highly reactive with polyisocyanates, the invention Polyurethane foams are created.

If the polymer chains are capped at the ends with ethylene oxide, it is preferred that at least one monomer unit of ethylene oxide is added per each polymer chain end. So for the preferred embodiment, the value of ρ is in the formula I equals 1. The number of ethylene oxide repeating units attached to each polymer chain end is given by those to the reaction mixture after the completion of the TCPO propylene oxide polymerization or the like added amounts of ethylene oxide are controlled.

Any desired number of recurring Ethylene oxide units are added, for example 10 or even more, as long as the desired chlorine content of the copolymers is not adversely affected. Polyether-poly-oils, the contain homopolymer chains of TCPO, TCBO or TCPENO preferably also end-capped with ethylene oxide before they are mixed with chlorine-free polyether polyols.

It can be seen that the above formula I, in which ρ = 0, is a chlorine-containing polyether-polyol according to the present invention which is not end-capped with ethylene oxide is. So if ρ = 0, then the copolymer does not contain any terminal primary hydroxyl groups.

In accordance with the invention, the chlorine-containing polyether polyols contain from 2 to about 6 polyether chains, depending on the number of reactive hydroxyl groups present in the polyhydroxy starting material. So if the starting material is, for example, ethylene glycol or propylene glycol, the final composition will contain 2 polyether-polyol chains. On the other hand, if pentaerythritol is used as the starting material, the polymer may contain 4 polyether-polyol chains.

In formula I, X represents the additional polyether-polyol chains

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of the composition according to the invention and w denotes the number of these chains present in the composition. So w is 0 when the formula defines a two-chain polyether-polyol, such as one based on an ethylene glycol or Propylene glycol starting material. The value of w in formula I can be 0, 1, 2, 3 or 4.

Chlorine-containing polyether triols are the most preferred compositions of the present invention for manufacture of flexible foams. These compounds are represented by Formula I where w = 1. An example of such a triplet on the basis of a trimethylol propane starting material (which is currently used in the manufacture of flexible, flame-retardant Foaming is preferred) is shown in Formula II below. This formula represents a composition according to the invention represents in which the polyether chain is a homopolymeric TCPO chain which preferably contains an endcapping with ethylene oxide. The polymer of formula II is with a chlorine-free polyol,. Wie mixed with a Pluracol TP 4040 to form a copolymer according to the invention to manufacture.

COl ₃

CH ₅ CH ₂ - C (CH ₂ - 0 [CH ₂ - CH - 0-L [CH ₂ - CH ₂ - O] H) ₃ II

The radicals R »in Formula I above represent part of the structure of the polyhydric alcohol starting material used to make the compositions of the invention. These radicals generally mean hydrogen or any organic or substituted organic radicals which can be bonded to the -COH-alcohol groups of the starting material. For example, if the starting material is glycerol, w in formula I is 1 and R ^{1 is} each hydrogen.

As is apparent to those skilled in the art from the various specific polyhydroxy starting materials listed above, R ^{1 can} also be an aliphatic or aromatic hydrocarbon

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mean radical which can optionally be substituted by halogen, amino or other groups. In some cases it exists
no direct bond between the alcohol carbon atoms of the polyhydroxy starting material. Instead, these alcohol carbon atoms can be bonded together to another radical.

An example of this is trimethylolpropane as the starting material, where the part written in formula I as follows:

Ri ₂ - c-0-

Rt -C-O-

actually looks like this:

CH ₂ - 0 -

^ CH ₀ - C - CH ₀ - 0 3 2 \ 2

CH _2-0

The brackets around the bonds between the alcohol carbon atoms in formula I are intended to indicate that such bonds can be present directly between the alcohol carbon atoms, as in the case of glycerol, or that these carbon atoms can be attached to a common aliphatic or aromatic organic radical, like in
Case of trimethylolpropane. All R ¹ in Formula I.
can be the same radicals or optionally different radicals.

The molecular weight of the polyether-polyol copolymers according to the invention is primarily controlled by the chain length of the polyether chains of the polymers. The molecular weight of these polymers is generally from about 700 to 10,000, and preferably

2 0 9.8 3 9/1 1 6 8

about 4000 "to 6000. The values of n, q and m in the above Formula I are such that the polymer molecular weights are achieved in this range.

The molecular weight of the polymers is also influenced to some extent by the value of ρ in formula I, which is the Number of repeating ethylene oxide units that form the end caps of the polymer chains "indicates this effect of the ethylene oxide content on the molecular weight of the polymer is generally minimal due to the presence of a repeating ethylene oxide unit per polymer chain end (or a value of ρ = 1) is preferred. The value of ρ in formula I above can be from 0, where there is no ethylene oxide endcapping, can vary up to about TO or even higher.

For example, without representing any limitation, it has been found that satisfactory polyether-polyol compositions according to the present invention are represented by Formula I, wherein η is from 0 to 32, q is from 1 to 21 and m is 1. These limits are only given by way of example, as any number of monomer units can be present in the polymer as long as the. above ■ Molecular weight conditions agree with it. "Of course, when η is 0, the polymers with chlorine-free polyols blended to make the copolymeric polyurethane precursors of the present invention.

Of course, the variables of the present compositions represented by m, q, n, p, y, X, R and R ¹ can vary from one polyether chain of the composition to another. Thus, within the scope of the present invention, a polymer can contain two copolymeric chains of TCPO and propylene oxide and one TCPO homopolymer chain; or the composition of polyether chains can vary from chain to chain, either in the proportions of monomers present or in the particular monomers present in each chain. The length of the A'thylenoxid end cap may of course vary from ^£ ette to chain. In addition, the amount of chlorine-free

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Polyoil, if any, with the chlorine-containing polymer is mixed, varied to achieve desired levels of chlorine content in the blended copolymers.

According to the present invention, it has been found that desired copolymers can be obtained by blending a chlorine-containing polyether-polyol of the above "described type and a chlorine-free polyether polyol will. For example, chlorine-containing polyether polyols which are either copolymeric or homopolymeric polyether chains are mixed with poly (propylene oxide) triplets with molecular weights from about 3000 to 5000, for example Pluracol TP 4040 (product of Wyandotte Chemical Co. of Wyandotte, Michigan). Other chlorine-free polyether polyols used in such blending processes for the preparation of the copolymers according to the invention may be used include, for example: polyethylene oxide, polypropylene oxide, copolymer triols ((e.g. Pluracol TPE 4542 also a product of Wyandotte Chemical Co.), poly (propylene oxide) diols such as Poly-G 2020P and Poly-G 1020P (Molecular weight 2000 and 1000, respectively) manufactured by Olin Mathieson Chemical Corp. and any other chlorine-free polyether polyol in general having a molecular weight between about 1,000 and 10,000.

When mixing the chlorine-containing polyether polyols of the present invention with such chlorine-free polyether polyols, the proportions of each must be kept so that the desired chlorine levels are achieved in the polyurethane foams made from such mixed copolymers. These mixtures should contain about $ 20 to $ 50 chlorine. Polyurethane foams produced in accordance with the invention should be at least 20 and preferably 24 fo contain up to 26 wt .- $ chlorine; the mixtures to be used for foam production should therefore contain at least about 30% by weight of chlorine.

The copolymer compositions of the invention are by cationic polymerization of the oxirane-containing monomers in

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Presence of the polyhydroxy initiator and a Lewis acid catalyst produced. Suitable catalysts include boron trifluoride, B1 _{5 -It 2} O, AlCl ₃ and other metal fluorides or chlorides such as those of Sb, Sn and Ti and the like.

Generally, about 0.5 to 50 weight percent of the catalyst is based used on the weight of the oxirane-containing monomer (s) to be polymerized. The catalyst should be added to the reaction mixture to initiate the reaction.

The reaction is exothermic and is generally carried out at temperatures between about -78 ⁰ C and +40 ⁰ C. It can be carried out in bulk or in solvent systems and is generally carried out in batches, although it can be subjected to continuous processes if desired. The reaction is carried out to completion, which is indicated by the termination of the exothermic reaction, and the acidic catalyst is then preferably neutralized.

If the use of homopolymer chains in inventive Mixtures are desired, the chlorine-containing monomer alone is introduced into the reaction vessel, which is the hydroxy1 starting material contains. If random copolymer chains are desired. are a mixture of chlorine-containing monomers and 1,2-lower alkylene oxide monomers introduced und'wenn a block copolymer structure is desired, certain amounts of this monomer are introduced successively in a conventional manner.

Used as a di-oil feedstock such as ethylene glycol or propylene glycol used, the copolymeric product is linear in nature. The copolymers can also have a multi-chain structure, such as for example where a glycerol or trimethylol propane starting material is used.

The copolymers are amorphous in nature.

The chlorine-containing polyether polyols according to the invention can thus

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probably for the production of rigid as well as flexible polyurethanes be used. These polyurethane compositions are flame retardant, hydrolytically stable and can either be used as rigid or flexible foams or as non-foamed products. They create an excellent combination of properties that are superior to those of previously available products.

The polyurethanes of the present invention include reaction products an organic polyisocyanate and the chlorine-containing polyether-polyol copolymers described above. The present invention thus creates a flame retardant, hydrolytic one stable polyurethane, which is a reaction product of (a) an organic polyisocyanate and (b) a polyether-polyol copolymer, the approximately 20 to 50% by weight of chlorine has a molecular weight between approximately 700 and approximately 10,000, preferably between approximately 4,000 and approximately 6,000. The chlorine is in that Polyether-polyol reagent contained in trichloromethyl groups attached to the polyether-polyol polymer chains.

Polyether polyols preferred for the production of polyurethane foams are polyether tri-oils and especially copolymer blends of chlorine-free polyether triols with polyether triols, the homopolymer Contain chains of TCPO or copolymer chains of TCPO and propylene oxide. On the other hand, polyether diols are based on Ethylene glycol or propylene glycol based, preferred in the production of non-foamed polyurethanes according to the invention.

The presence of thermal primary hydroxyl groups on the chlorine-containing polyether-polyol polymer chains is greatly facilitated their reaction with isocyanate groups to form polyurethane compositions. The end-capping of the polyether-polyol chains is corresponding with ethylene oxide to form such terminal, primary hydroxyl groups also particularly preferred if the Polyether-polyols can be used to form polyurethanes should.

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The polyisocyanate compounds that. for the production of the invention Polyurethanes used can include aromatic, aliphatic ^, or aliphatic-aromatic polyisocyanates. Presently preferred are toluene-2,4-diisocyanate, toluene-2,6-diisocyanate and the mixtures thereof.

Other polyisocyanates that can be used include a: pjp'-diisocyanato-diphenylmethane, dimethyl-diphenylmethane diisocyanate, Bi-toluylene diisocyanate, dibenzyl diisocyanate, diphenyl dimethyl methane diisocyanate, Hexamethylene diisocyanate, naphthalene-1,5-diisoeyanate, JETaphthalene triisocyanate, dichlorodiphenylmethane diisocyanate, meta-phenylene diisocyanate, para-phenylene diisocyanate, 1,3,5-benzene triisocyanate and the like.

The ratio of polyisocyanate to polyether-polyol copolymer can be varied widely in the preparation of the polyurethanes according to the invention. In general, about 0.95 to 1.25 equivalents of isocyanate per equivalent of polyether-hydroxyl are desirable. In the production of polyurethane foams, it is It is important to use a ratio such that the final polyurethane foam composition contains at least about 20 %, and preferably about 24 to 26 wt. -5.degree., chlorine. About 35 wt.% chlorine is generally in the polyol copolymer reagents less chlorine may be present in polyether polyols used in the manufacture of other types of polyurethane, such as potting compounds.

A small amount of water, for example about 0.5 to 5% by weight The polyether polyol is added to the reaction mixture as a blowing agent when a polyurethane foam is to be produced. The water can be added to the polyether-polyol reagent, or can be added at the same time as the other ingredients in one One-step process or so-called "one-shot" process in a foaming nozzle can be introduced. If a prepolymer is produced, so the ingredients are generally anhydrous

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Maintained shape and added the water around the time of foaming.

Other propellants including freons or liquid hydrocarbon gases, such as methane, ethane or the like can also be used as blowing agents for the production of polyurethane foams will. The use of these various propellants is common and described, for example, in U.S. Patent 3,072,582.

Usual amine catalysts can be introduced into the reaction mixture to facilitate the blowing reaction between the isocyanate residues and the water hydroxyl. Suitable amine catalysts include diethylenetriamine, triethylenetetramine and tertiary Amines, such as If-methylmorpholine, N-ethylmorpholine, 2 -ethanolpyridine, Dibutylaminoethanol and the like; These catalysts are generally present in amounts from 0.05 to about 3 percent by weight of the polyether-polyol reagent available.

The polyurethane foams of the present invention can be made in a one-shot process with all ingredients be pumped into the approach of a foaming machine, where they are intimately mixed and then into reaction vessels for foaming and Härfcurg can be run in or thrown in. The reaction mixture is heated to the extent necessary to achieve a perfect Reaction, evaporation of the propellant and cell formation is necessary. The foam can then be cured, and heated as desired aged and can be broken in the usual way by squeezing or wrestling.

To use the one-step process, preferable is the Possibility of using the polyurethane foams according to the invention from a prepolymer of the chlorine-containing polyether polyol and a polyisocyanate with subsequent addition of the blowing agent and foaming in the usual way. ·

The products according to the invention can be flexible, semi-rigid, rigid

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and cellular foams. These foams can be used to manufacture upholstery, insulation, mattresses, upholstery for furniture, Insulation for pipes, "sandwich" constructions for panels, Building walls, vehicles, boats and the like, reinforcement material for vehicles or aircraft structures and for many others different purposes can be used. The most important property of the polyurethane foams according to the invention is their flame-retardant, hydrolytically stable'EToor, due to its manufacture from the new, above-described, chlorine-containing polyether-polyol copolymers is achieved. The invention is particularly suitable for the production of flame-retardant flexible polyurethane foams .

If polyurethane foams are also a particularly preferred and important one Represent product of the present invention, so can of course also non-foamed polyurethanes in the form of elastomers, coatings, casting compounds, fibers, films and the like as flame-retardant, hydrolytically stable materials according to the present invention. In making this Products are followed the process steps described above, with the exception that the propellants, agents and catalysts, used for foam formation can be omitted.

The polyurethane compositions according to the invention can be customary Additives such as silicones, silicone oils, silanes, emulsifiers (preferably non-acidic and anionic or non-ionic), wetting agents, Fillers, pigments and dyes, antioxidants, non-decomposing substances, deodorants, fungicides, plasticizers and the like included. Of course, these materials are common additives for polyurethane resins and whatever or all of them can optionally include flame retardant polyurethane compositions can be added to the present invention.

The following examples are intended to give those skilled in the art a better understanding convey the present invention. They illustrate

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the preparation of the chlorine-containing polyether-polyol copolymers according to the invention and their use in the production of flame-retardant, hydrolytically stable polyurethane foams. These Examples serve to illustrate the invention without restricting it.

Production of chlorine-containing polyether polyols. example 1

A mixture of 1.24 g (0.02 mol) ethylene glycol, 3.48 g (0.06 mol) propylene oxide and 9.67 g (0.06 mol) TCPO is placed in a small flask equipped with a stirrer and nitrogen inlet, brought in. The flask is purged with nitrogen to remove the air. The mixture is kept at ⁰ ° C., 10 drops (2 ml) of BF-'ÄtpO catalyst are added and the polymerization is enabled for 3 1/2 hours at ⁰ ° C. and then for 16 more hours at room temperature. The acidic catalyst is neutralized by adding 2 ml of concentrated ammonium hydroxide and excess water is ^{removed by distillation at 100 °} C. and 2 mm Hg. The copolymeric reaction product is obtained with a yield of 95.8 fa and has a hydroxyl number of 153 mg KOH per gram of the polymer, a molecular weight of 733 and a chlorine content of 44% by weight . The theoretical molecular weight of the product is 720.

The polymeric reaction product is further indicated by its NMR spectrum characterized, which shows that the product has a ratio of OH protons to all other hydrogen atoms of 1 / 16.8 (calculated value 1 / 15.5).

Example 2

The procedure of Example 1 is repeated in the present example with the exception that 10.44 g (0.18 mol) of propylene oxide take the place of the 3.48 g of propylene oxide used there and 225 ml

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(0.25 mol ^c / o) BIV ₅ -GaS can be used as a catalyst. After the polymerization of the ÄG / TCPO / PO reaction mixture is complete, 8.8 g (0.04 mol) of ethylene oxide (ilo) are poured into the reaction vessel through a Dean-Stark trap fitted with a hanging "or inverted cylinder The AO is added to the reactive ends of the copolymer chains at a temperature of ⁰ ° C. The reaction vessel is kept in an ice water bath and the AO is prevented from escaping by connecting the nitrogen outlet tube to a U-tube hanometer. The copolymeric reaction product is obtained in a yield of 68.8 ^c / o . It has a molecular weight of 1457.1 (hydroxyl number 77). This corresponds to a theoretical molecular weight of 1156.5.

Example 3

A sample of 13.42 g (0.1 mol) of trimethyloipropane and 339.2 g (2.1 mol) of TCPO are placed in a flask equipped with a stirrer and nitrogen inlet. The mixture is ^{cooled to 0} ° C. under nitrogen and 2.8 ml. B] JyAt ₂ O are added at ^{0 ° C.} Ilach removing the ice bath, a slight temperature increase will occur at 70 ⁰ C. The mixture is ^{cooled to 0} ° C., the ice bath is then removed and the reaction is continued overnight at room temperature.

The reaction product is ^{heated to 60 °} C. in order to enable stirring of the poly mers and 17.6 g of ethylene oxide are added to end-cap the polyol. Concentrated ammonium hydroxide is added in order to neutralize the polymer and the reaction mixture is ^{freed from water in vacuo at 100 °} C. and 1-2 mm pressure. The product is obtained in 98.4 ° f yield and shows a Molekulargev / layer of 5870 and a chlorine content of 59.5 parts by weight This is similar to a theoretical Molekulargev / layer of 3702 and a theoretical chlorine content of 60.4 #.

30 g of the TCPO-IIomopolymer triol so produced are in one standard laboratory mixer with 25 g of a chlorine-free poly-

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(ρropylenoxid) -trio-Is with a molecular weight of about 4000 (Pluracol TP 4Ο4Ο) mixed to 55 g of an inventive to produce mixed copolymers. This MiseheopOIpolymer has an average molecular weight of about 5020 and a chlorine content of about 32.5 wt .- ^. It is referred to as 3Λ copolymer and is suitable for the production of polyurethanes according to the invention.

A separate 40 g sample of the TCPO homopolymer of this example is also used with 25 g of Pluracol TP 4040 in the same manner as described above, to form 65 g of a mixed copolymer mixed with an average molecular weight of about 5150 and a chlorine content of about 36.6% by weight. This Mixed copolymers is referred to as Copolymer 3B and is also suitable for polyurethane production.

Example 4

A mixture of 13.42 grams (0.1 moles) of trimethylolpropane, 185.6 grams (3.2 moles) of propylene oxide, and 177.65 grams (1.1 moles) of TCPO is placed in a small flask and purged with nitrogen to remove the air . The mixture is kept at ⁰ ° C. and 1.6 ml of A is added dropwise over a period of time

added from 5 minutes. The ice bath is then removed and an exothermic rise to 30.degree. C. is observed. The mixture is ^{cooled again to 0} ° C. and 1 ml of additional catalyst is added. No visible reaction takes place and the mixture is ^{heated to 60 °} C., from where an exothermic rise to 160 ^° C. takes place. The reaction product is ^{cooled to 35 °} C. and 8.8 g of ethylene oxide are added using the method described in Example 2. The reaction product is neutralized with 12 ml of concentrated ammonium hydroxide and the water is removed by stripping off in vacuo. The copolymeric product is obtained with a conversion of 88.8% and has a molecular weight of 4429, a hydroxyl number of 38 and a chlorine content of $ 33.3. These values are with a theoretical molecular weight of 3939, one

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A hydroxyl number of 42.7 and a chlorine content of 29.7 are comparable.

Example 5

A flask equipped with a magnetic stirrer, thermometer and nitrogen inlet is charged with 13.42 g of trimethylolpropane and 339.1 g of TCPO ι. The flask is immersed in an ice-water bath, the mixture is ^{cooled to 0} ° C. and 2 ml of BP ^ 'ÄtpO are slowly added and the flask is then removed from the bath. After about 5 minutes the temperature rises to 60 ^° C. and then slowly falls to room temperature. The reaction mixture is then cooled again to ⁰ ° C and additional 2 ml BIV-ÄtpO-catalyst is added, whereby the temperature rises to 180 ⁰ C exotherm. The mongrel is then cooled again with ice and left to stand at room temperature overnight. There is no further exothermic increase.

The polymeric reaction product is ^{heated to 60 °} C. in order to enable stirring and 17.6 g of ethylene oxide are slowly added in order to add primary hydroxyl groups to the reactive chain ends of the polymer. 10 ml of concentrated Ammonihydroxid be added to neutralize the catalyst and excess water in a vacuum (1-2 mm) at 100 ⁰ C removed. The resulting polymer is contained in 92 % yield, has a molecular weight of 5309 (hydroxyl number 31.7) and contains 60.7% chlorine.

A sample of 30 g of the resulting TCPO homopolymer triol is mixed with 25 g of a chlorine-free poly (propylene oxide) triol with a molecular weight of about 4000 (Pluracol TP 4040), around 55 g of a mixed copolymer with an average Molecular weight of about 4714 and a chlorine content of about 33.1% by weight. This product is for polyurethane production suitable.

209839/1168

Example 6

A sample of 13.42 grams of trimethylolpropane and 339.2 grams of TCPO is placed in a flask equipped with a stirrer and nitrogen inlet. The mixture is ^{cooled to 0} ° C. under nitrogen and 6 ml of ΒΕ-'Αΐ ,,, Ο are added at ⁰ ° C. After removing the ice bath, an exothermic reaction takes place. The mixture is ^{cooled to 0} ° C. and the ice bath is then removed again and the reaction is continued overnight at room temperature.

The reaction product is ^{heated to 60 °} C. in order to enable the polymer to be stirred, and 8.8 g of ethylene oxide are added to end-cap the polyol. Concentrated ammonium hydroxide is added to neutralize the polymer and the reaction mixture under vacuum at 100 ⁰ C and 1-2 mm pressure from the Y / ater freed. The product is obtained with a yield of 96.7 % and has a molecular weight of 4036 and a chlorine content of 6t, 1 wt .- ^. This is comparable to a theoretical molecular weight of 3702 and a theoretical chlorine content of 60.4 i ° *

A 30 g sample of the TCPO homopolymer triol of this example is made with 25 g of Pluracol. TP 4040 blended to form a mixed copolymer with an average molecular weight of about 4020 and to give a chlorine content of about 33.3 wt .-? 6. This mixed one Copolymers is suitable for polyurethane production.

Example 7

A mixture of 6.71 grams of trimethylol propane, 63.8 grams of propylene oxide, and 96.9 grams of TCPO is placed in a small flask and purged with nitrogen to remove the air. The mixture is kept at ⁰ ° C. and 2 ml of BF ~ * Et ₂ 0 catalyst are added dropwise over the course of 5 minutes. The ice bath is then removed and an exothermic reaction is observed. The reaction product is ^{cooled to 35 0} C and with 8.8 g of ethylene oxide to the end

209839/1168

blocking of the copolymer chains. The reaction product is neutralized with concentrated ammonium hydroxide and the water is removed by stripping off in vacuo. The copolymer product is obtained with a conversion of 71.5% , it has a molecular weight of 3619, a hydroxyl number of 46.5 and a chlorine content of 29.1 ° These values are based on a theoretical molecular weight of 3524, a hydroxyl number of 47, 7 and a chlorine content of 36.2 io .

Example 8

This example illustrates the preparation of a polyether polyol of the present invention containing block copolymer chains of TCPO and propylene oxide. A 6.2 g sample of ethylene glycol (1 molar equivalent) is placed in a flask equipped with a stirrer and nitrogen inlet. A sample of 29.0 g (5 MoI äquvalent ^ propylene oxide is added and to this mixture at ⁰ ° C 0.3 ml added slowly BFVAt ₂ O, wherein a exotherm to 8O ⁰ C. After cooling again to ⁰ C. The ice bath is removed and the mixture is left to react overnight at room temperature, 80.75 g (5 molar equivalents) of TCPO and 0.5 ml of BiVAt ₂ ^{O are added to the mixture again at 0} ° C. and the TCPO is allowed to react for 16 hours workup are added 3.8 ml HH.OH, whereupon vacuum stripped at 10O ⁰ C (2 mm). The product (86.5 g), (# 69 yield) has a hydroxyl number of 71.5 and contains 46 1 % chlorine, which is comparable to a theoretical hydroxyl number of 90 and a theoretical chlorine content of 42.6 fo _t

Example 9

A flask equipped with a stirrer and nitrogen inlet is charged with 6.71 g (1 mol equivalent) trimethylolpropane, 43.9 g (5 mol equivalent) TCBO and 14.5 g (5 mol equivalent) PO. 1 ml of BF, 'Ät ₂ O' is slowly added to the mixture at about ^{0 0} C. An exothermic temperature rise to 80 ⁰ C is

monitored and controlled using a dry ice acetone bath. The polymerization reaction is continued overnight. 8.8 g of ethylene oxide are added to the polymers at 4-0 ° in order to effect end-capping with primary hydroxyl groups. It is worked up in the usual way. The polymer is obtained with a yield of 93 $ , it has a hydroxyl number of 102 (theory 114) and a chlorine content of 37.0 (theory 36.1 $)

Manufacture of flame retardant polyurethane foams Example 10

3 components of a polyurethane foam reaction mixture manufactured as follows:

Component A

55.00 g of the mixed copolymer 3A,
produced in example 3

0.39 g stannous octoate
1.65 g of antimony trioxide

Component B

1.42 g of water

0.11 g Dabco catalyst (cyclic triethylenediamine, commercial product of Houdry Process Corp.) 0.44 g silicone oil L-540 (Union Carbide).

Component C

17.46 g of toluene-2,4-diisocyanate

In this example, component B is added to component A, whereupon component C is added. The mixture is then stirred until foaming begins (about 35 seconds) and poured into a paper cup (0.95 1, 1 qt.). After 6 1/2 minutes, the foam height is at a maxi space

209839/1 168

grown. The foam is cured approximately one hour at 7O ⁰ C. The final foam product contains 25.5 wt% chlorine. It "has" a brown color, is flexible and non-flammable.

Example 11

The procedure of Example 10 is repeated again in this example using the following foam formulations:

Component A

65.00 grams of mixed copolymer 3B prepared in Example 3, 0.46 grams of stannous octoate 3.25 g of antimony trioxide

Component B

0.93 g water 0.13 g Dabco catalyst 0.52 g silicone oil L-540

Component C

12.97 g of toluene-2,4-diisocyanate

The foam produced in this example contains 28.9% by weight of chlorine, is brown in color, easily bendable and non-flammable. After curing, the foam contracted a little.

Example 12

In this example, a polyurethane foam is made from the following foam compositions:

Component A

55.00 grams of the blended copolymer of Example 5, 2.75 grams of antimony trioxide 0.3 g dibutyl tin dilaurate

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Component B

0.0935 g Kaydol mineral oil
1.387 g H ₂ O

0.075 g DaTDGO WÜV catalyst
0.275 g of N-ethyl morpholine
0.44 g silicone oil L-520
1.375 g Witco Pormrez 77-86

Component 0

17.27 g Nacconate 80 (a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate, a commercial product of Allied Chemical + Dye Corp.)

In this example, component B is added to component A, and component C is then added to the mixture with their and mixing. After a period of 25 seconds in the creamy state, the mixture is poured into a paper cup (0.95 1, 1qt.). It foams for about 2 more minutes and then cured for one hour "at 70 ⁰ C. The foam product containing 23.9 wt .- ^ chlorine. It is creamy white in color, soft, flexible and self-extinguishing. The cells

are
of the foam is fine-grained, small and evenly distributed. The foam has quite good elasticity and shows very little shrinkage. A sample of this foam is placed in boiling water and held for one hour. There is no release of chlorine, which proves the excellent hydrolytic stability of the foam.

Example 13 and 14

The procedure of Example 10 is repeated in this example, using the following foam composition:

Component A

55.00 g of the blended copolymer of Example 5 0.78 g stannous octoate

209339/1168

2.65 g of antimony trioxide

Component B

1.56 g of water

0.06 g of Dabco catalyst

0.44 g silicone oil L-54O

Component 0

19.04 g of toluene-2,4-diisocyanate

The foam prepared according to this example contains 22.9 wt. -Fo chlorine. It is aremig white in color, flexible and fire retardant. The foam contracts a little after hardening.

The procedure of this example is repeated using the same foam composition, except that the amount of Dabco catalyst is increased to 0.11 g and that of stannous octoate is decreased to 0.37 g. This time, the foam contains 23.2 wt. -Fo chlorine. It is essentially identical in appearance and properties to the foam described above in this example.

Example 15

The procedure of Example 10 is followed, in this example, using the following foam composition, repeated:

Component A

25.00 g of the TCPO propylene oxide copolymer triol from Example 4 0.18 g stannous octoate
1.25 g of antimony trioxide

Component B

0.71 g v / water

0.05 g Dabco catalyst

0.20 g silicone oil L-540

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Component C

8.76 g of toluene-2,4-diisocyanate

The foam produced in this example contains $ 20.5 by weight Chlorine and is slightly brown in color. It is believed that because of the techniques used in the present manufacture, the foam becomes stiff after cooling from the oven curing step. The foam is fire retardant.

Example 16

In this example, a polyurethane foam is prepared using the method of Example 10 from the following foam composition:

Component A

55.00. g of the mixed copolymer of Example 6, 2.75 g of antimony trioxide
0.3 g dibutyl tin dilaurate

Component B

0.0935 g Kaydol mineral oil
1.5968 g H ₂ O

0.075 g Dabco WT catalyst
0.275 g of N-ethylmorpholine
0.44 g silicone oil L-520
1.375 g Witco 3? Ormrez 77-86

Component 0

19.92 g Nacconate 80 (a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate)

The resulting polyurethane foam product contains $ 24.29 by weight Chlorine. It has a creamy white color, is soft, flexible and fire retardant. The cell size of the foam is small, fine-grained and evenly distributed. The foam is not elastic

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and shows some shrinkage.

Example 17

The procedure of Example 10 is repeated in this example using the following foam composition:

Component A

25.00 g of the ICTO-PO copolymer triol from Example 7 0.175 g tin (II) oetoate 1.25 g antimony trioxide

Component B

0.7125 g water 0.05 g Dabco catalyst 0.20 g silicone oil L-540 0.125 g N-Ethy3morpholine

Component 0

9.13 g of toluene-2,4-diisoeyanate

The foam produced in this example contains 24.7 G-ew, - $ Chlorine. It is dark yellow in color, flexible, not elastic and fire retardant.

209839/1

Claims (20)

Claims 1. Polyether-polyol copolymer with a molecular weight between etv / a 700 and about 10,000 and a chlorine content between about 20 to 50 wt .- ^, wherein this chlorine in trichloromethyl groups present, which are attached to the polymer chain. 2. Chlorine-containing polyether-polyol copolymer having the formula ecu (CH ₂ Jy R £ - O - [(CH ₂ -CH-O) (CH ₂ - CH - O) _n J ₂ JCH ₂ - CH ₂ - 0} _p H ULl ca, (CH ₂ ) y C ^ - O - [(CH ₂ - CH - O) _q (CH ₂ - CH _{- O) n} J _x JCH ₂ - CH ₂ - OJ- _p H LU (X) _w where q. is in each case an integer of at least 1, y is in each case 0, 1 or 2, η is in each case an integer of at least 1, ρ is in each case from 0 to about 10, m, η, ρ and q are integers chosen such that the molecular weight of this polymer is about 700 to 10,000, w is 0, 1, 2, 3 or 4, R is in each case H, CHj or C ₂ ^H 5 * ^st » ^Rl ^ ^ewe ^ ^{ls H} or an organic or substituted organic radical to fill in the remaining valences of the formula and X 209839/1168 CCl, . ^l 3 "(CH ₂ ) y R - C - O - [(CH ₂ - CH - Oq (CII ₂ - CH - 0) _n ] _m [CH ₂ - CH ₂ - 0] _p H; and the polymer contains about 20 to 50 weight percent chlorine. 3. Polymer according to claim 2, characterized in that ρ at least 1 and the polymer contains terminal primary hydroxyl groups. 4. Chlorine-containing polyether triol with the formula of claim 2, where w is 1. 5. The polymer of claim 2, wherein y is O and said polymer contains recurring units of trichloropropylene oxide. 6. The polymer of claim 5, wherein η is 1, and R is CH, and the polymer contains copolymeric chains of trichloropropylene oxide and propylene oxide. 7. The polymer of claim 6, wherein ρ is at least 1 and the polymer contains terminal primary hydroxyl groups. 8. The polymer of claim 6 wherein w is 1 and the polymer comprises a triol having terminal primary hydroxyl groups contains. 9. Polymer according to claim 8 having the formula CCl ₃ CH, I, 3 C ₂ H ₅ -C (CH ₂ - O [[CH ₂ - CH - O] _q [CH ₂ - CH - O] _n J _1n [CH ₂ - CH ₂ - OJ _p H) ₃ where ρ in each polymer chain is 1 is. 10. The polymer of claim 2 having a molecular weight of about 4,000 to 6,000. 209839/1168 11. Polyether-polyol copolymer with an average Molecular weight between about 700 and 10,000 and with a content of between about 20 and 50 wt .- ^ chlorine, which is an intimate Mixture of (a) a polyether-polyol which contains chlorine in the form of trichloromethyl groups attached to the polymer chain hang, with (b) a chlorine-free polyether-polyol. 12. Copolymer according to claim 11, characterized in that it the chlorine-containing polyether polyol of claim 2 contains. 13. Copolymer according to claim 12, characterized in that η in the formula is 0 and said chlorine-containing polyether polyol possesses homopolymer chains of trichloropropylene oxide. 14. Copolymer according to claim 13, characterized in that in the formula w is 1 and the chlorine-containing polyether-polyol is a triol. 15. Copolymer according to claim 11, characterized in that the chlorine-free polyether polyol is a poly (propylene oxide) triol or a polypropylene oxide-polyethylene oxide triol having a molecular weight of about 1,000 to 10,000. 16. Copolymer according to claim 15, characterized in that the chlorine-free polyether polyol has a molecular weight of about 4,000 to 6,000. 17. Flame retardant hydrolytically stable polyurethane comprising a reaction product of (a) an organic polyisocyanate and (b) a polyether-polyol copolymer having a molecular weight between about 700 and about 10,000 with a content of about 30 to 50 wt .- # chlorine wherein the chlorine is present in trichloromethyl groups attached to the polyether-polyol polymer chain. 209839/1168 - · 35 - 18. Polyiirethanprodukt according to claim 17, characterized in that it in the form of a non-foamed elastomer, a coating of a potting compound, fibers, films or synthetic porous ones Materials available. 19. Flame-retardant, hydrolytically stable polyurethane cliaum with a content of at least about 20 wt .- ^ chlorine, which is a reaction product comprised of (a) an organic polyisocyanate and (b) a polyether-polyol copolymer, having a molecular weight between about 700 and about 10,000 and a chlorine content of about 30 "to 50 wt .- ^, the chlorine being in trichloromethy! groups, hanging on the polyether-polyol polymer chain. • 20. Flame-retardant, hydrolytically stable polyurethane foam according to Claim 19, with a chlorine content of about 20 to 26 wt .- ^, which comprises a reaction product of (a) an organic polyisocyanate and (b) the polyether-polyol copolymer of claim 2 . 21. Flame-retardant, hydrolytically stable polyurethane foam according to claim 19, with a chlorine content of about 20 to 26 wt .- ^, which comprises a reaction product of (a) an organic polyisocyanate and (b) the polyether-polyol copolymer of claim 4 . 22. Flame-retardant, hydrolytically stable polyurethane foam according to claim 19, with a chlorine content of about 20 to 26 wt .- $, which comprises a reaction product of (a) an organic polyisocyanate and (b) the copolymeric polyether triol of claim 6, wherein the polyether triol is copolymeric chains of trichloropropylene oxide and contains propylene oxide. 23. Flame-retardant, hydrolytically stable polyurethane foam according to Claim 19, with a content of at least 20 wt .- ^ chlorine, the a reaction product of (a) an organic polyisocyanate and 209839/1 168 (b) the mixed polyether-polyol copolymer of claim 11 includes. 24. Flexible polyurethane foam according to claim 19. 25. Flame-retardant, hydrolytically stable, flexible polyurethane foam according to claim 24 at a level of about 20 to 26% by weight Chlorine, which is a reaction product of (a) an organic polyisocyanate and (b) the mixed polyether-triol copolymer of Claim 14 includes. 26. Flame-retardant, hydrolytically stable, flexible polyurethane foam according to claim 24 containing from about 24 to 26% by weight of chlorine which is a reaction product of (a) at least one Toluene diisocyanate and (b) the mixed polyether-triol copolymer of claim 14 wherein the chlorine-free polyether polyol comprises a polypropylene oxide triol having a molecular weight of about 4000 is. 27. Process for the preparation of a chlorine-containing polyether polyol according to claim 1, characterized in that a) at least one oxirane monomer with the formula .0 wherein y is 0 to 2, with a CH ₂ - CH (CH ₂ ) CCl ₅ low-1,2-alkylene oxide in the presence of a polyhydroxy initiator with 2 to 6 hydroxyl groups and a cationic Lewis acid polymerization catalyst to cause the formation of chlorine-containing polyether copolymer chains, starting from the functional ones Hydroxyl groups of the initiator compound, each of the polyether chains ending in a hydroxyl group, copolymerized will. b) the proportion of each monomer that is present in the polymerization 209839/1168 Reaction is introduced, is controlled so that the polyether Copolymer chain lengths are sufficient to produce a polyether-polyol copolymer, having a molecular weight between about 700 and 10,000 and a chlorine content of about 20 "to 50 wt .- ^ are formed. 28. The method according to claim 27, characterized in that a triol is used as the polyhydroxy initiator which has 3 hydroxyl groups contains. 29. The method according to claim 28, characterized in that irimethylolpropane is used as the polyhydroxy initiator. 30. The method according to claim 28, characterized in that sufficient Oxirane monomer and 1,2-alkylene oxide introduced into the polymerization reaction to form a polyether-polyol copolymer with a molecular weight of about 4,000 to 6,000. 31. The method according to claim 27, characterized in that the oxirane monomer used includes TCPO and as a low-1,2-alkylene oxide Propylene oxide is used. 32. The method according to claim 27, characterized in that when the copolymerization of the oxirane monomer and the end 1,2-alkylene oxide, ethylene oxide added to the reaction product and is reacted with this product for end-capping the polyether chains with at least one ethylene oxide unit, wherein terminal, primary hydroxyl groups at the ends of the polyether chains are formed. 33. The method according to claim 32, characterized in that to sufficient ethylene oxide is added to the reaction product to to effect the end-capping of this polyether chain of the copolymeric product with at least one ethylene oxide unit. 209839/1168 34. Method of making a flame-retardant, hydrolytically stable polyurethane, characterized in that an organic isocyanate with a chlorine-containing polyether-polyol, the Contains chlorine in the form of trichlorinethyl groups attached to the Hang polymer chains and contains a chlorine-free polyether polyol, is copolymerized. 3p / i method of making a flame retardant, hydrolytically stable, flexible polyurethane foam, with at least about ., Characterized ° / o chlorine content that - 20 percent a) a chlorine-containing polyether-polyol with a molecular weight of about 700 to 10,000 is produced by polymerization of at least one oxirane monomer of the formula where y is 0 to 2 and mixtures of such monomers with a lower 1,2-alkylene oxide in the presence of a polyhydroxy initiator, the 2 to 6 hydroxyl groups and a cationic Lewis acid polymerization catalyst contains, starting out for the formation of polyether chains which have pendant trichloromethyl groups on the functional hydroxyl points of the initiator composition, where these polyether chains end in a hydroxyl group, b) Mixing this chlorine-containing polyether-polyol with a chlorine-free polyether-polyol with a molecular weight between about 1000 and 10 000, for the production of a mixed copolymer, which contains about 20 to 50 wt .- $ chlorine and c) Reaction of this mixed copolymer with an organic polyisocyanate in the presence of a blowing agent to form the polyurethane foam to obtain. 209839/1168 36. The method according to claim 35, characterized in that as chlorine-free polyether polyol a poly (propylene oxide) triol or a polyethylene oxide-polypropylene oxide triol is used. 37. The method according to claim 35, characterized in that the polyether chains of the chlorine-containing polyether polyol with primary Hydroxyl groups are end-capped by adding ethylene oxide to the polymerization reaction after the original Polyether chain formation is complete and addition of at least one repeating ethylene oxide unit to the reactive Ends of each polyethylene chain. 209839/1168