CA1049030A - 1,2-oxaphospholanes - Google Patents
1,2-oxaphospholanesInfo
- Publication number
- CA1049030A CA1049030A CA74208588A CA208588A CA1049030A CA 1049030 A CA1049030 A CA 1049030A CA 74208588 A CA74208588 A CA 74208588A CA 208588 A CA208588 A CA 208588A CA 1049030 A CA1049030 A CA 1049030A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- oxaphospholane
- oxo
- methyl
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5373—Esters of phosphonic acids containing heterocyclic rings not representing cyclic esters of phosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
Abstract
Abstract of the Disclosure 2-Oxo-2-alkoxy-5-phosphono-1,2-oxaphospholanes of the formula in which R1 to R7 are hydrocarbon radicals can be pre-pared from .alpha.,.beta.-unsaturated ketone and 2 or more moles of a dialkylphosphite. Obviously .gamma.-ketophosphonates are intermediates of this reaction as these compounds react with 1 or more moles of dialkylphosphite in yielding the oxaphospholanes too. Both reactions are promoted by al-kaline catalysts.
The new oxaphospholane derivatives are considerably stable against thermal decomposition. They are compatible with polymeric materials and can be used as flame protecting agent for plastics and resins, for example in polyurethane foams.
The new oxaphospholane derivatives are considerably stable against thermal decomposition. They are compatible with polymeric materials and can be used as flame protecting agent for plastics and resins, for example in polyurethane foams.
Description
The invention provides new 1,2-oxaphospholane-5-phosphonic acid esters, a process for their manufacture, a method of using them as flameproofing agents for thermoplastic polymers, polyurethanes, epoxy resins, cellulose and cellulose derivatives and also, as industrial product, the substrates protected by them.
The new compounds have the general formula I
~ C C - P ORl (I) R4~1 1 OR2 R5 \ p /
o~! \ OR3 wherein Rl and R2 each represents alkyl with 1 to 18 carbon : atoms, haloalkyl, alkoxy alkyl, having not more than 18 carbon : atoms, alkenyl with 3 to 18 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or tetrahydrofurfuryl, R3 represents alkyl with 1 to 8 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, alkenyl with 3 to 8 carbon atoms alkoxy alkyl with not more than 8 carbon atoms or tetrahydrofurfuryl, R4 represents hydrogen or : methyl, R5 represents hydrogen, alkyl with 1 to 8 carbon atoms, phenyl, methyl phenyl, methoxy phenyl or chlorophenyl or furyl, R6 represents hydrogen or methyl, and R7 represents lower `~ alkyl with 1 to 8 carbon atoms.
i ~i :
~L
qF
. ~.
~B 2 -.
A monovalent aliphatic radical represented by Rl, R2 or R3 can be a linear or branched alkyl or alkenyl radical which is unsubstituted or substituted by halogen or alkoxy groups. Examples of such radicals are methyl, ethyl, isopropyl, n-butyl, 2-ethylhexyl, isooctyl, n-dodecyl, n-octadecyl, allyl, methallyl, oleyl, 2-chloro-ethyl, 2-bromoethyl, 2,3-dibromopropyl, 2-ethoxy-ethyl, 2-butoxyethyl or 2-methoxypropyl. Where these same substituents represent a monovalent cycloaliphatic or araliphatic radical, such a radical can be, for example, cyclopentyl, cyclohexyl, cyclooctyl, benzyl, phenylethyl or 4-chlorobenzyl.
Alkyl radicals represented by R5 or R7 can be linear or branched alkyl radicals, ~ e.g. methyl, ethyl, isopropyl, tert, butyl, - n-hexyl, 2-ethylhexyl, n-octyl, isooctyl, n-dodecyl or n-octadecyl. By halogen is meant in this specification fluorine, chlorine or bromine.
, , ,:~ . :' '~ ~
;''' B~
:
. . . ... . .. . ,.... ~ ..
. . . . . . . . . .. . .. .
Compounds of the formula I which constitute a special class of these compounds are thosewherein each of Rl and R2 independently represents a monovalent aliphatic or cyclo-aliphatic, R3 is the same as either Rl or R2, each of R4 and R6 independently represents hydrogen or methyl, R5 represents alkyl or phenyl, methylphenyl, methoxyphenyl, : chlorophenyl or furyl and R7 represents . alkyl.
To this class of compounds belong the compounds of the formula I wherein `;( R3 is the same as either Rl or R2.
';
'"
..
,, ~:
.~'`"` .
~ ' :~`,. .
~, ,.
?
B~ ~ 4 ~
. ~ .
-, : . - . . . . . .
104gO30 Particularly preferred compounds of the formula I are those wherein Rl, R2 and R3 are identical and represent linear or branched alkyl radical with 1 to 8 carbon atoms, alkoxy-alkyl with 3 to 6 carbon atoms, chloroethyl, bromoethyl, alkenyl with 3 to 4 carbon atoms, cyclohexyl or benzyl, R4 represents hydrogen or methyl, R5 represents hydrogen, methyl -ethyl, phenyl, chlorinated phenyl or furyl, R6 represents hydrogen, and R7 represents methyl or ethyl.
. Examples of individual compounds of ~ the formula I are the following 1,2-oxaphospholane i derivatives:
The new compounds have the general formula I
~ C C - P ORl (I) R4~1 1 OR2 R5 \ p /
o~! \ OR3 wherein Rl and R2 each represents alkyl with 1 to 18 carbon : atoms, haloalkyl, alkoxy alkyl, having not more than 18 carbon : atoms, alkenyl with 3 to 18 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or tetrahydrofurfuryl, R3 represents alkyl with 1 to 8 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, alkenyl with 3 to 8 carbon atoms alkoxy alkyl with not more than 8 carbon atoms or tetrahydrofurfuryl, R4 represents hydrogen or : methyl, R5 represents hydrogen, alkyl with 1 to 8 carbon atoms, phenyl, methyl phenyl, methoxy phenyl or chlorophenyl or furyl, R6 represents hydrogen or methyl, and R7 represents lower `~ alkyl with 1 to 8 carbon atoms.
i ~i :
~L
qF
. ~.
~B 2 -.
A monovalent aliphatic radical represented by Rl, R2 or R3 can be a linear or branched alkyl or alkenyl radical which is unsubstituted or substituted by halogen or alkoxy groups. Examples of such radicals are methyl, ethyl, isopropyl, n-butyl, 2-ethylhexyl, isooctyl, n-dodecyl, n-octadecyl, allyl, methallyl, oleyl, 2-chloro-ethyl, 2-bromoethyl, 2,3-dibromopropyl, 2-ethoxy-ethyl, 2-butoxyethyl or 2-methoxypropyl. Where these same substituents represent a monovalent cycloaliphatic or araliphatic radical, such a radical can be, for example, cyclopentyl, cyclohexyl, cyclooctyl, benzyl, phenylethyl or 4-chlorobenzyl.
Alkyl radicals represented by R5 or R7 can be linear or branched alkyl radicals, ~ e.g. methyl, ethyl, isopropyl, tert, butyl, - n-hexyl, 2-ethylhexyl, n-octyl, isooctyl, n-dodecyl or n-octadecyl. By halogen is meant in this specification fluorine, chlorine or bromine.
, , ,:~ . :' '~ ~
;''' B~
:
. . . ... . .. . ,.... ~ ..
. . . . . . . . . .. . .. .
Compounds of the formula I which constitute a special class of these compounds are thosewherein each of Rl and R2 independently represents a monovalent aliphatic or cyclo-aliphatic, R3 is the same as either Rl or R2, each of R4 and R6 independently represents hydrogen or methyl, R5 represents alkyl or phenyl, methylphenyl, methoxyphenyl, : chlorophenyl or furyl and R7 represents . alkyl.
To this class of compounds belong the compounds of the formula I wherein `;( R3 is the same as either Rl or R2.
';
'"
..
,, ~:
.~'`"` .
~ ' :~`,. .
~, ,.
?
B~ ~ 4 ~
. ~ .
-, : . - . . . . . .
104gO30 Particularly preferred compounds of the formula I are those wherein Rl, R2 and R3 are identical and represent linear or branched alkyl radical with 1 to 8 carbon atoms, alkoxy-alkyl with 3 to 6 carbon atoms, chloroethyl, bromoethyl, alkenyl with 3 to 4 carbon atoms, cyclohexyl or benzyl, R4 represents hydrogen or methyl, R5 represents hydrogen, methyl -ethyl, phenyl, chlorinated phenyl or furyl, R6 represents hydrogen, and R7 represents methyl or ethyl.
. Examples of individual compounds of ~ the formula I are the following 1,2-oxaphospholane i derivatives:
2-oxo-2-methoxy-5-methyl-S-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-ethoxy-5-methyl-5-diethylphosphono-1,2- i ~:
,~ oxaphospholane ~ ' 2-oxo-2-iospropoxy-5-methyl-5-di-isopropylphosphono-1,2-oxaphospholane .'' `~
,;
~ ' " .
. _ 5 _ B~
.... . ~. . . ........ . .
.. . . . .
10490i~0 2-oxo-2-butoxy-5-methyl-5-dibutylphosphono-1,2-oxaphospholane 2-oxo-2-octoxy-5-methyl-5-dioctylphosphono-1,2-oxaphospholane 2-oxo-2-(2-ethyl-hexyloxy)-5-methyl-5-di-(2-ethylhexyl)-phosphono-1,2-oxaphospholane 2-oxo-2-octadecyloxy-5-methyl-5-di-octadecylphosphono-1,2-oxaphos-pholane 2-oxo-2-(2-chloroethyloxy)-5-methyl-5-di-(2-chloroethyl)-phosphono-1,2-oxaphospholane 2-oxo-2-(2-methoxyethyloxy)-5-methyl-5-di-(2-methoxyethyl)-phosphono-1,2-oxaphospholane 2-oxo-2-benzyloxy-5-methyl-5-di-benzylphosphono-1,2-oxaphospholane 2-oxo-2-(4-chlorobenzyloxy)-5-methyl-5-di-(4-chlorobenzyl)-phos-:. phono-1,2-oxaphospholane 2-oxo-2-(4-bromobenzyloxy)-5-methyl-5-di-(4-bromobenzyl)-phosphono-1,2-oxaphospholane 2-oxo-2-methoxy-5-ethyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-ethoxy-5-ethyl-5-diethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-ethoxy-5-phenyl-5-diethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3,5-dimethyl-5-dimethylphosphono-1,2-oxaphospholane ; 2-oxo-2-ethoxy-3,5-dimethyl-5-diethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3,4-dimethyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-ethoxy-3,4-dimethyl-5-diethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphos-pholane 2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane 2-oxo-2-isopropoxy-3,3,5-trimethyl-5-di-isopropylphosphono-1,2-oxaphospholane 2-oxo-2-butoxy-3,3,5-trimethyl-5-dibutylphosphono-1,2-oxaphospholane 2-oxo-2-(2-ethylhexyloxy)-3,3,5-trimethyl-5-di-(2-ethylhexyl)-phosphono-1,2-oxaphospholane 2-oxo-2-(2-chloroethoxy)-3,3,5-trimethyl-5-di-(2-chloroethyl)-phosphono-1,2-oxaphospholane 2-oxo-2-benzyloxy-3,3,5-trimethyl-5-dibenzylphosphono-1,2-oxaphos-pholane 2-oxo-2-cyclohexyloxy-3,3,5-~rimethyl-5-dicyclohexylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-phenyl-5-methyl-5-dimethylphosphono-1,2-oxaphos-pholane 2-oxo-2-ethoxy-3-phenyl-5-methyl-5-diethylphosphono-1,2-oxaphos-pholane 2-oxo-2-methoxy-3-(4-chlorophenyl)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane ; 2-oxo-2-methoxy-3-~4-bromophenyl)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-(4-methylbenzyl)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-(4-methoxyphenyl)-5-methyl-5-dimethylphosphono-~ 1,2-oxaphospholane 2-oxo-2-methoxy-3-(furyl-2)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane :
2-oxo-2-methoxy-3-(thienyl-2)-5-methyl-5-dimethylphosphono-1,2-. oxaphospholane 2-oxo-2-methoxy-3-(pyridyl-2)-5-methyl-5-dimethylphosphono-1,2-. oxaphospholane i 2-oxo-2-methoxy-3-methyl-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-methyl-5-(4-chlorophenyl)-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3,5-diphenyl-5-dimethylphosphono-1,2-oxaphospholane ~: 2-oxo-2-ethoxy-3,5-diphenyl-5-diethylphosphono-1,2-oxaphospholane . 30 2-oxo-2-methoxy-3-(4-chlorophenyl)-5-phenyl-5-dimethylphosphono-. 1,2-oxaphospholane - 2-oxo-2-methoxy-3,5-di-(4-chlorophenyl)-5-dimethylphosphono-1,2-.
.
~0490;~0 oxaphospholane 2-oxo-2-methoxy-3-phenyl-5-(4-chlorophenyl)-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-(4-methylphenyl)-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-(4-methoxyphenyl)-5-phenyl-5-dimethyl-phosphone-1,2-oxaphospholane 2-oxo-2-methoxy-3-phenyl-5-(4-methylphenyl)-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-(phenyl-2)-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-allyloxy-3,3,5-trimethyl-5-diallylphosphono-1,2-oxaphos-pholane 2-oxo-2-tetrahydrofurfuryl-3,3-5-trimethyl-5-di-(tetrahydrofurfuryl)-phosphono-(1,2-oxaphospholane) The surprising discovery has been made that it is possible to manu-facture the compounds of the formula I, in which R3 is the same as Rl or R2, by a novel process which comprises reacting an a,~-unsaturated ketone of the formula II
2Q 4 \ R6 (II) with atleast2 moles of a phosphite of the formula III
~0 /
H - P \ (III) . OR2 in the presence of a base, with or without the addition of a solvent.
Examples of a,B-unsaturated ketones of the formula II are methyl . .~
S vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, mesityl oxide, methyl isopropenyl ketone, benzalacetone, benzalacetophenone or 4-chlorobenzalace-tone. Such ketones can be manufactured by known methods, for example by condensation of the appropriate methyl ketones with aldehydes or ketones.
' '' 10'19030 The phosphites of the formula III are known compounds of industrial availability. Examples thereof are dialkyl phosphites, e.g. dimethyl, di-ethyl or dioctyl phosphite, dicycloalkyl phosphites, e.g. dicyclohexyl phosphite, diaralkyl phosphites, e.g. dibenzyl phosphite, and mixed phos-phites, e.g. methyl butyl phosphite, methyl benzyl phosphite or isopropyl cyclohexyl phosphite.
In the reaction there are used 2 moles, preferably 205 to 3.5 moles, of a compound of the formula III for each mole of the compound of the formula II.
Examples of bases which catalyse the reaction are principally alkali metals, alkali metal or alkaline earth metal alkoxides, alkali metal amides and hydrides. Particularly effective are the metals sodium and potassium, sodium methoxide, potassium tert. butoxide, lithium amide and calcium hydride; but the two metals are particularly suitablefor the purpose.
Normally, catalytic amounts of these bases suffice to initiate the reaction.
; It is sometimes advantageous to add further amounts of base during the reac-tion.
If the process according to the invention is carried out with the addition of a solvent, then suitable solvents are primarily hydrocarbons, e.g. benzene, toluene, xylene, ligroin, hexane or heptane, also alcohols, e.g. methanol, ethanol or isopropanol, or ethers, e.g. diethyl ether, dioxan or tetrahydrofuran.
The reaction can be carried out by dissolving the ketone of the formula II and adding dropwise a portion of the phosphite of the formula III
and the base. Upon onset of the reaction, the remainder of the phosphite and, if necessary, further amounts of base, are addedby gradual amounts. It is also possible to premix the phosphite with the catalyst and to add the ketone of the formula II dropwise.
In another embodiment, the compounds of the formula II and III
and optionally the solvent are first mixed and then the base, which can also be dissolved in the solvent, is added to this mixture and the reaction is brought to completion by heating.
_ g _ The oxaphospholanes of the formula I are isolated by customary methods, for example by distillation. Desirably the base is neutralised be-fore the isolation by an equivalent amount of an acid, for example acetic acid.
The reaction of dialkyl phosphites with a,B-unsaturated ketones has already been thoroughly investigated by various experts. It has hitherto been considered the rule that in the reaction only 1 mole of phosphite is added to the double bond forming the y-ketophosphonates (see Houben-Weyl, Methoden der Organischen Chemie, vol. 12/1, pages 465-467, G. Thieme Verlag, Stuttgart, 1963). If diphosphonates were also obtained, these occurred in moderate yield in addition to the monophosphonates (A.N. Pudovik, Zhurnal Obshch. Khim. 22 (1952), 1371, ref. Chem. Abstr. 47 (1953), 4837). It was therefore surprising that in the process described herein 2 moles of phosphite are added easily. It was furthermore surprising that the ~-phosphono-a-hydroxyphosphonates evidently formed as intermediate cyclise under the reaction contitions rapidly and virtually completely to give the 1,2-oxaphospholane-5-phosphonates.
It has furthermore been found that oxaphospholane derivatives of the formula I can also be manufactured from the known y-ketophosphonates by addition of dialkyl phosphites. This is an indication that the reaction discussed above probably proceeds via the stage of the y-ketophosphonates. It is therefore possible to carry out the reaction in two partial steps, the first being the known addition of 1 mole of phosphite to a,B-unsaturated ketones to form the y-ketophosphonates and the second being the reaction with a second mole of phosphite to form the oxaphospholanes. This second step is just as surprising and novel as the single step main process.
The invention therefore also provides a process for the manu-facture of compounds of the formula I, which comprises reacting a compound of the formula IV
0 R4 R6 j (R30)2P- C- CH -C -R7 (IV) with at least one mole of a phosphite of the formula III in the presence of a base, with or without the addition of a solvent. In the formula IV, the substituents R3 to R7 have the same meanings assigned to them as in respect of the compounds of the formula I. The catalysts and solvents suitable for use in this process are the same as those for the single step main process described hereinbefore, and the reaction and isolation of the products are carried out in the same way.
This modification is principally of importance for the manufacture of those compounds of the formula I in which R3 is different from Rl and R2.
The compounds of the formula I are outstanding flameproofing agents for thermoplastic polymers, polyurethanes, epoxy resins, cellulose and also for cellulose derivatives. It has long been known to use phosphorus-containing compounds as flameproofing agents for polymers, but it is normally necessary to use the phosphorus compounds in high concentrations, which results as a rule in a deterioration of the physical and technological properties of the polymers.
The surprising discovery has now been made that the new 1,2-oxa-phospholanes of the formula I impart an adequate flame resistance to the ; polymers even in relatively low concentrations. Moreover, on account of their considerable heat stability they have only a minute influence on the physical properties of the substrates. Further they are also usable in reactive systems, such as in polyurethane foams or in epoxy resins which,both in their manu-facture and use, are highly sensitive towards additives.
Examples of thermoplastic polymers which can be flame-protected with the compounds of the formula I are:
1. Polymers which are derived from simply or doubly unsaturated hydrocarbons, such as polyolefins, e.g. polyethylene, polypropylene, polyisobutylene, ' polymethylbutene-l, polymethylpentene-l, polybutene-l, polyisoprene, poly-butadiene, polystyrene, polyisobutylene, copolymers of the monomers based on the cited homopolymers, such as ethylene-propylene comonomers, propylene-butene-l copolymers, propylene-isobutylene copolymers, styrene-butadiene co-polymers, and terpolymers of ethylene and propylene with a diene, eOg.
~049030 hexadiene, dicyclopentadiene or ethylidene norbornene; mixtures of the above mentioned homopolymers, e.g. mixtures of polypropylene and polyethylene, polypropylene and polybutene-l, polypropylene and polyisobutylene.
2. Halogen-containing vinyl polymers, e.g. polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, but also polychloroprene and chlorinated rubbers.
,~ oxaphospholane ~ ' 2-oxo-2-iospropoxy-5-methyl-5-di-isopropylphosphono-1,2-oxaphospholane .'' `~
,;
~ ' " .
. _ 5 _ B~
.... . ~. . . ........ . .
.. . . . .
10490i~0 2-oxo-2-butoxy-5-methyl-5-dibutylphosphono-1,2-oxaphospholane 2-oxo-2-octoxy-5-methyl-5-dioctylphosphono-1,2-oxaphospholane 2-oxo-2-(2-ethyl-hexyloxy)-5-methyl-5-di-(2-ethylhexyl)-phosphono-1,2-oxaphospholane 2-oxo-2-octadecyloxy-5-methyl-5-di-octadecylphosphono-1,2-oxaphos-pholane 2-oxo-2-(2-chloroethyloxy)-5-methyl-5-di-(2-chloroethyl)-phosphono-1,2-oxaphospholane 2-oxo-2-(2-methoxyethyloxy)-5-methyl-5-di-(2-methoxyethyl)-phosphono-1,2-oxaphospholane 2-oxo-2-benzyloxy-5-methyl-5-di-benzylphosphono-1,2-oxaphospholane 2-oxo-2-(4-chlorobenzyloxy)-5-methyl-5-di-(4-chlorobenzyl)-phos-:. phono-1,2-oxaphospholane 2-oxo-2-(4-bromobenzyloxy)-5-methyl-5-di-(4-bromobenzyl)-phosphono-1,2-oxaphospholane 2-oxo-2-methoxy-5-ethyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-ethoxy-5-ethyl-5-diethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-ethoxy-5-phenyl-5-diethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3,5-dimethyl-5-dimethylphosphono-1,2-oxaphospholane ; 2-oxo-2-ethoxy-3,5-dimethyl-5-diethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3,4-dimethyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-ethoxy-3,4-dimethyl-5-diethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphos-pholane 2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane 2-oxo-2-isopropoxy-3,3,5-trimethyl-5-di-isopropylphosphono-1,2-oxaphospholane 2-oxo-2-butoxy-3,3,5-trimethyl-5-dibutylphosphono-1,2-oxaphospholane 2-oxo-2-(2-ethylhexyloxy)-3,3,5-trimethyl-5-di-(2-ethylhexyl)-phosphono-1,2-oxaphospholane 2-oxo-2-(2-chloroethoxy)-3,3,5-trimethyl-5-di-(2-chloroethyl)-phosphono-1,2-oxaphospholane 2-oxo-2-benzyloxy-3,3,5-trimethyl-5-dibenzylphosphono-1,2-oxaphos-pholane 2-oxo-2-cyclohexyloxy-3,3,5-~rimethyl-5-dicyclohexylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-phenyl-5-methyl-5-dimethylphosphono-1,2-oxaphos-pholane 2-oxo-2-ethoxy-3-phenyl-5-methyl-5-diethylphosphono-1,2-oxaphos-pholane 2-oxo-2-methoxy-3-(4-chlorophenyl)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane ; 2-oxo-2-methoxy-3-~4-bromophenyl)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-(4-methylbenzyl)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-(4-methoxyphenyl)-5-methyl-5-dimethylphosphono-~ 1,2-oxaphospholane 2-oxo-2-methoxy-3-(furyl-2)-5-methyl-5-dimethylphosphono-1,2-oxaphospholane :
2-oxo-2-methoxy-3-(thienyl-2)-5-methyl-5-dimethylphosphono-1,2-. oxaphospholane 2-oxo-2-methoxy-3-(pyridyl-2)-5-methyl-5-dimethylphosphono-1,2-. oxaphospholane i 2-oxo-2-methoxy-3-methyl-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-methyl-5-(4-chlorophenyl)-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3,5-diphenyl-5-dimethylphosphono-1,2-oxaphospholane ~: 2-oxo-2-ethoxy-3,5-diphenyl-5-diethylphosphono-1,2-oxaphospholane . 30 2-oxo-2-methoxy-3-(4-chlorophenyl)-5-phenyl-5-dimethylphosphono-. 1,2-oxaphospholane - 2-oxo-2-methoxy-3,5-di-(4-chlorophenyl)-5-dimethylphosphono-1,2-.
.
~0490;~0 oxaphospholane 2-oxo-2-methoxy-3-phenyl-5-(4-chlorophenyl)-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-(4-methylphenyl)-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-(4-methoxyphenyl)-5-phenyl-5-dimethyl-phosphone-1,2-oxaphospholane 2-oxo-2-methoxy-3-phenyl-5-(4-methylphenyl)-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-methoxy-3-(phenyl-2)-5-phenyl-5-dimethylphosphono-1,2-oxaphospholane 2-oxo-2-allyloxy-3,3,5-trimethyl-5-diallylphosphono-1,2-oxaphos-pholane 2-oxo-2-tetrahydrofurfuryl-3,3-5-trimethyl-5-di-(tetrahydrofurfuryl)-phosphono-(1,2-oxaphospholane) The surprising discovery has been made that it is possible to manu-facture the compounds of the formula I, in which R3 is the same as Rl or R2, by a novel process which comprises reacting an a,~-unsaturated ketone of the formula II
2Q 4 \ R6 (II) with atleast2 moles of a phosphite of the formula III
~0 /
H - P \ (III) . OR2 in the presence of a base, with or without the addition of a solvent.
Examples of a,B-unsaturated ketones of the formula II are methyl . .~
S vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, mesityl oxide, methyl isopropenyl ketone, benzalacetone, benzalacetophenone or 4-chlorobenzalace-tone. Such ketones can be manufactured by known methods, for example by condensation of the appropriate methyl ketones with aldehydes or ketones.
' '' 10'19030 The phosphites of the formula III are known compounds of industrial availability. Examples thereof are dialkyl phosphites, e.g. dimethyl, di-ethyl or dioctyl phosphite, dicycloalkyl phosphites, e.g. dicyclohexyl phosphite, diaralkyl phosphites, e.g. dibenzyl phosphite, and mixed phos-phites, e.g. methyl butyl phosphite, methyl benzyl phosphite or isopropyl cyclohexyl phosphite.
In the reaction there are used 2 moles, preferably 205 to 3.5 moles, of a compound of the formula III for each mole of the compound of the formula II.
Examples of bases which catalyse the reaction are principally alkali metals, alkali metal or alkaline earth metal alkoxides, alkali metal amides and hydrides. Particularly effective are the metals sodium and potassium, sodium methoxide, potassium tert. butoxide, lithium amide and calcium hydride; but the two metals are particularly suitablefor the purpose.
Normally, catalytic amounts of these bases suffice to initiate the reaction.
; It is sometimes advantageous to add further amounts of base during the reac-tion.
If the process according to the invention is carried out with the addition of a solvent, then suitable solvents are primarily hydrocarbons, e.g. benzene, toluene, xylene, ligroin, hexane or heptane, also alcohols, e.g. methanol, ethanol or isopropanol, or ethers, e.g. diethyl ether, dioxan or tetrahydrofuran.
The reaction can be carried out by dissolving the ketone of the formula II and adding dropwise a portion of the phosphite of the formula III
and the base. Upon onset of the reaction, the remainder of the phosphite and, if necessary, further amounts of base, are addedby gradual amounts. It is also possible to premix the phosphite with the catalyst and to add the ketone of the formula II dropwise.
In another embodiment, the compounds of the formula II and III
and optionally the solvent are first mixed and then the base, which can also be dissolved in the solvent, is added to this mixture and the reaction is brought to completion by heating.
_ g _ The oxaphospholanes of the formula I are isolated by customary methods, for example by distillation. Desirably the base is neutralised be-fore the isolation by an equivalent amount of an acid, for example acetic acid.
The reaction of dialkyl phosphites with a,B-unsaturated ketones has already been thoroughly investigated by various experts. It has hitherto been considered the rule that in the reaction only 1 mole of phosphite is added to the double bond forming the y-ketophosphonates (see Houben-Weyl, Methoden der Organischen Chemie, vol. 12/1, pages 465-467, G. Thieme Verlag, Stuttgart, 1963). If diphosphonates were also obtained, these occurred in moderate yield in addition to the monophosphonates (A.N. Pudovik, Zhurnal Obshch. Khim. 22 (1952), 1371, ref. Chem. Abstr. 47 (1953), 4837). It was therefore surprising that in the process described herein 2 moles of phosphite are added easily. It was furthermore surprising that the ~-phosphono-a-hydroxyphosphonates evidently formed as intermediate cyclise under the reaction contitions rapidly and virtually completely to give the 1,2-oxaphospholane-5-phosphonates.
It has furthermore been found that oxaphospholane derivatives of the formula I can also be manufactured from the known y-ketophosphonates by addition of dialkyl phosphites. This is an indication that the reaction discussed above probably proceeds via the stage of the y-ketophosphonates. It is therefore possible to carry out the reaction in two partial steps, the first being the known addition of 1 mole of phosphite to a,B-unsaturated ketones to form the y-ketophosphonates and the second being the reaction with a second mole of phosphite to form the oxaphospholanes. This second step is just as surprising and novel as the single step main process.
The invention therefore also provides a process for the manu-facture of compounds of the formula I, which comprises reacting a compound of the formula IV
0 R4 R6 j (R30)2P- C- CH -C -R7 (IV) with at least one mole of a phosphite of the formula III in the presence of a base, with or without the addition of a solvent. In the formula IV, the substituents R3 to R7 have the same meanings assigned to them as in respect of the compounds of the formula I. The catalysts and solvents suitable for use in this process are the same as those for the single step main process described hereinbefore, and the reaction and isolation of the products are carried out in the same way.
This modification is principally of importance for the manufacture of those compounds of the formula I in which R3 is different from Rl and R2.
The compounds of the formula I are outstanding flameproofing agents for thermoplastic polymers, polyurethanes, epoxy resins, cellulose and also for cellulose derivatives. It has long been known to use phosphorus-containing compounds as flameproofing agents for polymers, but it is normally necessary to use the phosphorus compounds in high concentrations, which results as a rule in a deterioration of the physical and technological properties of the polymers.
The surprising discovery has now been made that the new 1,2-oxa-phospholanes of the formula I impart an adequate flame resistance to the ; polymers even in relatively low concentrations. Moreover, on account of their considerable heat stability they have only a minute influence on the physical properties of the substrates. Further they are also usable in reactive systems, such as in polyurethane foams or in epoxy resins which,both in their manu-facture and use, are highly sensitive towards additives.
Examples of thermoplastic polymers which can be flame-protected with the compounds of the formula I are:
1. Polymers which are derived from simply or doubly unsaturated hydrocarbons, such as polyolefins, e.g. polyethylene, polypropylene, polyisobutylene, ' polymethylbutene-l, polymethylpentene-l, polybutene-l, polyisoprene, poly-butadiene, polystyrene, polyisobutylene, copolymers of the monomers based on the cited homopolymers, such as ethylene-propylene comonomers, propylene-butene-l copolymers, propylene-isobutylene copolymers, styrene-butadiene co-polymers, and terpolymers of ethylene and propylene with a diene, eOg.
~049030 hexadiene, dicyclopentadiene or ethylidene norbornene; mixtures of the above mentioned homopolymers, e.g. mixtures of polypropylene and polyethylene, polypropylene and polybutene-l, polypropylene and polyisobutylene.
2. Halogen-containing vinyl polymers, e.g. polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, but also polychloroprene and chlorinated rubbers.
3. Polymers which are derived from a,~-unsaturated acids and derivatives thereof, e.g. polyacrylates and polymethacrylates, polyacrylamides and poly-acrylonitrile and copolymers thereof with other vinyl compounds, such as acrylonitrile/butadiene/styrene, acrylonitrile/styrene and acrylonitrile/
styrene/acrylic ester copolymers.
styrene/acrylic ester copolymers.
4. Polymers which are derived from unsaturated alcohols and amines and their acryl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, and copolymers thereof with other vinyl compounds, e.g. ethylene/vinyl acetate copolymers.
5. Polyacetals, e.g. polyoxymethylene and polyoxyethylene, and also those polyoxymethylenes that contain ethylene oxide as comonomer.
6. Polyphenylene oxides.
7. Polycarbonates.
8. Polysulphones.
9. Polyamides and copolyamides which are derived from diamines and dicarboxy-lic acids and/or aminocarboxylic acids or from the corresponding lactams, e.g. polyamide 6, polyamide 6/6, polyamide 6/lO, polyamide ll, polyamide 12.
` 10. Polyesters which are derived from dicarboxylic acids and dialcohols and/or the corresponding lactones, e.g. polyethylene glycol terephthalate, polybutyrene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate~
` The flameproofing of cellulose and cellulose derivatives is possible in those cases where the polymer is processed from solution or from the melt, so that the flameproofing agent can be added to this solution or melt. The cellulose xanthogenate solutions which are known as viscose solutions and which are used for the manufacture of fibres and sheets of :
. . .. ... ..
regenerated cellulose are one example. Solutions of cellulose acetate in organic solvents are another example.
Polyurethanes which can be given a flameproof finish with the compounds of the formula I can be both linear and branched polyurethanes such as are used for the manufacture of films, fibres, brushes, coatings, elastic materials and rigid and soft foam plastics. The flameproofing of polyurethane foam plastics is of particular importance since such foams, like all materials having a large surface area, burn more easily than compact materials.
It is common knowledge that such polyurethane foams or coating compositions are manufactured from polyhydroxy compounds, e.gO polyesters or polyethers which contain hydroxy groups on the one hand and polyisocyanates, - e.g. toluylene diisocyanate, on the other. The introduction of flameproofing agents of the formula I can be accomplished by adding them to the starting components mentioned hereinbefore, i.e. simultaneously with the manufacture of the polyurethanes, since the oxaphospholane derivatives scarcely influence the pot life and curing time. Non-inflammable polyurethane foam plastics or coatings with excellent mechanical properties and very good resistance to ageing are thereby obtained.
The same applies to the flameproofing of epoxy resins. These resins are usually manufactured by mixing an epoxide component with a hardener component, whereupon a poly-addition reaction takes place between the two components. The flameproofing agents of the formula I can be mixed both with ` the epoxide and with the hardener component since they are compatible with both and such mixtures are storable. But it is also possible to add the flameproofing agent only during the manufacture of the resin as third com-ponent so long as the resin is still liquid and not yet formed.
Epoxy resins are used frequently in those cases where a high ` thermal stability of a resin under load is required~ Many organic flame-proofing agents, for example phosphorus esters of chloroparaffins, effect a perceptible reduction in the thermomechanical stability of epoxy resins.
However, such small amounts of the compounds of the formula I are required for an effective flameproofing of epoxy resins that the thermomechanical , .
stability of these latter is not noticeably impaired.
The compounds of the formula I are normally added to the cited substrates in an amount of 2 to 30% by weight, preferably 2 to 10% by weight, based on the substrate. The addition can be carried out before or during the manufacture of the substrate by polymerisation; but frequently the compounds are added to the finished polymers before or during their processing.
In addition to the flameproofing agents of the formula I, it is also possible to add to the polymeric substrates other flameproofing agents, e.g. organic halogen compounds, antimony oxide or other phosphorus compounds.
It is furthermore possible to add other customary and known additives, e.g.
antioxidants, heat stabilisers, UV absorbers, fluorescent brighteners, anti-static agents, lubricants, softeners, emulsifiers, pigments, carbon black, asbestos, kaolin, talcum, glass fibres or other fillers and reinforcing agents.
The manufacture and utility of the oxaphospholanes of the formula I are illustrated in re detail in the following Examples.
Example 1 Preparation of 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphos-pholane , .,
` 10. Polyesters which are derived from dicarboxylic acids and dialcohols and/or the corresponding lactones, e.g. polyethylene glycol terephthalate, polybutyrene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate~
` The flameproofing of cellulose and cellulose derivatives is possible in those cases where the polymer is processed from solution or from the melt, so that the flameproofing agent can be added to this solution or melt. The cellulose xanthogenate solutions which are known as viscose solutions and which are used for the manufacture of fibres and sheets of :
. . .. ... ..
regenerated cellulose are one example. Solutions of cellulose acetate in organic solvents are another example.
Polyurethanes which can be given a flameproof finish with the compounds of the formula I can be both linear and branched polyurethanes such as are used for the manufacture of films, fibres, brushes, coatings, elastic materials and rigid and soft foam plastics. The flameproofing of polyurethane foam plastics is of particular importance since such foams, like all materials having a large surface area, burn more easily than compact materials.
It is common knowledge that such polyurethane foams or coating compositions are manufactured from polyhydroxy compounds, e.gO polyesters or polyethers which contain hydroxy groups on the one hand and polyisocyanates, - e.g. toluylene diisocyanate, on the other. The introduction of flameproofing agents of the formula I can be accomplished by adding them to the starting components mentioned hereinbefore, i.e. simultaneously with the manufacture of the polyurethanes, since the oxaphospholane derivatives scarcely influence the pot life and curing time. Non-inflammable polyurethane foam plastics or coatings with excellent mechanical properties and very good resistance to ageing are thereby obtained.
The same applies to the flameproofing of epoxy resins. These resins are usually manufactured by mixing an epoxide component with a hardener component, whereupon a poly-addition reaction takes place between the two components. The flameproofing agents of the formula I can be mixed both with ` the epoxide and with the hardener component since they are compatible with both and such mixtures are storable. But it is also possible to add the flameproofing agent only during the manufacture of the resin as third com-ponent so long as the resin is still liquid and not yet formed.
Epoxy resins are used frequently in those cases where a high ` thermal stability of a resin under load is required~ Many organic flame-proofing agents, for example phosphorus esters of chloroparaffins, effect a perceptible reduction in the thermomechanical stability of epoxy resins.
However, such small amounts of the compounds of the formula I are required for an effective flameproofing of epoxy resins that the thermomechanical , .
stability of these latter is not noticeably impaired.
The compounds of the formula I are normally added to the cited substrates in an amount of 2 to 30% by weight, preferably 2 to 10% by weight, based on the substrate. The addition can be carried out before or during the manufacture of the substrate by polymerisation; but frequently the compounds are added to the finished polymers before or during their processing.
In addition to the flameproofing agents of the formula I, it is also possible to add to the polymeric substrates other flameproofing agents, e.g. organic halogen compounds, antimony oxide or other phosphorus compounds.
It is furthermore possible to add other customary and known additives, e.g.
antioxidants, heat stabilisers, UV absorbers, fluorescent brighteners, anti-static agents, lubricants, softeners, emulsifiers, pigments, carbon black, asbestos, kaolin, talcum, glass fibres or other fillers and reinforcing agents.
The manufacture and utility of the oxaphospholanes of the formula I are illustrated in re detail in the following Examples.
Example 1 Preparation of 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphos-pholane , .,
10 ml of diethyl phosphite are added to a solution of 98.1 g (1 mole) of mesityl oxide in 300 ml of benzene and the mixture is then heated to 80C. About 200 mg of metallic sodium are added to the almost boiling solution, whereupon an exothermic reaction commences. The reaction is brought to completion over the course of 10 minutes by gradual addition of altogether 345.0 g (2.5 moles) of diethyl phosphite and 402 g of sodiw. The reaction mixture is stirred for further 10 minutes, neutralised with 11 g of glacial acetic and evaporated in vacuum. The residue is distilled in a high vacuum.
The main fraction distills as an almost colourless oil at 136-139C and ; 0.035 mm Hg. After analysis, nuclear magnetic resonance and mass spectrum this fraction is 2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane of the empirical formula C12H2606P2 (M = 328029).
Analysis:
calc.: C 43.90 H 7.99 P 18.92 10490;~0 found: C 44.30 H 8.00 P 18.0 The yield is 45.3% of theory.
The same reaction is carried out with 392 g (4 moles) of mesityl oxide and 1660 g (12 moles) of diethyl phosphite in 1200 ml of benzene and in the presence of 9.5 g of sodium. Upon completion of the reaction (40 minutes), the reaction mixture is neutralised with 24.8 g of glacial acetic acid and distilled to yield 995.7 g of 2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphone-12-oxaphospholane which melts at 136-140C at 0.02-0.04 Torr. This corresponds to a yield of 75.9% of theoryO
Example 2 Preparation of 2-Oxo-2-methoxy-3,3,5-trimethyl-S-dimethyl-phosphono-1,2-oxaphospholane A solution of 30.0 g of sodium methoxide in 90 ml of methanol is added dropwise to a mixture of 220 g of dimethyl phosphite and 98 g of mesityl oxide over the course of 2 hours in such a way that the reaction temperature does not exceed 65C. The clear solution is subsequently heatet for 2 hours to 70C. The reaction mixture is concentrated in vacuo and the residue is taken up in 200 ml of tolueneO The solution is filtered and the filtrate tistilled. The 2-oxo-2-methoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphospholane distills at 158-160C in the form of a colourless, viscous oil.
Analysis, calc. for CgH20P206 (M = 286.20) ` calc.: C 37.80 H 7.05 P 21.65 fount: C 37.79 H 7.C4 P 21.32 ~ ExamPle 3 `~` Flameproofing of a polyurethane foam A soft polyurethane foam is manufactured by mixing the following materials:
100 g of a polyhydroxy compound on a polyether basis with a molecular weight of about 3000 and a OH number of 56 1 g of a siloxane-oxyalkylene copolymer 0.1 g of tin (II) octoate 3.5 g of water 48.2 g of toluylene diisocyanate (80:20 mixture of the 2,4-and the 2,5-isomers) x g of 2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane (compound of Example 1).
The foam so manufactured is tested for its flammability by the ASIMD 1692 test method. For this purpose, test specimens each measuring 150 mm x 50 mm x 13 mm are fixed with the 50 mm x 13 mm surface in the horizontal positionO Marks are made at 25 mm and 100 mm. The bottom end of the 10specimen is then ignited with a gas burner. The ignition time is 60 seconds~
The foam is termed flameproof if the burned zone is not longer than 25 mm.
If the specimen burns beyond the 25 mm mark and the burned zone is smaller than 125 mm, then the foam is termed self-extinguishing. The length of the burned zone is indicated in mm. If the specimen burns beyond the 125 mm, the foam is termed combustible.
:. :
., .
,, :
~ - 16 -.
:
_ ~ N 00 N Ln _~
1~ ~ .
_ X
~ O O O O _l ~ 1~
~.
1~49030 Individual foam specimens are also subjected to the flameproofing test after an ageing at 140C dry and 90C humid over the course of 1, 2, 4 and 7 days.
~: b O O O O O u~ o ~ u~
0~ 'D `D u~ ~
~0 bO ~:
~000 . .
¦ ~a ~ ¦ O u~ O ¦ :
1 ~2~ 1 :,.
::' .
`:
~3 u~ , ~ ~ 3 ., a~ ~ , ~ ~ I~
b b b b ~ @ ~ b b b ~t ~ ~O ~
.~ u~-~ ~ cd nl u~cn ~d cd t~ td ., ~.. , .~ . . .
These figures show that a storage resistant flameproofing is obtained with 2-oxo-3,3,5-trimethyl-S-diethylphosphone-1,2-oxaphospholane even if only 4 g of this compound per 100 g of polyol is used.
ExamPle 4 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylPhosphono-1,2-oxaPhospholane 98 g of mesityl oxide (1.0 mole) and 415 g of diethyl phosphite (3.0 moles) are dissolved in 300 ml of benzene and 200 ml of this solution are heated to the boil. A catalytic amount of sodium is added whereupon a vigorous exothermic reaction commences and the mixture boils by itself after removal of the heating bath. After the sodium has dissolved the reaction comes practically to a stop and is initiated a fresh by addition of a further amount of sodium. In this manner sodium is added until the main reaction is over. Then about one third of the remaining solution is passed in and this is reacted as previously by adding sodium. The remaining two-thirds of the solution are reacted in the same way. Altogether 3.0 g of sodium are used -over the course of 25 minutes. The reaction mixture is allowed to continue to react for 15 minutes at boiling temperature, then it is neutralised with 8 g of glacial acetic acid and diluted with 350 ml of benzene. After the reaction solution has cooled, it is washed with two portions of water of 75 and 20 ml respectively. The combined aqueous phases are extracted with 50 ml of benzene twice to give a solution in benzene which is combined with the chief portion, dried with Na2SO4 and concentrated in a rotary evaporator.
Distillation yields 118.5 g of first runnings of b.p. 46-68C/8 mm Hg, which largely consists of diethyl phosphite, and 280.8 g (85.6% of theory) of the oxaphospholane which boils at 122-132C at 0.008 mm Hg. Gas chromatography shows the product to be about 95% pure. 8.2 g remain as distillation residue.
Example S
2-Oxo-2-isopropoxy-3,3,5-trimethyl-5-diisopropylphosphono-l~2-oxaphospholane As described in Example 4, a mixture of 19.6 g of mesityl oxide (0.20 mole), 99.6 g of diisopropyl phosphite (0.60 mole) and 100 ml of benzene ` is reacted with 2.1 g of sodium as catalyst over the course of 10 minutes.
The reaction is vigorously exothermic. After a subsequent reaction of 15 .~ - 19 -.
104~10 minutes at boiling temperature the reaction mixture is neutralised with 5.5 g of glacial acetic acid and diluted with 150 ml of benzene. After the ; reaction solution has cooled it is extracted with 20 ml of benzene twice and the extract is combined with the chief portion, dried over Na2SO4 and concen-trated in a rotary evaporator. The distillation yields 27.5 g of first runnings with a boiling point of 68-75C/10 mm Hg and consisting of virtually pure diisopropyl phosphite as well as 58.0 g (78.3%) of the oxaphospholane which boils at 120/0.02 mm Hg to 125C/0.05 mm Hg; 5.3 g remain as residue.
Analysis~ for C15H326P2 (M = 370-37) calc.: C 48.64 H 8.71 P 16.73 found: C 48.77 H 8.92 P 16.37 The mass spectrum shows the molecular peak at m/e 370.
ExamPle 6 2-Oxo-2-ethoxy-4,5-dimethyl-5-diethylphosphono-1,2-oxaphosPholane In analogous manner to Example 4, a mixture of 25 g of freshly distilled methyl isopropenyl ketone (0.30 mole), 124 g of diethyl phosphite (0,90 mole) and 75 ml of benzene are reacted with 2.5 g of sodium over the course of 10 minutes. The reaction is vigorously exothermic. After a subsequent reaction of 10 minutes at boiling temperature, the reaction mixture ~; 20 is neutralised with glacial acetic acid and diluted with 300 ml of benzene.
After the reaction solution has cooled, it is extracted with 60 ml of H20.
The aqueous phase is extracted twice with 60 and 30 ml of benzene respectively and the extract is combined with the chief portion, dried over Na2SO4 and concentrated in a rotary evaporator. The distillation yields 49.2 g (52.2%
of theory) of the oxaphospholane of b.p. 128-132C/0.002 mm Hg.
AnalysiS, for CllH24O6P2 (M = 314-26) . .~
calc.: C 42.04 H 7.70 P 19.71 ~ found: C 41.78 H 7.69 P 19.39 - The mass spectrum shows the molecular peak at m/e 314.
Example 7 2-Oxa-2-butoxy-3,3,5-trimethyl-5-dibutylphosphono-1,2-oxaphospholane A reaction solution is prepared from 194 g (1 mole) of freshly distilled dibutyl phosphite and 32.4 g (0.33 mole) of mesityl oxide in 200 ml of absolute benzene.
30 ml of this mixture are put into the reaction flask and treated with about 50 mg of sodium. An exothermic reaction commences and the tempera-ture rises to 70C. After the reaction has subsided, the reaction mixture is broughtto reflux temperature by addition of reaction solution in small amounts and of 1.5 g of s~dium. Stirring is continued for 1 hour at 70C and the reaction mixture is subsequently neutralised with glacial acetic acid.
Distillation yields the product with a boiling point of 158-162C/O.Ol mm.
Example 8 2-Oxa-2-cyclohexoxy-3,3,5-trimethyl-dicyclohexylphosPhono-l~2-oxaphospholane ` 88 g (0.35 mole) of freshly distilled dicylohexyl phosphite are dissolved in 150 ml of absolute benzene and the solution is warmed to 50C.
After addition of 2 g of sodium, 15 g (0.14 mole) of freshly distilled mesityl oxide are added dropwise. The exothermic reaction causes the temperature of the mixture to rise to 70C. After termination of the reaction, the reaction mixture is stirred for further 2 hours and then neutralised with glacial acetic acid. The filtered solution is distilled and the product with a boiling point of 150-153C/O.Ol mm Hg is obtained.
Example 9 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaPhosPholane 690 g of diethyl phosphite and 50 g of a sodium methoxide solution (17 g of sodium dissolved in 83 g of ethanol) are mixed in a sulphurating flask. With stirring, 245.5 g of mesityloxide are dropped into this solution over the course of 40 minutes. During the dropwise addition an exothermic reaction takes place, the reaction temperature rising from 20C to 101C when ` up to half the a unt of mesityl oxide has been added. The temperature then falls to 75C when the second half of the mesityl oxide is added. The colour-less, clear solution is stirred for 50 minutes and the temperature in the reaction mixture falls to 39C. Then a further 25 g of sodium methoxide solution are added all at once, whereupon the temperature of the reaction ~049030 mixture rises from 39 to 84C. The reaction mixture is stirred for 30 minutes and then 25 g of sodium methoxide solution are added. The resultant reaction mixture is stirred for 3 hours at room temperature and subsequently neutralised with 15 g of glacial acetic acid. Distillation of this reaction mixture yields at 162-167C/0.05 mm 626 g of 2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane as a colourless liquid. Chromatographic analysis shows a purity of 99.1%.
Example 10 2-Oxo-2-ethoxy-5-methyl-5-diethylphosphono-1,2-oxaphosPholane 276 g (2 moles) of freshly distilled diethyl phosphite are treated with a solution of 3.5 g of sodium methoxide in 20 ml of absolute ethanol and 70 g (1 mole) of freshly distilled methyl vinyl ketone are added dropwise thereto. The exothermic reaction causes the temperature of the mixture to rise to about 70C. After the whole amount of methyl vinyl ketone has been dropped in, stirring is continued for 2 lt2 hours and the reaction mixture is neutralised with glacial acetic acid. After a first runnings which con-sists largely of diethyl phosphite and methyl vinyl ketone, the distillation at 0.01 mm yields the product with a boiling point of 120-133C.
ExamPle 1 1 2-Oxo-2-ethoxy-5-ethyl-diethylphosphono-1,2-oxaphospholane 138 g (1 mole) of freshly distilled diethyl phosphite are treated with a solution of 1.75 g (0O075 mole) of sodium in 10 ml of absolute ethanol and 42 g (0.5 mole) of ethyl vinyl ketone are added dropwise thereto. The exothermic reaction causes the temperature of the mixture to rise to 70C.
After the whole amount of ethyl vinyl ketone has been dropped in, the reaction i ; is brought to completion by adding once more 1 g (0.04 mole) of sodium in 10 ml of absolute alcohol when again a rise in temperature to 60C is observed.
`t Stirring is continued for 2 hours and the reaction mixture is then neutra-lised with glacial acetic acid. After a first runnings which consists largely of diethyl phosphite and ethyl vinyl ketone, the distillation at 0.1 mm yields the product having a boiling point of 132-138C.
; ~. ~ ' '' :.
Example 12 2-Oxo-2-ethoxy-3-phenyl-5-methyl-5-diethylphosphono-1,2-oxaphospholane 276 g (2 moles) of freshly distilled diethyl phosphite are treated with a solution of 3.5 g (0.15 mole) of sodium in 20 ml of absolute ethanol.
At 40C, 146 g (1 mole) of benzalacetone are dissolved in 50 ml of absolute ethanol and this solution is added dropwise to the first solution. The exo-thermic reaction causes the temperature of the mixture to rise to 90C over the course of 1 hour. After completion of the addition of benzalacetone, the reaction mixture is stirred for 3 hours and neutralised with glacial acetic acid. The product is isolated in the subsequent distillation at 187-210C/0.01 mm.
Example 13 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphosPholane 10 ml of a mixture of 70.8 g of 4-methyl-4-~diethylphosphono)-pentanone-2 (prepared from mesityl oxide and diethyl phosphite) and 82.8 g of diethyl phosphite are dissolved in 100 ml of toluene and the solution is heated to 80C. A catalytic amount of sodium is added and a vigorous exo-thermic reaction commences. The reaction temperature is held between 80C and 90C by alternately adding the previously prepared mixture and small pieces of sodium. Altogether 1.65 g of sodium are used as catalyst. The reaction takes ! 20 minutes. The reaction mixture is subsequently stirred at 80C-90C for 30 minutes with heating, then cooled and neutralised with 4.5 g of glacial acetic acid. This reaction mixture is distilled to yield 2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane with a boiling point of 156C-161C/l.l mm. This substance is identical with the oxaphospholane manufac-tured ascording to Example 4.
Example 14 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphospholane By carrying out the same procedure as described in Example 13, 2-ethoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphospholane with a boiling point of 146-148C/0.5 mm is obtained from 70.8 g of 4-methyl-4-(diethyl-phosphono)-pentanone-2- and 66.0 g of dimethyl phosphite with 1.65 g of sodium as catalyst.
Example 15 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-di-(isopropyl)-phosphono-l~2-oxaphospholane By carrying out the same procedure as described in Example 13, 2-ethoxy-3,3,5-trimethyl-5-di-(isopropyl)-phosphono-1,2-oxaphospholane with a boiling point of 180-185C/2 mm is obtained from 70.8 g of 4-methyl-4-(diethylphosphono)-pentanone-2 and 99.6 g of diisopropyl phosphite with 4.6 g of sodium as catalyst.
Example 16 2-Oxo-2-methoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane By carrying out the same procedure as described in Example 13, 2-oxo-2-methoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane with a boiling point of 144-146C/0.6 mm is obtained from 83.2 g of 4-methyl-4-(dimethylphosphono)-pentanone-2 and 110.4 g of diethyl phosphite with 1.15 g of sodium as catalyst. The p31 spectrum shows for the phosphorus atom in the 5-ring a shift of -48 ppm compared with H3PO4 as standard.
Example 17 2-Oxo-2-ethoxy-3,3,S-trimethyl-5-di-(isooctyl)-phosphono-1,2-oxaphospholane By carrying out the same procedure as described in Example 13, 2-oxo-2-ethoxy-3,3,5-trimethyl-S-di-(isooctyl)-phosphono-1,2-oxaphospholane is obtained as a viscous, colourless oil from 47.2 g of 4-methyl-4-(diethyl-phosphono)-pentanone-2 and 84.6 g of di-isooctyl phosphite with 1.15 g of sodium as catalyst. The p31 spectrum of this oil shows for the phosphorus atom in the ring a shift of -49 ppm compared with H3PO4 as standard.
Example 18 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-di-n-octylPhosphono-1,2-oxaphospholane : By carrying out the same procedure as described in Example 13, ~ 2-oxo-2-ethoxy-3,3,5-trimethyl-5-di-n-octylphosphono-1,2-oxaphospholane is obtained as a viscose, pale yellow oil from 47.2 g of 4-methyl-4-(diethyl-Y` 30 phosphono)-pentanone-2 and 84.6 g of di-n-octylphosphite with 1.15 g of sodium as catalyst. The p31 spectrum of this oil shows for the phosphorus atom in the ring a shift of -49 ppm compared with H3PO4.
- .' '.' ' ' ... ' ~ ~ ' ..
Example l9 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-di-(-2-chloroethyl)-phosphono-1,2-oxaphos-lane By carrying out the same procedure as described in Example 13, 2-oxo-2-ethoxy-3,3,5-trimethyl-5-di-(2-chloroethyl~-phosphono-1,2-oxaphos-pholane is obtained from 47.2 g of 4-methyl-4-(diethylphosphono)-pentanone-2 and 45.2 g of bis(2-chloroethyl)-phosphite. In the p31 spectrum, this com-pound shows for the phosphorus atom in the ring a shift of -50.2 ppm compared with H3PO4 as standard.
Example 20 2-Oxo-2-propyloxy-3,3,5-trimethyl-5-dipropylphosphono-1,2-oxaphospholane
The main fraction distills as an almost colourless oil at 136-139C and ; 0.035 mm Hg. After analysis, nuclear magnetic resonance and mass spectrum this fraction is 2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane of the empirical formula C12H2606P2 (M = 328029).
Analysis:
calc.: C 43.90 H 7.99 P 18.92 10490;~0 found: C 44.30 H 8.00 P 18.0 The yield is 45.3% of theory.
The same reaction is carried out with 392 g (4 moles) of mesityl oxide and 1660 g (12 moles) of diethyl phosphite in 1200 ml of benzene and in the presence of 9.5 g of sodium. Upon completion of the reaction (40 minutes), the reaction mixture is neutralised with 24.8 g of glacial acetic acid and distilled to yield 995.7 g of 2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphone-12-oxaphospholane which melts at 136-140C at 0.02-0.04 Torr. This corresponds to a yield of 75.9% of theoryO
Example 2 Preparation of 2-Oxo-2-methoxy-3,3,5-trimethyl-S-dimethyl-phosphono-1,2-oxaphospholane A solution of 30.0 g of sodium methoxide in 90 ml of methanol is added dropwise to a mixture of 220 g of dimethyl phosphite and 98 g of mesityl oxide over the course of 2 hours in such a way that the reaction temperature does not exceed 65C. The clear solution is subsequently heatet for 2 hours to 70C. The reaction mixture is concentrated in vacuo and the residue is taken up in 200 ml of tolueneO The solution is filtered and the filtrate tistilled. The 2-oxo-2-methoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphospholane distills at 158-160C in the form of a colourless, viscous oil.
Analysis, calc. for CgH20P206 (M = 286.20) ` calc.: C 37.80 H 7.05 P 21.65 fount: C 37.79 H 7.C4 P 21.32 ~ ExamPle 3 `~` Flameproofing of a polyurethane foam A soft polyurethane foam is manufactured by mixing the following materials:
100 g of a polyhydroxy compound on a polyether basis with a molecular weight of about 3000 and a OH number of 56 1 g of a siloxane-oxyalkylene copolymer 0.1 g of tin (II) octoate 3.5 g of water 48.2 g of toluylene diisocyanate (80:20 mixture of the 2,4-and the 2,5-isomers) x g of 2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane (compound of Example 1).
The foam so manufactured is tested for its flammability by the ASIMD 1692 test method. For this purpose, test specimens each measuring 150 mm x 50 mm x 13 mm are fixed with the 50 mm x 13 mm surface in the horizontal positionO Marks are made at 25 mm and 100 mm. The bottom end of the 10specimen is then ignited with a gas burner. The ignition time is 60 seconds~
The foam is termed flameproof if the burned zone is not longer than 25 mm.
If the specimen burns beyond the 25 mm mark and the burned zone is smaller than 125 mm, then the foam is termed self-extinguishing. The length of the burned zone is indicated in mm. If the specimen burns beyond the 125 mm, the foam is termed combustible.
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1~49030 Individual foam specimens are also subjected to the flameproofing test after an ageing at 140C dry and 90C humid over the course of 1, 2, 4 and 7 days.
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These figures show that a storage resistant flameproofing is obtained with 2-oxo-3,3,5-trimethyl-S-diethylphosphone-1,2-oxaphospholane even if only 4 g of this compound per 100 g of polyol is used.
ExamPle 4 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylPhosphono-1,2-oxaPhospholane 98 g of mesityl oxide (1.0 mole) and 415 g of diethyl phosphite (3.0 moles) are dissolved in 300 ml of benzene and 200 ml of this solution are heated to the boil. A catalytic amount of sodium is added whereupon a vigorous exothermic reaction commences and the mixture boils by itself after removal of the heating bath. After the sodium has dissolved the reaction comes practically to a stop and is initiated a fresh by addition of a further amount of sodium. In this manner sodium is added until the main reaction is over. Then about one third of the remaining solution is passed in and this is reacted as previously by adding sodium. The remaining two-thirds of the solution are reacted in the same way. Altogether 3.0 g of sodium are used -over the course of 25 minutes. The reaction mixture is allowed to continue to react for 15 minutes at boiling temperature, then it is neutralised with 8 g of glacial acetic acid and diluted with 350 ml of benzene. After the reaction solution has cooled, it is washed with two portions of water of 75 and 20 ml respectively. The combined aqueous phases are extracted with 50 ml of benzene twice to give a solution in benzene which is combined with the chief portion, dried with Na2SO4 and concentrated in a rotary evaporator.
Distillation yields 118.5 g of first runnings of b.p. 46-68C/8 mm Hg, which largely consists of diethyl phosphite, and 280.8 g (85.6% of theory) of the oxaphospholane which boils at 122-132C at 0.008 mm Hg. Gas chromatography shows the product to be about 95% pure. 8.2 g remain as distillation residue.
Example S
2-Oxo-2-isopropoxy-3,3,5-trimethyl-5-diisopropylphosphono-l~2-oxaphospholane As described in Example 4, a mixture of 19.6 g of mesityl oxide (0.20 mole), 99.6 g of diisopropyl phosphite (0.60 mole) and 100 ml of benzene ` is reacted with 2.1 g of sodium as catalyst over the course of 10 minutes.
The reaction is vigorously exothermic. After a subsequent reaction of 15 .~ - 19 -.
104~10 minutes at boiling temperature the reaction mixture is neutralised with 5.5 g of glacial acetic acid and diluted with 150 ml of benzene. After the ; reaction solution has cooled it is extracted with 20 ml of benzene twice and the extract is combined with the chief portion, dried over Na2SO4 and concen-trated in a rotary evaporator. The distillation yields 27.5 g of first runnings with a boiling point of 68-75C/10 mm Hg and consisting of virtually pure diisopropyl phosphite as well as 58.0 g (78.3%) of the oxaphospholane which boils at 120/0.02 mm Hg to 125C/0.05 mm Hg; 5.3 g remain as residue.
Analysis~ for C15H326P2 (M = 370-37) calc.: C 48.64 H 8.71 P 16.73 found: C 48.77 H 8.92 P 16.37 The mass spectrum shows the molecular peak at m/e 370.
ExamPle 6 2-Oxo-2-ethoxy-4,5-dimethyl-5-diethylphosphono-1,2-oxaphosPholane In analogous manner to Example 4, a mixture of 25 g of freshly distilled methyl isopropenyl ketone (0.30 mole), 124 g of diethyl phosphite (0,90 mole) and 75 ml of benzene are reacted with 2.5 g of sodium over the course of 10 minutes. The reaction is vigorously exothermic. After a subsequent reaction of 10 minutes at boiling temperature, the reaction mixture ~; 20 is neutralised with glacial acetic acid and diluted with 300 ml of benzene.
After the reaction solution has cooled, it is extracted with 60 ml of H20.
The aqueous phase is extracted twice with 60 and 30 ml of benzene respectively and the extract is combined with the chief portion, dried over Na2SO4 and concentrated in a rotary evaporator. The distillation yields 49.2 g (52.2%
of theory) of the oxaphospholane of b.p. 128-132C/0.002 mm Hg.
AnalysiS, for CllH24O6P2 (M = 314-26) . .~
calc.: C 42.04 H 7.70 P 19.71 ~ found: C 41.78 H 7.69 P 19.39 - The mass spectrum shows the molecular peak at m/e 314.
Example 7 2-Oxa-2-butoxy-3,3,5-trimethyl-5-dibutylphosphono-1,2-oxaphospholane A reaction solution is prepared from 194 g (1 mole) of freshly distilled dibutyl phosphite and 32.4 g (0.33 mole) of mesityl oxide in 200 ml of absolute benzene.
30 ml of this mixture are put into the reaction flask and treated with about 50 mg of sodium. An exothermic reaction commences and the tempera-ture rises to 70C. After the reaction has subsided, the reaction mixture is broughtto reflux temperature by addition of reaction solution in small amounts and of 1.5 g of s~dium. Stirring is continued for 1 hour at 70C and the reaction mixture is subsequently neutralised with glacial acetic acid.
Distillation yields the product with a boiling point of 158-162C/O.Ol mm.
Example 8 2-Oxa-2-cyclohexoxy-3,3,5-trimethyl-dicyclohexylphosPhono-l~2-oxaphospholane ` 88 g (0.35 mole) of freshly distilled dicylohexyl phosphite are dissolved in 150 ml of absolute benzene and the solution is warmed to 50C.
After addition of 2 g of sodium, 15 g (0.14 mole) of freshly distilled mesityl oxide are added dropwise. The exothermic reaction causes the temperature of the mixture to rise to 70C. After termination of the reaction, the reaction mixture is stirred for further 2 hours and then neutralised with glacial acetic acid. The filtered solution is distilled and the product with a boiling point of 150-153C/O.Ol mm Hg is obtained.
Example 9 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaPhosPholane 690 g of diethyl phosphite and 50 g of a sodium methoxide solution (17 g of sodium dissolved in 83 g of ethanol) are mixed in a sulphurating flask. With stirring, 245.5 g of mesityloxide are dropped into this solution over the course of 40 minutes. During the dropwise addition an exothermic reaction takes place, the reaction temperature rising from 20C to 101C when ` up to half the a unt of mesityl oxide has been added. The temperature then falls to 75C when the second half of the mesityl oxide is added. The colour-less, clear solution is stirred for 50 minutes and the temperature in the reaction mixture falls to 39C. Then a further 25 g of sodium methoxide solution are added all at once, whereupon the temperature of the reaction ~049030 mixture rises from 39 to 84C. The reaction mixture is stirred for 30 minutes and then 25 g of sodium methoxide solution are added. The resultant reaction mixture is stirred for 3 hours at room temperature and subsequently neutralised with 15 g of glacial acetic acid. Distillation of this reaction mixture yields at 162-167C/0.05 mm 626 g of 2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane as a colourless liquid. Chromatographic analysis shows a purity of 99.1%.
Example 10 2-Oxo-2-ethoxy-5-methyl-5-diethylphosphono-1,2-oxaphosPholane 276 g (2 moles) of freshly distilled diethyl phosphite are treated with a solution of 3.5 g of sodium methoxide in 20 ml of absolute ethanol and 70 g (1 mole) of freshly distilled methyl vinyl ketone are added dropwise thereto. The exothermic reaction causes the temperature of the mixture to rise to about 70C. After the whole amount of methyl vinyl ketone has been dropped in, stirring is continued for 2 lt2 hours and the reaction mixture is neutralised with glacial acetic acid. After a first runnings which con-sists largely of diethyl phosphite and methyl vinyl ketone, the distillation at 0.01 mm yields the product with a boiling point of 120-133C.
ExamPle 1 1 2-Oxo-2-ethoxy-5-ethyl-diethylphosphono-1,2-oxaphospholane 138 g (1 mole) of freshly distilled diethyl phosphite are treated with a solution of 1.75 g (0O075 mole) of sodium in 10 ml of absolute ethanol and 42 g (0.5 mole) of ethyl vinyl ketone are added dropwise thereto. The exothermic reaction causes the temperature of the mixture to rise to 70C.
After the whole amount of ethyl vinyl ketone has been dropped in, the reaction i ; is brought to completion by adding once more 1 g (0.04 mole) of sodium in 10 ml of absolute alcohol when again a rise in temperature to 60C is observed.
`t Stirring is continued for 2 hours and the reaction mixture is then neutra-lised with glacial acetic acid. After a first runnings which consists largely of diethyl phosphite and ethyl vinyl ketone, the distillation at 0.1 mm yields the product having a boiling point of 132-138C.
; ~. ~ ' '' :.
Example 12 2-Oxo-2-ethoxy-3-phenyl-5-methyl-5-diethylphosphono-1,2-oxaphospholane 276 g (2 moles) of freshly distilled diethyl phosphite are treated with a solution of 3.5 g (0.15 mole) of sodium in 20 ml of absolute ethanol.
At 40C, 146 g (1 mole) of benzalacetone are dissolved in 50 ml of absolute ethanol and this solution is added dropwise to the first solution. The exo-thermic reaction causes the temperature of the mixture to rise to 90C over the course of 1 hour. After completion of the addition of benzalacetone, the reaction mixture is stirred for 3 hours and neutralised with glacial acetic acid. The product is isolated in the subsequent distillation at 187-210C/0.01 mm.
Example 13 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphosPholane 10 ml of a mixture of 70.8 g of 4-methyl-4-~diethylphosphono)-pentanone-2 (prepared from mesityl oxide and diethyl phosphite) and 82.8 g of diethyl phosphite are dissolved in 100 ml of toluene and the solution is heated to 80C. A catalytic amount of sodium is added and a vigorous exo-thermic reaction commences. The reaction temperature is held between 80C and 90C by alternately adding the previously prepared mixture and small pieces of sodium. Altogether 1.65 g of sodium are used as catalyst. The reaction takes ! 20 minutes. The reaction mixture is subsequently stirred at 80C-90C for 30 minutes with heating, then cooled and neutralised with 4.5 g of glacial acetic acid. This reaction mixture is distilled to yield 2-oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane with a boiling point of 156C-161C/l.l mm. This substance is identical with the oxaphospholane manufac-tured ascording to Example 4.
Example 14 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphospholane By carrying out the same procedure as described in Example 13, 2-ethoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphospholane with a boiling point of 146-148C/0.5 mm is obtained from 70.8 g of 4-methyl-4-(diethyl-phosphono)-pentanone-2- and 66.0 g of dimethyl phosphite with 1.65 g of sodium as catalyst.
Example 15 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-di-(isopropyl)-phosphono-l~2-oxaphospholane By carrying out the same procedure as described in Example 13, 2-ethoxy-3,3,5-trimethyl-5-di-(isopropyl)-phosphono-1,2-oxaphospholane with a boiling point of 180-185C/2 mm is obtained from 70.8 g of 4-methyl-4-(diethylphosphono)-pentanone-2 and 99.6 g of diisopropyl phosphite with 4.6 g of sodium as catalyst.
Example 16 2-Oxo-2-methoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane By carrying out the same procedure as described in Example 13, 2-oxo-2-methoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane with a boiling point of 144-146C/0.6 mm is obtained from 83.2 g of 4-methyl-4-(dimethylphosphono)-pentanone-2 and 110.4 g of diethyl phosphite with 1.15 g of sodium as catalyst. The p31 spectrum shows for the phosphorus atom in the 5-ring a shift of -48 ppm compared with H3PO4 as standard.
Example 17 2-Oxo-2-ethoxy-3,3,S-trimethyl-5-di-(isooctyl)-phosphono-1,2-oxaphospholane By carrying out the same procedure as described in Example 13, 2-oxo-2-ethoxy-3,3,5-trimethyl-S-di-(isooctyl)-phosphono-1,2-oxaphospholane is obtained as a viscous, colourless oil from 47.2 g of 4-methyl-4-(diethyl-phosphono)-pentanone-2 and 84.6 g of di-isooctyl phosphite with 1.15 g of sodium as catalyst. The p31 spectrum of this oil shows for the phosphorus atom in the ring a shift of -49 ppm compared with H3PO4 as standard.
Example 18 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-di-n-octylPhosphono-1,2-oxaphospholane : By carrying out the same procedure as described in Example 13, ~ 2-oxo-2-ethoxy-3,3,5-trimethyl-5-di-n-octylphosphono-1,2-oxaphospholane is obtained as a viscose, pale yellow oil from 47.2 g of 4-methyl-4-(diethyl-Y` 30 phosphono)-pentanone-2 and 84.6 g of di-n-octylphosphite with 1.15 g of sodium as catalyst. The p31 spectrum of this oil shows for the phosphorus atom in the ring a shift of -49 ppm compared with H3PO4.
- .' '.' ' ' ... ' ~ ~ ' ..
Example l9 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-di-(-2-chloroethyl)-phosphono-1,2-oxaphos-lane By carrying out the same procedure as described in Example 13, 2-oxo-2-ethoxy-3,3,5-trimethyl-5-di-(2-chloroethyl~-phosphono-1,2-oxaphos-pholane is obtained from 47.2 g of 4-methyl-4-(diethylphosphono)-pentanone-2 and 45.2 g of bis(2-chloroethyl)-phosphite. In the p31 spectrum, this com-pound shows for the phosphorus atom in the ring a shift of -50.2 ppm compared with H3PO4 as standard.
Example 20 2-Oxo-2-propyloxy-3,3,5-trimethyl-5-dipropylphosphono-1,2-oxaphospholane
11.8 g of mesityl oxide and 9.8 g of dipropyl phosphite are heated in 40 ml of benzene to 80C. At this temperature, 0.1 g of sodium is added, whereupon an exothermic reaction commences. The reaction temperature is held at 80-90C with external heating by alternately adding 40.0 g of dipropyl phosphite and 0.4 g of sodium. After all the sodium has been added, stirring is continued for 30 minutes, the reaction mixture is cooled and neutralised with 1.4 g of glacial acetic acid. The reaction mixture is concentrated in a rotary evaporator and then distilled in a high vacuum to yield 2-oxo-2-ethoxy-3,3,5-trimethyl-5-dipropylphosphono-1,2-oxaphospholane in the form of a colourless oil with a boiling point of 153-154C/0.1 mm.
The p31 spectrum shows for the phosphorus atom in the ring a shift of -67.2 ppm compared with triphenylphosphate as standard.
Example 21 :, 2-Oxo-2-t2-methoxyethoxy)-3,3,5-trimethyl-5-di-(2-methoxyethyl)-phosphono-1,2-oxaphospholane 15.7 g of mesityl oxide and 9.2 g of di-(2-methoxyethyl)-phosphite are heated to 80C in 50 ml of benzene. At this temperature, 0.1 g of sodium is added whereupon an exothermic reaction commences. The reaction temperature 3Q is held between 80-90C without external heating by alternately adding 70.0 g of di-~2-methoxyethyl)-phosphite and 0.6 g of sodium. After all the sodium has been added, the reaction mixture is stirred for 30 minutes at 80C, ... .
cooled and neutralised with 1.75 g of glacial acetic acid. The reaction mixture is concentrated in a rotary evaporator and the residue is distilled in a high vacuum to yield 2-oxo-2-(2-methoxyethoxy)-3,3,5-trimethyl-5-di-(2-methoxyethyl)-phosphono-1,2-oxaphospholane in the form of a colourless oil with a boiling point of 193-196~C/0.07 mm. The p31 spectrum shows for the phosphorus atom in the ring a shift of -67.2 ppm compared with triphenylphos-phate as standard.
Example 22 2-Oxo-2-allyloxy-3,3,5-trimethyl-5-diallylphosphono-1,2-oxaphospholane 11.5 g of mesityl oxide and 7.4 g of diallylphosphite are heated to 80C in 40 ml of benzene. At this temperature, 0.1 g of sodium is added.
An exothermic reaction starts and the reaction temperature is held at 80-90C without external heating by alternately adding 40.0 g of diallylphosphite and 0.4 g of sodium. After all the sodium has been added, the reaction mixture is stirred for 30 minutes at 80C, then cooled and neutralised with 1.3 g of glacial acetic acid. The reaction mixture is concentrated in a ` rotary evaporator to yield as residue 2-oxo-2-allyloxy-3,3,5-trimethyl-5-; diallylphosphono-1,2-oxaphospholane in the form of a pale yellow oil. The p31 spectrum shows for the phosphorus atom in the ring a shift of -68.5 ppm comparet with triphenylphosphate as standard.
Example 23 2-Oxo-2-ethoxy-3-(4-methoxyphenyl)-5-methyl-5-diethylphosphono-1,2-oxaphos-pholane A mixture is prepared of 69.0 g of diethyl phosphite and 5 g of a 17% sodium ethoxide solution in ethanol. To this reaction mixture are added in small amounts 44 g of p-methoxy-benzalacetone, whereupon the temperature rises from 25C to 89C. The reaction mixture is stirred for 50 minutes and then a further 2.5 g of the 17% sodium ethoxide solution are added. After a further 30 minutes 3.5 g of diethyl phosphite and 2.5 g of sodium ethoxide solution are added to give a pale yellow, clear solution which is concentrated in a rotary evaporator. The p31 spectrum for the phosphorus atom in the ring of the 2-oxo-2-ethoxy shows a shift of -58 ppm compared with triphenylphos-r. :
~''`- '` , ' ~ ' ' phateO
Example 24 2-Oxo-2-ethoxy-3-(4-methylphenyl)-5-methyl-5-diethylphosphono-1,2-oxaPhosPholane By carrying out ~he same procedure as described in Example 23, 2-oxo-2-ethoxy-3-(4-methylphenyl)-5-methyl-5-diethylphosphono-1,2-oxa-phospholane is obtained from 3002 g of 4-methyl-benzalacetone and 5407 g of diethyl phosphite with 7.8 g of a 17% sodium ethoxide solution in ethanol.
The p31 spectrum of the product shows a shift of -58 ppm for the phosphorus atom in the ring.
Example 25 2-Oxo-2-ethoxy-3-(4-chlorophenyl)-5-methyl-5-diethylphosphono-1,2-oxa-phospholane By carrying out the same procedure as described in Example 23, 2-oxo-2-ethoxy-3-(4-chlorophenyl)-4-methyl-5-diethylphosphono-1,2-oxaphos-pholane is obtained from 4502 g of 4-chloro-benzalacetone ant 72.5 g of diethyl phosphate with 10 g of a 17% sodium ethoxide solution in ethanol. The p31 spectrum of the product shows a shift of -57.5 ppm for the phosphorus atom in the ring compared with triphenylphosphate.
ExamPle 26 :' 2-Oxo-ethoxy-3-furyl-5-methyl-diethylPhosphono-1,2-oxaphosPholane By otherwise carrying out the same procedure as described in Example 23, 2-oxoethoxy-3-furyl-5-methyl-diethylphosphono-1,2-oxaphospholane is obtained from 34.0 g of furfurylidene acetone and 7205 g of diethyl phosphite with 10 g of a 17% sodium ethoxide solution in ethanol. The p31 spectrum of the product shows a shift of -5503 ppm for the phosphorus atom in the ring compared with triphenylphosphate.
Example 27 Flameproofing of polyethylene terePhthalate 15 parts of a commercially available polyethylene terephthalate are dissolved in 85 parts of hexafluoroisopropanol. This solution is mixed with the corresponding amount of flame-proofing agent and stirred until it is _ 27 -.
~049030 homogeneous. Using a film drawing rod, half of the solution is applied to a glass plate to a thickness of 0.5 mm. A glass cloth is then pressed on the film and is coated by the second half of the solution in a thickness of l mm.
Drying in vacuo at 120C over 16 hours is subsequently effected. The dried film is drawn from the glass plate and the fl _ ability is determined by the LOI method described by C.P. Fenimore and J.F. Martin in "Combustions and Flame" 10, No. 2, 135-139 (June 1966). In this test, the film is ignited in an atmosphere of nitrogen and oxygen of different volume composition and the volume ratio is ascertained at which it is still just possible to maintain combustion of the test specimens. The LOI value is the minimum oxygen concen-tration in a nitrogen-oxygen mixture at which the specimen just still burns.
The higher the LOI value the lower the flammability of the sheeting, i.eO the more effective the addition of flameproofing agentO
.
flameproofing agentamount of flameproofing agent* LOI
.~
flameproofing agent 5~ 0,225 according to Example 1 flameproofing agent 10% 0,250 according to Example l without flameproof- __ 0,200 ing agent *based on polyethylene terephthalate ExamPle 28 FlameProofing of a Polyamide 15 parts of a commercially available nylon 6 are dissolved in 85 parts of trifluoroethanol. This solution is mixed with the corresponding amount of flameproofing agent and homogeneously stirredO Films are prepared in a manner analogous to that described in Example 27 for polyethylene tere-phthalate and the LOI values are determined. The following Table shows how the LOI value is increased by addition of the flameproofing agents according -` to the invention as compared with nylon 6 without flameproofing agentO
flameproofing agentamount of flameproofing agent* LOI
.
flameproofing agent 5% 0~216 according to Exsmple 1 flameproofing agent 10% 0~231 according to Example 1 without flameproof- __ 0~ 196 ing agent *based on nylon 6 Example 29 Flameproofing of polyacrylonitrile 201 parts of commercially available polyacrylonitrile are dis-solved in 80 parts of dimethyl formamide. This solution is mixed with the corresponding amount of flameproofing agent and stirred to homogeneity.
Sheetings are prepared in a manner analogous to that described in Example 27 for polyethylene terephthalate and the LOI values are determined. The follow-ing Table shows how the LOI value is increased by addition of the flameproof-ing agents according to the invention as compared with polyacrylonitrile without flameproofing agent.
~; flameproofing agentamount of flameproofmg agent LOI
flameproofing agent 5% 0,207 according to Example 1 flameproofing agent 10% 0~224 according to Example 1 without flameproof- __ 0~189 ing agent Example 30 2-Oxo-2-tetrahydrofuryloxy-3,3,5-trimethyl-5-di-(tetrahydrofurfuryl)-phosphono-1,2-oxaphospholane As described in Example 1, a mixture of 3?o6 g of di-tetrahydro-furfuryl phosphite and 4~9 g of mesityl oxide in 80 ml of benzene is reacted ~ 29 ~
by heating in the presence of 1.3 g of sodium over the course of 1 hourO The reaction is vigorously exothermicO The sodium is neutralised by adtition of 3.4 g of glacial acetic acid, then inorganic salt is extracted from the mix-ture with 2 times 20 ml of waterO The benzene is removed in a rotary evapora-tor leaving as residue 32.6 g of crude product which still contains di-tetrahydrofurfuryl phosphite. Distillation of 4.3 g of the crude product in a bulb tube oven in a high vacuum yields the reaction product at an oven temperature between 185C and 230C and a pressure of 0.01 mm Hg.
Yield: 2.07 Analysis: C21H38P209 (M = 496048) calc.: C 5008 H 7.7 P 1205 found: C 49O5 H 7.7 P 12.6 Although the mass spectrum does not show the molecular peak at m/e 496 it does show instead the MIH peak at /e 497. Fragments character-istic of this compound occur at m/e 426 (M -C4H60) and 413 (M -C5H70).
ExamPle 31 Flameproofing of ePOxy resins A rigid foam based on epoxide resin was manufactured from the following constituents:
~` 20 resin: 105 parts of epoxide resin based on bisphenol A with an epoxide equivalent weight of 190 45 parts of epoxide resin based on bisphenol A with an epoxide equivalent weight of 400 2 parts of foam stabiliser Si 3193 (MessrsO Rhodia;
a glycol-silicone copolymer) 5 parts of pentane 5 parts of trichloromonofluoromethane hardener: 7 parts of die*hylene triamine 7 parts of di-~aminomethyl)-cyclohexylmethane 1 part of bisphenol A
The p31 spectrum shows for the phosphorus atom in the ring a shift of -67.2 ppm compared with triphenylphosphate as standard.
Example 21 :, 2-Oxo-2-t2-methoxyethoxy)-3,3,5-trimethyl-5-di-(2-methoxyethyl)-phosphono-1,2-oxaphospholane 15.7 g of mesityl oxide and 9.2 g of di-(2-methoxyethyl)-phosphite are heated to 80C in 50 ml of benzene. At this temperature, 0.1 g of sodium is added whereupon an exothermic reaction commences. The reaction temperature 3Q is held between 80-90C without external heating by alternately adding 70.0 g of di-~2-methoxyethyl)-phosphite and 0.6 g of sodium. After all the sodium has been added, the reaction mixture is stirred for 30 minutes at 80C, ... .
cooled and neutralised with 1.75 g of glacial acetic acid. The reaction mixture is concentrated in a rotary evaporator and the residue is distilled in a high vacuum to yield 2-oxo-2-(2-methoxyethoxy)-3,3,5-trimethyl-5-di-(2-methoxyethyl)-phosphono-1,2-oxaphospholane in the form of a colourless oil with a boiling point of 193-196~C/0.07 mm. The p31 spectrum shows for the phosphorus atom in the ring a shift of -67.2 ppm compared with triphenylphos-phate as standard.
Example 22 2-Oxo-2-allyloxy-3,3,5-trimethyl-5-diallylphosphono-1,2-oxaphospholane 11.5 g of mesityl oxide and 7.4 g of diallylphosphite are heated to 80C in 40 ml of benzene. At this temperature, 0.1 g of sodium is added.
An exothermic reaction starts and the reaction temperature is held at 80-90C without external heating by alternately adding 40.0 g of diallylphosphite and 0.4 g of sodium. After all the sodium has been added, the reaction mixture is stirred for 30 minutes at 80C, then cooled and neutralised with 1.3 g of glacial acetic acid. The reaction mixture is concentrated in a ` rotary evaporator to yield as residue 2-oxo-2-allyloxy-3,3,5-trimethyl-5-; diallylphosphono-1,2-oxaphospholane in the form of a pale yellow oil. The p31 spectrum shows for the phosphorus atom in the ring a shift of -68.5 ppm comparet with triphenylphosphate as standard.
Example 23 2-Oxo-2-ethoxy-3-(4-methoxyphenyl)-5-methyl-5-diethylphosphono-1,2-oxaphos-pholane A mixture is prepared of 69.0 g of diethyl phosphite and 5 g of a 17% sodium ethoxide solution in ethanol. To this reaction mixture are added in small amounts 44 g of p-methoxy-benzalacetone, whereupon the temperature rises from 25C to 89C. The reaction mixture is stirred for 50 minutes and then a further 2.5 g of the 17% sodium ethoxide solution are added. After a further 30 minutes 3.5 g of diethyl phosphite and 2.5 g of sodium ethoxide solution are added to give a pale yellow, clear solution which is concentrated in a rotary evaporator. The p31 spectrum for the phosphorus atom in the ring of the 2-oxo-2-ethoxy shows a shift of -58 ppm compared with triphenylphos-r. :
~''`- '` , ' ~ ' ' phateO
Example 24 2-Oxo-2-ethoxy-3-(4-methylphenyl)-5-methyl-5-diethylphosphono-1,2-oxaPhosPholane By carrying out ~he same procedure as described in Example 23, 2-oxo-2-ethoxy-3-(4-methylphenyl)-5-methyl-5-diethylphosphono-1,2-oxa-phospholane is obtained from 3002 g of 4-methyl-benzalacetone and 5407 g of diethyl phosphite with 7.8 g of a 17% sodium ethoxide solution in ethanol.
The p31 spectrum of the product shows a shift of -58 ppm for the phosphorus atom in the ring.
Example 25 2-Oxo-2-ethoxy-3-(4-chlorophenyl)-5-methyl-5-diethylphosphono-1,2-oxa-phospholane By carrying out the same procedure as described in Example 23, 2-oxo-2-ethoxy-3-(4-chlorophenyl)-4-methyl-5-diethylphosphono-1,2-oxaphos-pholane is obtained from 4502 g of 4-chloro-benzalacetone ant 72.5 g of diethyl phosphate with 10 g of a 17% sodium ethoxide solution in ethanol. The p31 spectrum of the product shows a shift of -57.5 ppm for the phosphorus atom in the ring compared with triphenylphosphate.
ExamPle 26 :' 2-Oxo-ethoxy-3-furyl-5-methyl-diethylPhosphono-1,2-oxaphosPholane By otherwise carrying out the same procedure as described in Example 23, 2-oxoethoxy-3-furyl-5-methyl-diethylphosphono-1,2-oxaphospholane is obtained from 34.0 g of furfurylidene acetone and 7205 g of diethyl phosphite with 10 g of a 17% sodium ethoxide solution in ethanol. The p31 spectrum of the product shows a shift of -5503 ppm for the phosphorus atom in the ring compared with triphenylphosphate.
Example 27 Flameproofing of polyethylene terePhthalate 15 parts of a commercially available polyethylene terephthalate are dissolved in 85 parts of hexafluoroisopropanol. This solution is mixed with the corresponding amount of flame-proofing agent and stirred until it is _ 27 -.
~049030 homogeneous. Using a film drawing rod, half of the solution is applied to a glass plate to a thickness of 0.5 mm. A glass cloth is then pressed on the film and is coated by the second half of the solution in a thickness of l mm.
Drying in vacuo at 120C over 16 hours is subsequently effected. The dried film is drawn from the glass plate and the fl _ ability is determined by the LOI method described by C.P. Fenimore and J.F. Martin in "Combustions and Flame" 10, No. 2, 135-139 (June 1966). In this test, the film is ignited in an atmosphere of nitrogen and oxygen of different volume composition and the volume ratio is ascertained at which it is still just possible to maintain combustion of the test specimens. The LOI value is the minimum oxygen concen-tration in a nitrogen-oxygen mixture at which the specimen just still burns.
The higher the LOI value the lower the flammability of the sheeting, i.eO the more effective the addition of flameproofing agentO
.
flameproofing agentamount of flameproofing agent* LOI
.~
flameproofing agent 5~ 0,225 according to Example 1 flameproofing agent 10% 0,250 according to Example l without flameproof- __ 0,200 ing agent *based on polyethylene terephthalate ExamPle 28 FlameProofing of a Polyamide 15 parts of a commercially available nylon 6 are dissolved in 85 parts of trifluoroethanol. This solution is mixed with the corresponding amount of flameproofing agent and homogeneously stirredO Films are prepared in a manner analogous to that described in Example 27 for polyethylene tere-phthalate and the LOI values are determined. The following Table shows how the LOI value is increased by addition of the flameproofing agents according -` to the invention as compared with nylon 6 without flameproofing agentO
flameproofing agentamount of flameproofing agent* LOI
.
flameproofing agent 5% 0~216 according to Exsmple 1 flameproofing agent 10% 0~231 according to Example 1 without flameproof- __ 0~ 196 ing agent *based on nylon 6 Example 29 Flameproofing of polyacrylonitrile 201 parts of commercially available polyacrylonitrile are dis-solved in 80 parts of dimethyl formamide. This solution is mixed with the corresponding amount of flameproofing agent and stirred to homogeneity.
Sheetings are prepared in a manner analogous to that described in Example 27 for polyethylene terephthalate and the LOI values are determined. The follow-ing Table shows how the LOI value is increased by addition of the flameproof-ing agents according to the invention as compared with polyacrylonitrile without flameproofing agent.
~; flameproofing agentamount of flameproofmg agent LOI
flameproofing agent 5% 0,207 according to Example 1 flameproofing agent 10% 0~224 according to Example 1 without flameproof- __ 0~189 ing agent Example 30 2-Oxo-2-tetrahydrofuryloxy-3,3,5-trimethyl-5-di-(tetrahydrofurfuryl)-phosphono-1,2-oxaphospholane As described in Example 1, a mixture of 3?o6 g of di-tetrahydro-furfuryl phosphite and 4~9 g of mesityl oxide in 80 ml of benzene is reacted ~ 29 ~
by heating in the presence of 1.3 g of sodium over the course of 1 hourO The reaction is vigorously exothermicO The sodium is neutralised by adtition of 3.4 g of glacial acetic acid, then inorganic salt is extracted from the mix-ture with 2 times 20 ml of waterO The benzene is removed in a rotary evapora-tor leaving as residue 32.6 g of crude product which still contains di-tetrahydrofurfuryl phosphite. Distillation of 4.3 g of the crude product in a bulb tube oven in a high vacuum yields the reaction product at an oven temperature between 185C and 230C and a pressure of 0.01 mm Hg.
Yield: 2.07 Analysis: C21H38P209 (M = 496048) calc.: C 5008 H 7.7 P 1205 found: C 49O5 H 7.7 P 12.6 Although the mass spectrum does not show the molecular peak at m/e 496 it does show instead the MIH peak at /e 497. Fragments character-istic of this compound occur at m/e 426 (M -C4H60) and 413 (M -C5H70).
ExamPle 31 Flameproofing of ePOxy resins A rigid foam based on epoxide resin was manufactured from the following constituents:
~` 20 resin: 105 parts of epoxide resin based on bisphenol A with an epoxide equivalent weight of 190 45 parts of epoxide resin based on bisphenol A with an epoxide equivalent weight of 400 2 parts of foam stabiliser Si 3193 (MessrsO Rhodia;
a glycol-silicone copolymer) 5 parts of pentane 5 parts of trichloromonofluoromethane hardener: 7 parts of die*hylene triamine 7 parts of di-~aminomethyl)-cyclohexylmethane 1 part of bisphenol A
12 parts of 1,6-diamino-2,4,4-trimethylhexane 3 parts of phenol .
Resin and hardener are thorougly mixed at room temperature and poured into a wooden mould~ The foam is removed after 1 hour; it has a density of 0.1 g/cm2.
Specimen rods measuring 10 x 15 x 120 mm are cut from the rigid foam and subjected to a flammability test according to ASTM 635. In this test, the rod is hung at an angle of 45 and ignited at its bottom end with a gas flame. The combustion time up to the 10 cm mark is measured and the combustion speed is calculated therefrom. The rigid epoxide foam has a com-bustion speed of 2 secO/cm.
An epoxide foam of the same composition is manufactured except that 25 parts of 2-oxo-2-ethoxy-3,3J5-trimethyl-5-diethyl-phosphono-1,2-oxaphospholane are additionally mixed with the resin. The test of this foam by ASTM 635 shows that the resin is self-extinguishing: the measurement mark is not reached ., .
~ - 31 -.
:, :
' ' '
Resin and hardener are thorougly mixed at room temperature and poured into a wooden mould~ The foam is removed after 1 hour; it has a density of 0.1 g/cm2.
Specimen rods measuring 10 x 15 x 120 mm are cut from the rigid foam and subjected to a flammability test according to ASTM 635. In this test, the rod is hung at an angle of 45 and ignited at its bottom end with a gas flame. The combustion time up to the 10 cm mark is measured and the combustion speed is calculated therefrom. The rigid epoxide foam has a com-bustion speed of 2 secO/cm.
An epoxide foam of the same composition is manufactured except that 25 parts of 2-oxo-2-ethoxy-3,3J5-trimethyl-5-diethyl-phosphono-1,2-oxaphospholane are additionally mixed with the resin. The test of this foam by ASTM 635 shows that the resin is self-extinguishing: the measurement mark is not reached ., .
~ - 31 -.
:, :
' ' '
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Compounds of the formula I
(I) wherein R1 and R2 each represents alkyl with 1 to 18 carbon atoms, haloalkyl, alkoxy alkyl, having not more than 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or tetrahydrofurfuryl, R3 represents alkyl with 1 to 8 carbon atoms, cycloalkyl with S to 8 carbon atoms, alkenyl with 3 to 8 carbon atoms, alkoxy alkyl with not more than 8 carbon atoms or tetrahydrofurfuryl, R4 represents hydrogen or methyl, R5 represents hydrogen, alkyl with 1 to 8 carbon atoms, phenyl, methyl phenyl, methoxy phenyl or chlorophenyl or furyl, R6 represents hydrogen or methyl, and R7 represents lower alkyl with 1 to 8 carbon atoms.
(I) wherein R1 and R2 each represents alkyl with 1 to 18 carbon atoms, haloalkyl, alkoxy alkyl, having not more than 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or tetrahydrofurfuryl, R3 represents alkyl with 1 to 8 carbon atoms, cycloalkyl with S to 8 carbon atoms, alkenyl with 3 to 8 carbon atoms, alkoxy alkyl with not more than 8 carbon atoms or tetrahydrofurfuryl, R4 represents hydrogen or methyl, R5 represents hydrogen, alkyl with 1 to 8 carbon atoms, phenyl, methyl phenyl, methoxy phenyl or chlorophenyl or furyl, R6 represents hydrogen or methyl, and R7 represents lower alkyl with 1 to 8 carbon atoms.
2. Compounds according to claim 1 wherein R1, R2 and R3 are the same.
3. A process for the manufacture of compounds of the formula I
(I) wherein R1 and R2 each represents alkyl with 1 to 18 carbon atoms, haloalkyl, alkoxy alkyl, having not more than 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or tetrahydrofurfuryl, R3 represents alkyl with 1 to 8 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, alkenyl with 3 to 8 carbon atoms, alkoxy alkyl with not more than 8 carbon atoms or tetrahydrofurfuryl, R4 represents hydrogen or methyl, R5 represents hydrogen, alkyl with 1 to 8 carbon atoms, phenyl, methyl phenyl, methoxy phenyl or chlorophenyl or furyl, R6 represents hydrogen or methyl, and R7 represents lower alkyl with 1 to 8 carbon atoms, which process comprises reacting an .alpha.,.beta.-unsaturated ketone of the formula II
(II) wherein R4 represents hydrogen or methyl, R5 represents hydrogen, alkyl with 1 to 8 carbon atoms, phenyl, methylphenyl, methoxy-phenyl, chlorophenyl or furyl, R6 represents hydrogen or methyl and R7 represents alkyl with 1 to 8 carbon atoms, at least 2 moles of a phosphite of the formula III
(III) wherein each of R1 and R2 independently represents alkyl with 1 to 18 carbon atoms, haloalkyl, alkoxy alkyl, having not more than 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or tetrahydrofurfuryl in the presence of a base, with or without the addition of a solvent.
(I) wherein R1 and R2 each represents alkyl with 1 to 18 carbon atoms, haloalkyl, alkoxy alkyl, having not more than 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or tetrahydrofurfuryl, R3 represents alkyl with 1 to 8 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, alkenyl with 3 to 8 carbon atoms, alkoxy alkyl with not more than 8 carbon atoms or tetrahydrofurfuryl, R4 represents hydrogen or methyl, R5 represents hydrogen, alkyl with 1 to 8 carbon atoms, phenyl, methyl phenyl, methoxy phenyl or chlorophenyl or furyl, R6 represents hydrogen or methyl, and R7 represents lower alkyl with 1 to 8 carbon atoms, which process comprises reacting an .alpha.,.beta.-unsaturated ketone of the formula II
(II) wherein R4 represents hydrogen or methyl, R5 represents hydrogen, alkyl with 1 to 8 carbon atoms, phenyl, methylphenyl, methoxy-phenyl, chlorophenyl or furyl, R6 represents hydrogen or methyl and R7 represents alkyl with 1 to 8 carbon atoms, at least 2 moles of a phosphite of the formula III
(III) wherein each of R1 and R2 independently represents alkyl with 1 to 18 carbon atoms, haloalkyl, alkoxy alkyl, having not more than 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, cycloalkyl with 5 to 8 carbon atoms or tetrahydrofurfuryl in the presence of a base, with or without the addition of a solvent.
4. A process according to claim 3, which comprises the use of 2.5 to 3.5 moles of a compound of the formula III for each mole of a compound of the formula II.
5. A process according to claim 3, which comprises the use of an alkali metal, an alkali metal alkoxide or an alkaline earth metal alkoxide, an alkali metal amide or a metal hydride as base.
6. A process according to claim 5, which comprises the use of metallic sodium or potassium, sodium methoxide, potassium tert. butoxide, lithium amide, sodium amide or calcium hydride as base.
7. A process according to claim 3, which comprises the use of a hydrocarbon, an alcohol or an ether as solvent.
8. A process according to claim 7, which comprises the use of benzene, toluene, xylene, ligroin, hexane or heptane as solvent.
9. A process according to claim 3, which comprises carrying out the reaction at elevated temperature.
10. 2-Oxo-2-methoxy-3,3,5-trimethyl-5-dimethylphosphono-1,2-oxaphospholane.
11. 2-Oxo-2-isopropoxy-3,3,5-trimethyl-5-diisopropyl-phosphonol,2-oxaphospholane.
12. 2-Oxo-2-ethoxy-3,3,5-trimethyl-5-diethylphosphono-1,2-oxaphospholane.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1289073 | 1973-09-07 | ||
| CH698174 | 1974-05-21 | ||
| CH1046574 | 1974-07-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049030A true CA1049030A (en) | 1979-02-20 |
Family
ID=27175658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA74208588A Expired CA1049030A (en) | 1973-09-07 | 1974-09-05 | 1,2-oxaphospholanes |
Country Status (15)
| Country | Link |
|---|---|
| JP (2) | JPS5055641A (en) |
| AR (1) | AR203399A1 (en) |
| AU (1) | AU7271274A (en) |
| BR (1) | BR7407457D0 (en) |
| CA (1) | CA1049030A (en) |
| DE (1) | DE2441998A1 (en) |
| DK (1) | DK439274A (en) |
| ES (1) | ES429804A1 (en) |
| FR (1) | FR2257600B1 (en) |
| GB (1) | GB1443114A (en) |
| IE (1) | IE39888B1 (en) |
| IL (1) | IL45509A (en) |
| IT (1) | IT1021153B (en) |
| LU (1) | LU70856A1 (en) |
| NL (1) | NL7411754A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4042649A (en) * | 1975-09-18 | 1977-08-16 | Ciba-Geigy Corporation | 1,2-Oxaphospholanes |
| US6353080B1 (en) | 1997-06-26 | 2002-03-05 | The Dow Chemical Company | Flame retardant epoxy resin composition |
| CN116987262A (en) * | 2022-04-26 | 2023-11-03 | 中国科学院化学研究所 | Nylon, anti-dripping flame-retardant material containing nylon and preparation method |
-
1974
- 1974-08-16 DK DK439274A patent/DK439274A/da unknown
- 1974-08-21 IL IL45509A patent/IL45509A/en unknown
- 1974-08-27 AU AU72712/74A patent/AU7271274A/en not_active Expired
- 1974-09-02 DE DE2441998A patent/DE2441998A1/en active Pending
- 1974-09-04 NL NL7411754A patent/NL7411754A/en unknown
- 1974-09-05 IE IE1846/74A patent/IE39888B1/en unknown
- 1974-09-05 LU LU70856A patent/LU70856A1/xx unknown
- 1974-09-05 AR AR255476A patent/AR203399A1/en active
- 1974-09-05 CA CA74208588A patent/CA1049030A/en not_active Expired
- 1974-09-05 GB GB3881074A patent/GB1443114A/en not_active Expired
- 1974-09-05 JP JP49102456A patent/JPS5055641A/ja active Pending
- 1974-09-06 FR FR7430276A patent/FR2257600B1/fr not_active Expired
- 1974-09-06 ES ES429804A patent/ES429804A1/en not_active Expired
- 1974-09-06 IT IT27030/74A patent/IT1021153B/en active
- 1974-09-06 BR BR7457/74A patent/BR7407457D0/en unknown
- 1974-12-07 JP JP49141065A patent/JPS50126665A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU7271274A (en) | 1976-06-17 |
| IL45509A0 (en) | 1974-11-29 |
| JPS50126665A (en) | 1975-10-04 |
| NL7411754A (en) | 1975-03-11 |
| IT1021153B (en) | 1978-01-30 |
| JPS5055641A (en) | 1975-05-15 |
| FR2257600A1 (en) | 1975-08-08 |
| IE39888L (en) | 1975-03-07 |
| ES429804A1 (en) | 1976-10-01 |
| GB1443114A (en) | 1976-07-21 |
| DE2441998A1 (en) | 1975-03-13 |
| AR203399A1 (en) | 1975-09-08 |
| DK439274A (en) | 1975-05-05 |
| FR2257600B1 (en) | 1976-10-22 |
| BR7407457D0 (en) | 1975-07-08 |
| IE39888B1 (en) | 1979-01-17 |
| LU70856A1 (en) | 1975-06-11 |
| IL45509A (en) | 1977-02-28 |
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