IE41812B1 - Unsaturated phophorus-containing carboxylic acid derivatives - Google Patents
Unsaturated phophorus-containing carboxylic acid derivativesInfo
- Publication number
- IE41812B1 IE41812B1 IE2261/75A IE226175A IE41812B1 IE 41812 B1 IE41812 B1 IE 41812B1 IE 2261/75 A IE2261/75 A IE 2261/75A IE 226175 A IE226175 A IE 226175A IE 41812 B1 IE41812 B1 IE 41812B1
- Authority
- IE
- Ireland
- Prior art keywords
- formula
- compound
- reaction
- carbon atoms
- carried out
- Prior art date
Links
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000012442 inert solvent Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 12
- -1 alkyl radical Chemical class 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000012433 hydrogen halide Substances 0.000 claims description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052717 sulfur Chemical group 0.000 claims description 2
- 239000011593 sulfur Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 3
- 150000003017 phosphorus Chemical class 0.000 abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 238000013019 agitation Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 8
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical class C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 7
- 229950000688 phenothiazine Drugs 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 5
- ZLVVDNKTHWEIOG-UHFFFAOYSA-N chloro(dimethyl)phosphane Chemical compound CP(C)Cl ZLVVDNKTHWEIOG-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- UDQBLBPJVKUWET-UHFFFAOYSA-N 2-[methyl(2-methylpropoxy)phosphoryl]ethanol Chemical compound CC(C)COP(C)(=O)CCO UDQBLBPJVKUWET-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical class OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- NDDHRUYSMAMAIC-UHFFFAOYSA-N 1-[methyl(2-methylpropoxy)phosphoryl]propan-2-ol Chemical compound CC(C)COP(C)(=O)CC(C)O NDDHRUYSMAMAIC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- PSDFYYGWUDGDCJ-UHFFFAOYSA-N 2-[ethoxy(methyl)phosphoryl]ethanol Chemical compound CCOP(C)(=O)CCO PSDFYYGWUDGDCJ-UHFFFAOYSA-N 0.000 description 1
- COQLNRZLMHMONI-UHFFFAOYSA-N 2-[methyl(2-methylpropoxy)phosphinothioyl]ethanol Chemical compound CC(C)COP(C)(=S)CCO COQLNRZLMHMONI-UHFFFAOYSA-N 0.000 description 1
- TWZSTPDHGBPDHM-UHFFFAOYSA-N 3-[butyl(propan-2-yloxy)phosphoryl]propan-1-ol Chemical compound CCCCP(=O)(OC(C)C)CCCO TWZSTPDHGBPDHM-UHFFFAOYSA-N 0.000 description 1
- FYRFKBVIOFNDJA-UHFFFAOYSA-N 3-[methyl(2-methylpropoxy)phosphoryl]propan-1-ol Chemical compound CC(C)COP(C)(=O)CCCO FYRFKBVIOFNDJA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- SLVYMKIHXNKKTE-UHFFFAOYSA-N [methyl(2-methylpropoxy)phosphoryl]methanol Chemical compound CC(C)COP(C)(=O)CO SLVYMKIHXNKKTE-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical class COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3211—Esters of acyclic saturated acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Novel unsaturated phosphorus-containing carboxylic acid derivatives of the formula I are prepared by reacting an alcohol of the formula II with a compound of the formula III. The individual symbols are as defined in Claim 1. The reaction is carried out in an inert solvent. The resultant compounds of the formula I are suitable as monomers or comonomers in the preparation of polymers.
Description
This invention relates to unsaturated phosphorus-containing carboxylic acid derivatives.
Unsaturated phosphorus-containing carboxylic acid derivatives of tho formula
CH
0 0 \ H , s » x P-(CH„) OC-C-CH,
Z I
CH„ in which R^ is hydrogen or a methyl radical and n is 1, 2 or 3, are already known (German Offenlegungsschrift No. 2,052,569).
They are derivatives of tertiary phosphine oxides which have good flame retarding properties. The starting material for their preparation is generally dimethylchlorophosphine which, simultaneously with methyldichlorophosphine, is obtained industrially by reacting methyl chloride with phosphorus at about 350°C (German Auslegeschrift No. 1,568,928). A similar flame-proofing application for methyldichlorophosphine is not known, and this makes the use of dimethylchlorophosphine uneconomic.
The present acid derivatives invention provides phosphorus-containing carboxylic of the formula ,1
R X 0 \JI II
P-Y-0-C-C=CH„ X I 2 r20 r3 (I) in which each of R^ and R2 is an alkyl radical having up to 8 carbon atoms, preferably an alkyl radical having from 1 to 4 carbon atoms; R^ is hydrogen or a methyl radical; X is oxygen or
41813 sulfur, preferably oxygen; and Y is a linear or branched alkylene radical having up to 6, preferably from 1 to 3, carbon atoms.
The present invention also provides a process for the preparation of compounds of the formula (I), which comprises reacting an alcohol of the formula
P-Y-OH (II) r2o in which Rp Rp X and Y have the meanings given above, with a compound of the formula ίο z-co-c=ch2 (III) R3 in which Z is a halogen atom, preferably a chlorine atom; and R^ has the meaning given above, in the presence of an inert solvent and in the absence of water.
The acylation according to the present invention of alcohols of the formula (ll) with acrylic or methacrylic acid halides of the formula III is carried out in known manner, preferably in the presence of a hydrogen halide-binding compound, for example a tertiary amine such as triethylamine or pyridine, at a temperature of from -30 to +100°C, preferably from 20 to 7θ°0. The hydrogen halide-binding compound is used in an equimolar amount relative to the acid halide of the formula (III), or in a slight excess of up to about 10%.
It is also preferred to use one of the polymerization inhibitors known for acrylic acid derivatives, for example phenothiazine, hydroquinone, hydroquinone-monomethyl ether and/or metal salt inhibitors. The amount of inhibitor is chosen within the usual range, for example from 0.01 to 1 weight %, relative to the compound of the formula (III), The presence of active polymerization inhibitors is important also for the optional distillation work-up of the crude reaction mixture.
The starting compounds of the formulae (II) and (III) are generally used in about equimolar amounts; the acid halide of the formula (III) optionally being in a slight excess of up to 10%.
The reaction is carried out with the exclusion of water.
Tho reaction is advantageously carried out as follows: the alcohol of the formula (E) and the optional tertiary amine in the inert solvent are first introduced into the reaction vessel at room termpera.-fcui'i2}arid the acid chloride of the formula (III) is added dropwise, while the mixture is continuously and thoroughly mixed, for example by means of an agitator.
The reaction temperature is not critical and may rise within the above mentioned temperature range, that is, up to 100°C because of the reaction heat liberated during the reaction, and this may be advantageous for the course of the reaction. The starting compounds of the formula (II) are easily obtainable.
For example hydroxymethyl-alkylphosphinic acid esters according to the process of German Offenlegungsschrift No. 2,226,406. 2hydroxyethyl-alkylphosphinic acid esters are obtained in good yields from 2-acetoxy-ethyl-alkylphosphinic acid esters according to the process of German Offenlegungsschrift No. 2,335,852, and 3, hydroxypropyl-alkylphosphinic acid esters may be prepared in an analogous manner.
Typical phosphorus containing carboxylic acid derivatives of the formula (I) are for example: the acrylic and methacrylic acid esters of methylhydroxymethyl-phosphinic acid methyl, ethyl, propyl and isobutyl esters; ethyl-hydroxymethylphosphinic acid methyl, ethyl, propyl and isobutyl esters; ethyl-hydroxymethylphosphinic acid methyl, ethyl, propyl and isobutyl esters; methyl-2hydroxyethylphosphinic acid isobutyl ester; methyl-2-hydroxyethylthiophosphinic acid isobutyl ester; propyl-2-hydroxyethyl- 4 41812 phosphinic acid propyl ester; methyl-(2-hydroxy-2-melhylethyl)phosphj.nic acid methyl, ethyl, propyl, n-butyl, isobutyl and pentyl esters; methyl-3-hydroxypropylphosphinic acid isobutyl ester; and butyl-3-hydroxypropylphosphinic acid isopropyl ester.
As inert solvents theremay be used for example those solvents which are usually employed for esterification and/or ester interchange reactions, such as benzene, toluene, xylene, chlorobenzene, carbon tetrachloride, chloroform, diisopropyl ether, acetonitrile and mixtures of such compounds. The amount of inert solvent is not critical and depends advantageously on the stirability of the reaction mixture after complete reaction, in which the hydrogen halide-binding compound optionally used precipitates generally as a hydrohalide in the form of crystals. Therefore, the inert solvent is generaly used in an amount of up to 10 times, preferably from 2 to 5 times, the weight of the alcohol of formula (ll).
Xylene or toluene are the preferred inert solvents.
Because of their unsaturated carbon-carbon bonds, the carboxylic acid derivatives of the formula (I) are suitable as monomers or comonomers for the preparation of polymers. For example, by copolymerization with monomers such as acrylic derivatives, styrene or vinyl compounds, flame retarding polymers having improved dyeability and anti-static properties are obtained. Copolymers consisting of acrylonitrile, vinyl chloride, vinyl bromide and/or vinylidene chloride and compounds of the formula (I) have surprisingly good flame retarding properties. Furthermore, filaments and fibres made from these copolymers have an unexpected high thermostability, that is, their tendency to yellowing under thermal stress is considerably less than that of similar materials known in the art.
By ester interchange of the phosphinic acid ester groups «Rg (preferably when Rg is an alkyl radical having from 1 bo 4 carbon atoms, especially methyl or ethyl) with glycols such as
- 5 41812 ethylene glycol, diethylene glycol, propylene glycol or higher glycols, the polymers obtained may also be cross-linked. When using methyldichloropfiosphine as the starting material for the preparation of the alcohol of the formula (IX). The phosphinic acid esters of the formula (I) are more easily obtainable than the analogous tertiary phosphine oxides, which require the use of dimethylchlorophosphine as starting material. In contrast to dimethylchlorophosphine, methyldichlorophosphine is easily manufactured on an industrial scale, since it may be obtained in known manner and as exclusive product from the reaction of methane with PC13 at 600°C.
The following Examples illustrate the invention.
EXAMPLE 1
252 g (1.52 mol) of methylhydroxymethylphosphinic acid isobutyl ester, 153 g (l.52 mol) of triethylamine and 1 g of phenothiazine are dissolved in toluene and, with agitation and slight cooling, 137-5 g (1.52 mol) of acrylic acid chloride are added dropwise at 2O-3O°C. Agitation is continued for 15 hours. After one further hour, the triethylamine hydrochloride precipitated is suction-filteVed. After having distilled off the solvent and after addition of polymerization inhibitors, the filtrate is distilled in vacuo. 185 g of
CH, 0 < ||
P-CH,-O-C-CH=CH , “ li (CH3)2CHCH2O 0 boiling point 95-9S°C at 0.1 mm Hg, are obtained, which corresponds to a yield of 55-5$ of the theoretical yield.
Analysis:
found: C 49.3$; H 7.7$; P 14.0$ calculated: C 49.1$; H 7.72$; P 14.1$.
- 6 41812
EXAMPLE 2
500 g (2.78 mol) of methyl-2-hydroxyethylphosphinic acid isobutyl ester, 28l g (2.78 mol) of triethylamine and 1.5 g of phenothiazine are dissolved in 1.67 1 of toluene and, with vigorous agitation and without cooling, 252 g (2.78 mol) of acrylic acid chloride are added dropwise. The temperature rises to 50°C. After the chloride is added, agitation is continued for 15 hours. Subsequently, the batch is cooled to 1O°C, and the triethylamine hydrochloride precipitated is eliminated by suctionfiltration. After having distilled off the solvent in a water jet vacuum and after addition of polymerization inhibitors, the residue is distilled in vacuo. 4§5 g of
CH, 0 < if
P-CH„-CH„-0-C-CH=CH_ / II (CH3)2CHCH2O 0 boiling point 145°C at 2 mm Hg, are obtained, which corresponds to a yield of 75% of the theoretical yield.
Analysis:
found: C 51.4%; H 8.10%; P 13.0% calculated: C 51.3%; H 8.12%; P 13.25%.
EXAMPLE 3
188 g (1.04 mol) of methyl-2-hydroxyethylphosphinic acid isobutyl ester, 105 g (1.04 mol) of triethylamine and 0.5 g of phenothiazine are dissolved in 620 ml of toluene and, with vigorous agitation and without cooling, 109 g (1.04 mol) of methacrylic acid chloride are added dropwise. The temperature rises to 50-6O°C.
After the chloride is added, agitation is continued for 10 hours, and the batch is cooled to -10°C. The triethylamine hydrochloride precipitated in the form of crystals is eliminated by suctionfiltration, and the filtrate is substantially liberated from the toluene at 120°C and 35 mm Hg. After addition of polymerization inhibitors, the residue is distilled in vacuo. 220 g of
- 7 10
CH
Ο il
PCH2CH2OC~C=CH2 (ch3)2chch2o ΰ CH3 boiling' point 125-131°C at 0.45 mm Hg, are obtained, which corresponds to a yield of 85%.
Analysis:
found: C53.2#; Η 8.47#; P 12.5# calculated: C53.6#; H 8.5#; P 12.4#.
EXAMPLE 4 g (0.385 mol) of methyl-(2-hydroxy-2-methylethyl)-phosphinic acid isobutyl ester, 39 g of triethylamine (0.385 mol) and 0.3 g of phenothiazine are dissolved in toluene and, with slight cooling 35 g (0.385 mol) of acrylic acid chloride are added dropwise. Agitation is continued for 12 hours. After a further hour, methylene chloride is added, and the triethylamine hydrochloride is suction-filtered. The filtrate, after having eliminated the solvent and added polymerization inhibitors, is distilled under reduced pressure. 57.5 g of
CH_
0
II li
P-CH2-CHOC-CH=CH2 (ch3)2chch2o ' CH3 boiling point 95“1θθ°^ θ·1 1111,1 Hg, are obtained, to a yield of 60# of the theoretical yield. Analysis:
found: C 53.4#; H 8.5#;
calculated: C 53.6#; H 8.5#;
which corresponds
P 12.5# P 12.4#.
EXAMPLE 5
196 g (1 mol) of methyl-2-hydroxyethylthipphosphinic acid isobutyl ester, 101 g of triethylamine (1 mol) and 0.4 g of phenothiazine are dissolved in 500 ml of toluene and, with vigorous agitation and without cooling, 104.5 g (l mol) of methacrylic acid
- 8 25
41813 chloride are added dropwise. The temperature rises to 50°C. Agitation is continued for 5 hours, and the batch is allowed to stand overnight. Subsequently, it is cooled, and the triethylamine hydrochloride is suction-filtered. The filtrate is stirred with water, the organic phase is separated and dried with Na2S0^. After having distilled off the solvent at room temperature and 1 mm Hg, the residue, after addition of polymerization inhibitors, is distilled in a thin-layer evaporator at l80°C and 0.5 mm Hg.
200 g of
CH. S
Λ, ll
PCH.CH„OC-C=CH_ / II I (CH3)2CHCH2O 0 CH3 are obtained which corresponds to a yield of 76% of the theoretical yield.
Analysis:
found: C 50.0%; Η 7·9Ο%; P 11.3%; S 12.05% calculated:C 50.0%; H 7-95%; P 11.75%; S 12.13%.
EXAMPLE 6
100 g (0.66 mol) of methyl-2-hydroxyethylphosphinic acid ethyl ester, 66.8 g (0.66 mol) of triethylamine and 0,.3 g of phenothiazine are dissolved in a mixture of toluene and methylene chloride, and, with vigorous agitation and cooling, 69 g (0,66 mol) of methacrylic acid chloride are added dropwise. After this addition is complete, agitation is continued for 1 hour, the batch is then cooled to 0°C, and is distilled in vacuo. 116 g of
CH. 0 0
Λ ί ll'
P - CH. - CH„-O-C-C=CH„ / X Ζ I z
CH3 boiling point 147°C at 1.2 mm Hg, are obtained, which corresponds to a yield of 80% of the theoretical yield.
Analysis:
found: C 49.2%; H 7.8%; P 14.1% calculated:_9_C 49.1%’; H 7.8%; P 13.9%
Claims (12)
1, A compound of the formula ’-Y-O-C-C=CI1, '2 R. ’3 in which each of R^ and Rg is an alkyl radical haying up to 8 5 carbon atoms; Rg is hydrogen or a methyl radical; X is oxygen or sulfur; and Y is a linear or branched alkylene radical having up to ό carbon atoms.
2. A compound as claimed in claim 1, wherein each of R^ and Rg is an alkyl· radical having from 1 to 4 carbon atoms. 10
3. A compound as claimed in claim 1 or claim 2, wherein Y is an alkylene radical having from 1 to 3 carbon atoms.
4. A process for the preparation of a compound as claimed in claim 1, which comprises reacting an alcohol of the formula P-Y-OH in which R^, Rg, X and Y have the meanings specified in claim 1, with a compound of the formula Z-CO-C=CH, '2 in which Z is a halogen atom, and Rg has the meaning specified in claim 1, in the presence of an inert solvent and in the absence of 20 water.
5. A process as claimed in claim 4 , wherein Z is a chlorine atom
6. A process as claimed in claim 4 or claim 5, wherein the reaction is carried out in the presence of a polymerization inhibitor for the acrylyl or methacrylyl group. 10 41812
7. A process as claimed in any one of claims 4 to 6, wherein the reaction is carried out in the presence of a hydrogen halide-binding compound.
8. A process as claimed in claim 7, wherein the hydrogen halide5 binding compound is a tertiary amine.
9. A process as claimed in any one of claims 4 to 8, wherein the inert solvent is toluene or xylene,
10. A process as claimed in any one of claims 4 to 9> wherein the reaction is carried out at a temperature of from -30 to 10 +100°C.
11. A process as claimed in claim 4 carried out substantially as described in any one of Examples 1 to 6 herein.
12. A compound as claimed in claim 1 whenever prepared by a process as claimed in any one of claims 4 to 11.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2449466A DE2449466C2 (en) | 1974-10-19 | 1974-10-19 | New unsaturated phosphorus-containing carboxylic acid derivatives and processes for their preparation |
Publications (2)
Publication Number | Publication Date |
---|---|
IE41812L IE41812L (en) | 1976-04-19 |
IE41812B1 true IE41812B1 (en) | 1980-03-26 |
Family
ID=5928547
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE2261/75A IE41812B1 (en) | 1974-10-19 | 1975-10-17 | Unsaturated phophorus-containing carboxylic acid derivatives |
Country Status (15)
Country | Link |
---|---|
JP (1) | JPS5626676B2 (en) |
AT (1) | AT334398B (en) |
BE (1) | BE834672A (en) |
CA (1) | CA1053690A (en) |
CH (1) | CH616431A5 (en) |
DE (1) | DE2449466C2 (en) |
DK (1) | DK467675A (en) |
ES (1) | ES441741A1 (en) |
FR (1) | FR2288097A1 (en) |
GB (1) | GB1472699A (en) |
IE (1) | IE41812B1 (en) |
IT (1) | IT1043463B (en) |
LU (1) | LU73602A1 (en) |
NL (1) | NL7512062A (en) |
SE (1) | SE7511677L (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2841941A1 (en) * | 1978-09-27 | 1980-04-17 | Hoechst Ag | ORGANIC PHOSPHORUS COMPOUNDS WITH 3-HYDROXYALKYLPHOSPHINIC ACID ESTER GROUPS |
DE2918161A1 (en) * | 1979-05-05 | 1980-11-13 | Bayer Ag | PHOSPHONOMAL ACID ESTER AND METHOD FOR THE PRODUCTION THEREOF |
DE102006012878A1 (en) * | 2006-03-21 | 2007-09-27 | Clariant International Limited | Phosphorus-containing mixtures, a process for their preparation and their use |
DE102006012881A1 (en) * | 2006-03-21 | 2007-09-27 | Clariant International Limited | Phosphorus-containing mixtures, a process for their preparation and their use |
JP2008222677A (en) * | 2007-03-15 | 2008-09-25 | Chisso Corp | Flame retardant, polymer composition using the same |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES396221A1 (en) * | 1970-10-27 | 1974-04-16 | Hoechst Ag | Phosphorus-containing unsaturated carboxylic acid derivatives |
-
1974
- 1974-10-19 DE DE2449466A patent/DE2449466C2/en not_active Expired
-
1975
- 1975-10-13 ES ES441741A patent/ES441741A1/en not_active Expired
- 1975-10-14 NL NL7512062A patent/NL7512062A/en not_active Application Discontinuation
- 1975-10-15 CH CH1340675A patent/CH616431A5/en not_active IP Right Cessation
- 1975-10-17 DK DK467675A patent/DK467675A/en unknown
- 1975-10-17 LU LU73602A patent/LU73602A1/xx unknown
- 1975-10-17 JP JP12448775A patent/JPS5626676B2/ja not_active Expired
- 1975-10-17 AT AT791175A patent/AT334398B/en not_active IP Right Cessation
- 1975-10-17 CA CA239,930A patent/CA1053690A/en not_active Expired
- 1975-10-17 FR FR7531811A patent/FR2288097A1/en active Granted
- 1975-10-17 IE IE2261/75A patent/IE41812B1/en unknown
- 1975-10-17 IT IT28410/75A patent/IT1043463B/en active
- 1975-10-17 SE SE7511677A patent/SE7511677L/en unknown
- 1975-10-17 GB GB4271675A patent/GB1472699A/en not_active Expired
- 1975-10-20 BE BE161076A patent/BE834672A/en unknown
Also Published As
Publication number | Publication date |
---|---|
CH616431A5 (en) | 1980-03-31 |
ATA791175A (en) | 1976-05-15 |
FR2288097A1 (en) | 1976-05-14 |
IT1043463B (en) | 1980-02-20 |
DE2449466A1 (en) | 1976-04-29 |
NL7512062A (en) | 1976-04-21 |
DE2449466C2 (en) | 1982-07-15 |
GB1472699A (en) | 1977-05-04 |
LU73602A1 (en) | 1976-08-19 |
IE41812L (en) | 1976-04-19 |
JPS5180823A (en) | 1976-07-15 |
CA1053690A (en) | 1979-05-01 |
BE834672A (en) | 1976-04-20 |
SE7511677L (en) | 1976-04-20 |
AT334398B (en) | 1976-01-10 |
FR2288097B1 (en) | 1979-01-05 |
JPS5626676B2 (en) | 1981-06-19 |
DK467675A (en) | 1976-04-20 |
ES441741A1 (en) | 1977-03-16 |
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