GB2102427A - Substituted phosphonic acids - Google Patents
Substituted phosphonic acids Download PDFInfo
- Publication number
- GB2102427A GB2102427A GB08222017A GB8222017A GB2102427A GB 2102427 A GB2102427 A GB 2102427A GB 08222017 A GB08222017 A GB 08222017A GB 8222017 A GB8222017 A GB 8222017A GB 2102427 A GB2102427 A GB 2102427A
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- United Kingdom
- Prior art keywords
- formula
- compounds
- salts
- vinyl
- phenyl
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- 150000003009 phosphonic acids Chemical class 0.000 title description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 150000002148 esters Chemical class 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 150000005690 diesters Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 25
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 14
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 11
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910052801 chlorine Chemical group 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 abstract description 7
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- 150000008062 acetophenones Chemical class 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- -1 for example Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical class [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- FIDRMXZKSYDDJO-UHFFFAOYSA-N (1-chloro-1-phenylethyl)phosphonic acid Chemical compound OP(=O)(O)C(Cl)(C)C1=CC=CC=C1 FIDRMXZKSYDDJO-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- UDEVCZRUNOLVLU-UHFFFAOYSA-N 1-phenyloctan-1-one Chemical compound CCCCCCCC(=O)C1=CC=CC=C1 UDEVCZRUNOLVLU-UHFFFAOYSA-N 0.000 description 1
- LXUIUVLDNRQBQJ-UHFFFAOYSA-N 1-phenyltetradecan-1-one Chemical compound CCCCCCCCCCCCCC(=O)C1=CC=CC=C1 LXUIUVLDNRQBQJ-UHFFFAOYSA-N 0.000 description 1
- LHJBFOGCFZHBAJ-UHFFFAOYSA-N 1-phenylundecan-1-one Chemical compound CCCCCCCCCCC(=O)C1=CC=CC=C1 LHJBFOGCFZHBAJ-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000011646 cupric carbonate Substances 0.000 description 1
- 235000019854 cupric carbonate Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
-
- 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3826—Acyclic unsaturated 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 Table
- 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 ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4015—Esters of acyclic unsaturated acids
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
There are described 1-phenyl- vinyl-1-phosphonic acids of formula (I) wherein R represents an optionally substituted, optionally branched alkyl group, suitably a C3-20 alkyl group, and the salts, half esters, salts of the half esters and diesters derived from such acids, as well as processes for the preparation thereof and uses thereof as monomers or comonomers for radical polymerization and as polymerizable emulsifiers. <IMAGE>
Description
SPECIFICATION
Substituted phosphonic acids
The present invention relates to substituted phosphonic acids, in particular to substituted 1phenyl-vinyl-1-phosphonic acids, and to the use thereof.
Phosphonic acids which contain polymerisable units, and the salts, half esters and esters thereof, are useful monomers since the homopolymers or copolymers synthesised from them may be used, for example, as flameproofing agents, corrosion-proof metal coatings, ion exchangers, dispersants and adhesion promoters.
Copolymers of 1 -phenyl-vinyl-1 -phosphonic acid have been recommended, for example, for the after-treatment of phosphated metal surfaces (German Offenlegungsschriften 26 1 5 489 and 24 55 624).
For the technical synthesis of 1-phenyl-vinyl-1-phosphonic acid, a process is known which starts from acetophenone.
In this process, acetophenone is reacted with phosphorus trichloride, for example in the presence of glacial acetic acid. The product formed initially is assumed to have the structure of a cyclic phosphonic acid. When it is reacted with water or hydrochloric acid the 1-hydroxy- or 1 -chloro-1 - phenyl-ethane-1-phosphonic acid is obtained therefrom. When thermal energy is supplied, these compounds react to form 1-phenyl-vinyl-1 -phosphonic acid (PhVP), with the elimination of water or hydrochloric acid.
The phosphonic acids of the prior art, such as 1-phenyl-vinyl-1-phosphonic acid, are unable to meet all the requirements of industry in the various fields of application. Thus, for example, the solubility of PhVP in apolar organic solvents and, more particularly, in other useful comonomers, is inadequate. Moreover, it does not have the emulsifying effect required for certain fields of use.
It has now been found that certain 1 -phenyl-vinyl-1 -phosphonic acids in which the phenyl group is substituted substantially meet these industrial requirements.
According to one aspect of the invention there are provided compounds of formula (I)
wherein R represents an optionally substituted, optionally branched alkyl group, preferably a C320 alkyl group, especially preferably a Cm~,2 alkyl group) and salts, half esters, salts of the half esters, and diesters thereof.
According to a further aspect of the invention there is provided a process for the preparation of compounds of formula (I), or of salts, half esters, salts of half esters, and diesters thereof comprising reacting an acetophenone of formula (II)
(wherein R is as hereinbefore defined) with phosphorus trichloride, preferably in the presence of glacial acetic acid, reacting the resulting reaction product with a compound of formula (III) HX (III) (wherein X represents a hydroxy group or a chlorine atom); and thermally eliminating from the reaction product of formula (IV)
(wherein R and X are as herein before defined), thereby obtained a compound of formula HX (wherein X is as defined above); and, if desired, converting the acid of formula (I) thereby obtained into a salt, a half ester, a salt of a half ester, or a diester thereof. The product of formula (I) can be worked up in a manner known per se.
The substituents for the groups R in formula (I) as defined preferably include substituents such as, for example, alkyl, aryl, ether, amino and alkyl-amino groups, which are stable under the reaction conditions referred to above.
The substituted acetophenone of formula (II) is preferably reacted with at least stoichiometric quantities of phosphorus trichloride and glacial acetic acid, generally at a temperature below 350C, preferably in the range of ambient temperature to 350C. The concentration of the free acetic acid in the reacting mixture is advantageously kept as low as possible, e.g. by adding the acetic acid slowly, dropwise, to the mixture of phosphorus trichloride and acetophenone. Preferably, a total of 2 moles of acetic acid are added per mole of phosphorus trichloride used. Subsequently, a compound of formula (IV) wherein X represents OH may be prepared by hydrolysis of the reaction mixture with a quantity of water at least equivalent to the quantity of acetic acid added and preferably slightly in excess.In order to prepare the compound of formula (IV) wherein X represents chlorine, the reaction mixture obtained by reacting the compound of formula (II) with stoichiometric quantities of phosphorus trichloride and glacial acetic acid may also be saturated with hydrochloric acid at a temperature of not more than 35"C.
The crude products from the two different embodiments of the process may be used, without further purification, for the thermal elimination of the compound HX.
The thermal elimination of HX from the compound of formula (IV) may advantageously be effected using the process described in German Auslegeschrift 20 60 218, e.g. by heating compound (IV) in a suitable inert solvent such as 1,1,2,2-tetrachloroethane to temperatures of about 11 0CC to 1 400C. The elimination reaction is preferably carried out by suspending the compound (IV) in 3 to 5 times the quantity of 1,1 2,2-tetrachloroethane and heating to the reaction temperature, with simultaneous stirring. With a vigorous generation of water or HCI, the suspensions are converted into solutions from which the compounds of formula (I) may be obtained in a manner known per se, for example by crystallisation (possibly after they have been concentrated by evaporation).The compounds of formula (I) are generally crystalline substances but the tendency to crystallisation decreases as the chain length increases. From the substituted 1-phenyl-vinyl-1-phosphonic acids of formula (I), the salts, half esters, salts of the half esters and diesters thereof may be obtained in a manner known per se (vide. K. Sasse in Houben-Weyl, volume Xl 1/1, page 383ff., Georg-Thieme
Verlag, Stuttgart 1963). In this respect, the alkali metal, alkaline earth metal and heavy metal salts, for example, deserve particular mention.
The alkali metal salts may be prepared for example, from aqueous solutions of the acids by adding, per mole of acid, 1 - or 2-molar quantities of the corresponding hydroxides or carbonates and may be isolated if required by extraction with a solvent.
The alkaline earth metal salts may be obtained analogously, e.g. by reacting the free acids of formula (I) with alkaline earth hydroxides or carbonates. They do not dissolve readily in water.
Copper (II) and zinc salts are precipitated, for example, from an aqueous solution when copper (II) or zinc carbonate is added to the free acids of formula (I). Lead (II) salts are preferably prepared using lead (II) acetate, whilst mono-silver salts may be prepared by reacting with silver oxide and di-silver salts may be precipitated from ammoniacal solutions of the acids of formula I with silver nitrate.
The salts of the phosphonic acids of formula (I) with amines, e.g. with aromatic amines, may be obtained by heating the components in solvents such as, for example, alcohol or benzene.
Direct esterification of the phosphonic acids of formula (I) may be effected by the conventional methods e.g. those which involve treating the silver or lead (II) salts with alkyl halides of formula (Vl)
R,Z (Vi) (wherein R, represents an alkyl group, preferably with 1 to 8 carbon atoms, or a benzyl group; and Z represents a halogen atom such as chlorine, bromine or iodine) to form the esters of formula (IA)
(wherein R, is as hereinbefore defined).
By saponification of the diesters of formula (IA) in a basic medium, under moderate reaction conditions, the monoalkyl phosphonates of formula IB may be prepared,
(wherein R and R, are as hereinbefore defined and A represents the cation corresponding to the base
AOH used).
By acidifying an aqueous solution of a compound formula (IB) it is possible to obtain the free acid (A replaced by H) which is usually precipitated.
Suitable bases for the preparation of the compounds of formula (IB) include, for example, aqueous sodium hydroxide solution, baryta water or alcoholic alkali.
The metal salts of formula (IB) may also be prepared by cleaving the diesters of formula (IA) with neutral metal salts at elevated temperature.
If R, in formula (IB) represents benzyl, these compounds are also suitable for the preparation of the free acids derived from (IB) for the preparation of the compound of formula (I) itself.
The substituted 1 -phenyl-vinyl-1 -phosphonic acids of formula (I) according to the invention and the derivatives thereof are, for example, highly suitable as monomers or comonomers for the preparation of synthetic resins.
Special mention should be made, for example, of copolymers with acrylic and methacrylic acid, and (meth)acrylic acid esters, styrene, vinyl acetate, vinylimidazole and combinations thereof.
The phosphonic acids of the invention have an emulsifying effect, both as the free acids and also in the form of the salts.
Another interesting aspect of the application of emulsifier prepared from the substituted phosphonic acids or salts thereof according to the invention is that the emulsifiers are polymerised into the latex particles in the course of polymerisation.
According to yet further aspects of the invention there are thus provided the uses of compounds of formula (I) or salts, half esters or salts thereof, or diesters thereof as monomers or comonomers in radical polymerization and as polymerizable emulsifiers in dispersion polymers.
The following Examples are intended to illustrate the preparation of the compounds of formula (I) according to the invention without restricting the invention to these embodiments. Percentages are by weight unless otherwise indicated.
Examples
Examples 1 to 4 (Preparative)
Preparation of the substituted acetophenones
2.4 mol of powdered aluminium trichloride are placed in 500 ml of 1,2-dichloroethane and then 2.1 mol of acetyl chloride are added with stirring and cooling. Subsequently, 2 mol of the corresponding alkylbenzene are added dropwise at 10 to 200C and the mixture is stirred at ambient temperature for a further 1 to 2 hours. The reaction mixture is carefully added to 900 g of ice, the organic phase is separated off and the aqueous phase is extracted with dichloroethane. The combined organic phases are washed with water, with 2% sodium hydroxide solution, and again with water, dried with potassium carbonate and subjected to fractional vacuum distillation.
Yields of the substituted acetophenones:
Example No. Substítuted Acetophenone Yield (% of theory) 1 methylacetophenone 78
2 n-hexylacetophenone 89
3 n-nonylacetophenone 82
4 n-dodecylacetophenone 68
Examples 5 to 8
Preparation of the substituted 1-phenyl-vinyl-1-phosphonic acids
The substituted acetophenone and phosphorus trichloride are put together and mixed thoroughly at ambient temperature for 20 minutes and then the acetic acid is slowly added dropwise. The development of gas occurs, the mixture becomes cloudy and the temperature at the bottom begins to increase. The reaction temperature is maintained at 23 OC by occasional cooling. The mixture is then stirred for 1 hour, during which it becomes clear and the temperature increases to about 280C.Acetyl chloride and excess PCl3 are removed in vacuo up to a temperature at the bottom of 430C and the remaining honey-like substance is mixed with ice. After the addition of 1,1,2,2-tetrachloroethane, the mixture is heated using a water separator and the theoretical quantity of water is eliminated. As the residue is cooled or concentrated, the desired substituted 1-phenyl-vinyl-1-phosphonic acid crystallises out.
Yield of 1-alkyl- Acetic phenylvinyl- 1- Example Alkylacetophenone PCl3 acid /ce phosphonic acid Melting
No. Alkyl (Mol) (Mol) (Mol) (Mol) % oftheory point OC.
5 Methyl 1.5 1.875 3.75 4.5 72 105
6 Hexyl 0.5 0.625 1.25 1.5 73 61
7 Nonyl 1.2 1.5 3.0 3.6 70 84
8 Dodecyl 0.3 0.375 0.75 0.9 78 78
Example 9
Polymer dispersion containing 1-(hexylphenyl)-vinyl-1-phosphonic acid as comonomer
A solution of
0.05 g of sodium salt of 1-(hexylphenyl)-vinyl-1-phosphonic acid and
0.5 g of potassium peroxodisulphate in
400 g of distilled water is placed in a polymerisation vessel fitted with a stirrer, reflux condenser and thermometer, and heated to 800C.
Within a period of 4 hours, an emulsion prepared from
500 g of methylmethacrylate
500 g of butylacrylate
5 g of sodium salt of 1-(hexylphenyl)-vinyl-1-phosphonic acid
1.5 g of potassium peroxodisulphate and
600 g of water is added dropwise to this solution at 800C.
After all the emulsion has been added the resulting mixture is left for 2 hours at 80"C. After cooling to ambient temperature, a coagulate-free dispersion is obtained which is easy to filter.
Solids content: 49.2%
Viscosity: 10 mPa.s.
Claims (9)
1. Compounds of formula (I)
(wherein R represents an optionally substituted, optionally branched alkyl group) and salts, half esters, salts of the half esters and diesters thereof.
2. Compounds as claimed in claim 1, wherein R represents an optionally substituted, optionally branched C320 alkyl group.
3. Compounds as claimed in claim 1, wherein R represents an optionally substituted, optionally branched C,~,2 alkyl group.
4. Compounds as claimed in claim 1 selected from:
(a) 1 -(methyl-phenyl)-vinyl-1 -phosphonic acid;
(b) 1-(hexyl-phenyl)-vinyl-1-phosphonic acid;
(c) 1-(nonyl-phenyl)-vinyl-1-phosphonic acid; and
(d) 1-(dodecyl-phenyl)-vinyl-1-phosphonic acid; and the salts, half esters, salts of the half esters, and diesters thereof.
5. Process for the preparation of compounds as claimed in claim 1 comprising reacting an acetophenone of formula (II)
(wherein R is as defined in claim 1) with phosphorus trichloride; reacting the resulting reaction product with a compound of formula (III) HX (III) (wherein X represents a hydroxy group or a chlorine atom); and thermally eliminating from the reaction product of formula (IV)
(wherein R and X are as hereinbefore defined) thereby obtained a compound of formula HX (wherein X is as hereinbefore defined); and, if desired, converting the acid of formula (I) thereby obtained into a salt, a half ester, a salt of a half ester, or a diester thereof.
6. A process as claimed in claim 5 wherein the reaction with phosphorus trichloride is effected in the presence of glacial acetic acid.
7. A process for the preparation of compounds of formula (I) (as defined in claim 1) and derivatives thereof substantially as herein described.
8. A process for the preparation of compounds of formula (I) (as defined in claim 1) and derivatives thereof substantially as herein described with reference to any of Examples 5 to 8.
9. The use of compounds as claimed in claim 1 as monomers or comonomers in radical polymerisation.
1 0. The use of compounds claimed in claim 1 as polymerisable emulsifiers for dispersion polymers.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813130628 DE3130628A1 (en) | 1981-08-01 | 1981-08-01 | SUBSTITUTED 1-PHENYL-VINYL-1-PHOSPHONIC ACIDS AND THEIR USE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2102427A true GB2102427A (en) | 1983-02-02 |
| GB2102427B GB2102427B (en) | 1984-12-12 |
Family
ID=6138440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08222017A Expired GB2102427B (en) | 1981-08-01 | 1982-07-30 | Substituted phosphonic acids |
Country Status (4)
| Country | Link |
|---|---|
| DE (1) | DE3130628A1 (en) |
| FR (1) | FR2510578B1 (en) |
| GB (1) | GB2102427B (en) |
| NL (1) | NL188580C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0130439A1 (en) * | 1983-06-29 | 1985-01-09 | Hoechst Aktiengesellschaft | Process for the preparation of vinylphosphonic acid or vinylpyrophonic acid |
| US4962228A (en) * | 1987-03-09 | 1990-10-09 | Mobil Oil Corporation | Layered divalent metal phosphates containing pendent substituent groups and their preparation |
| GB2235201A (en) * | 1989-08-25 | 1991-02-27 | Colgate Palmolive Co | Antibacterial antiplaque oral composition containing styrene-phosphonic acid copolymer |
| GB2276388A (en) * | 1993-03-24 | 1994-09-28 | Albright & Wilson | Bulk polymerisation process and product |
| US5391816A (en) * | 1993-11-08 | 1995-02-21 | Akzo Nobel N.V. | Formation of 1-phenylvinyl-1-phosphonic acid |
| US5728756A (en) * | 1987-01-30 | 1998-03-17 | Colgate Palmolive Company | Antiplaque antibacterial oral composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2060218C3 (en) * | 1970-12-08 | 1980-06-04 | Hoechst Ag, 6000 Frankfurt | Process for the preparation of 1-phenyl-vinyl-1-phosphonic acid |
| DE2060259C3 (en) * | 1970-12-08 | 1980-01-03 | Hoechst Ag, 6000 Frankfurt | Phenyl vinyl phosphonic acids and processes for their production |
| DE2455624A1 (en) * | 1974-11-23 | 1976-05-26 | Hoechst Ag | PROCESS FOR AFTER-TREATMENT OF PHOSPHATED METAL SURFACES |
| DE2615489A1 (en) * | 1976-04-09 | 1977-10-27 | Hoechst Ag | PROCESS FOR AFTER-TREATMENT OF PHOSPHATED METAL SURFACES |
-
1981
- 1981-08-01 DE DE19813130628 patent/DE3130628A1/en active Granted
-
1982
- 1982-05-28 NL NLAANVRAGE8202201,A patent/NL188580C/en not_active IP Right Cessation
- 1982-06-11 FR FR8210189A patent/FR2510578B1/en not_active Expired
- 1982-07-30 GB GB08222017A patent/GB2102427B/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0130439A1 (en) * | 1983-06-29 | 1985-01-09 | Hoechst Aktiengesellschaft | Process for the preparation of vinylphosphonic acid or vinylpyrophonic acid |
| US5728756A (en) * | 1987-01-30 | 1998-03-17 | Colgate Palmolive Company | Antiplaque antibacterial oral composition |
| US4962228A (en) * | 1987-03-09 | 1990-10-09 | Mobil Oil Corporation | Layered divalent metal phosphates containing pendent substituent groups and their preparation |
| GB2235201A (en) * | 1989-08-25 | 1991-02-27 | Colgate Palmolive Co | Antibacterial antiplaque oral composition containing styrene-phosphonic acid copolymer |
| GB2235201B (en) * | 1989-08-25 | 1994-02-16 | Colgate Palmolive Co | Antibacterial antiplaque oral composition containing novel styrene-phosphonic acid copolymer |
| GB2276388A (en) * | 1993-03-24 | 1994-09-28 | Albright & Wilson | Bulk polymerisation process and product |
| US5439999A (en) * | 1993-03-24 | 1995-08-08 | Albright & Wilson Limited | Bulk polymerisation process and product |
| GB2276388B (en) * | 1993-03-24 | 1996-11-27 | Albright & Wilson | Bulk polymerisation process and product |
| US5391816A (en) * | 1993-11-08 | 1995-02-21 | Akzo Nobel N.V. | Formation of 1-phenylvinyl-1-phosphonic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| NL8202201A (en) | 1983-03-01 |
| FR2510578A1 (en) | 1983-02-04 |
| NL188580C (en) | 1992-08-03 |
| NL188580B (en) | 1992-03-02 |
| GB2102427B (en) | 1984-12-12 |
| FR2510578B1 (en) | 1985-07-05 |
| DE3130628C2 (en) | 1990-09-20 |
| DE3130628A1 (en) | 1983-02-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19970730 |