GB812390A - Polymeric phosphate esters and their production - Google Patents
Polymeric phosphate esters and their productionInfo
- Publication number
- GB812390A GB812390A GB17280/56A GB1728056A GB812390A GB 812390 A GB812390 A GB 812390A GB 17280/56 A GB17280/56 A GB 17280/56A GB 1728056 A GB1728056 A GB 1728056A GB 812390 A GB812390 A GB 812390A
- Authority
- GB
- United Kingdom
- Prior art keywords
- hydroxyl
- heated
- phosphate ester
- formula
- phosphate
- 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
Links
- 150000003014 phosphoric acid esters Chemical class 0.000 title 1
- -1 phosphate ester Chemical class 0.000 abstract 38
- 229910019142 PO4 Inorganic materials 0.000 abstract 23
- 239000010452 phosphate Substances 0.000 abstract 23
- 229920000388 Polyphosphate Polymers 0.000 abstract 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 14
- 239000001205 polyphosphate Substances 0.000 abstract 14
- 235000011176 polyphosphates Nutrition 0.000 abstract 14
- 150000002148 esters Chemical class 0.000 abstract 13
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 8
- 239000002253 acid Substances 0.000 abstract 8
- 239000003054 catalyst Substances 0.000 abstract 8
- 238000010438 heat treatment Methods 0.000 abstract 8
- 229910015900 BF3 Inorganic materials 0.000 abstract 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 6
- 125000003118 aryl group Chemical group 0.000 abstract 5
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 abstract 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 abstract 4
- 150000008065 acid anhydrides Chemical class 0.000 abstract 4
- 230000002378 acidificating effect Effects 0.000 abstract 4
- 238000006243 chemical reaction Methods 0.000 abstract 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 abstract 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract 3
- 125000000217 alkyl group Chemical group 0.000 abstract 3
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 3
- 125000001188 haloalkyl group Chemical group 0.000 abstract 3
- 125000003106 haloaryl group Chemical group 0.000 abstract 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 3
- 239000003879 lubricant additive Substances 0.000 abstract 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract 3
- 229910052753 mercury Inorganic materials 0.000 abstract 3
- 238000000034 method Methods 0.000 abstract 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 3
- 239000007858 starting material Substances 0.000 abstract 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 abstract 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 abstract 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 abstract 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical class OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 abstract 2
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 abstract 2
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 abstract 2
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 abstract 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 abstract 2
- 150000007513 acids Chemical class 0.000 abstract 2
- 125000001931 aliphatic group Chemical group 0.000 abstract 2
- 150000005215 alkyl ethers Chemical class 0.000 abstract 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract 2
- SUSAGCZZQKACKE-UHFFFAOYSA-N cyclobutane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC1C(O)=O SUSAGCZZQKACKE-UHFFFAOYSA-N 0.000 abstract 2
- TXWOGHSRPAYOML-UHFFFAOYSA-N cyclobutanecarboxylic acid Chemical compound OC(=O)C1CCC1 TXWOGHSRPAYOML-UHFFFAOYSA-N 0.000 abstract 2
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 abstract 2
- 230000032050 esterification Effects 0.000 abstract 2
- 238000005886 esterification reaction Methods 0.000 abstract 2
- 150000005826 halohydrocarbons Chemical class 0.000 abstract 2
- 239000003960 organic solvent Substances 0.000 abstract 2
- 150000002924 oxiranes Chemical class 0.000 abstract 2
- 239000012188 paraffin wax Substances 0.000 abstract 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 abstract 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 abstract 2
- 125000005999 2-bromoethyl group Chemical group 0.000 abstract 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 abstract 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 abstract 1
- KKZUMAMOMRDVKA-UHFFFAOYSA-N 2-chloropropane Chemical group [CH2]C(C)Cl KKZUMAMOMRDVKA-UHFFFAOYSA-N 0.000 abstract 1
- PZMAYGGZDSYWQF-UHFFFAOYSA-N 3-chlorocyclopentane-1-carboxylic acid Chemical compound OC(=O)C1CCC(Cl)C1 PZMAYGGZDSYWQF-UHFFFAOYSA-N 0.000 abstract 1
- PMGHIGLOERPWGC-UHFFFAOYSA-N Bis-(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(O)OCCCl PMGHIGLOERPWGC-UHFFFAOYSA-N 0.000 abstract 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 abstract 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 abstract 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 abstract 1
- 239000000654 additive Substances 0.000 abstract 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- GFQMBVPKXZQUHJ-UHFFFAOYSA-N bis(2-ethylhexyl) 2-hydroxyethyl phosphate Chemical compound CCCCC(CC)COP(=O)(OCCO)OCC(CC)CCCC GFQMBVPKXZQUHJ-UHFFFAOYSA-N 0.000 abstract 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000005690 diesters Chemical class 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- PCIBVZXUNDZWRL-UHFFFAOYSA-N ethylene glycol monophosphate Chemical compound OCCOP(O)(O)=O PCIBVZXUNDZWRL-UHFFFAOYSA-N 0.000 abstract 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 abstract 1
- 239000002917 insecticide Substances 0.000 abstract 1
- 239000000314 lubricant Substances 0.000 abstract 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 abstract 1
- 239000002480 mineral oil Substances 0.000 abstract 1
- 125000002347 octyl 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])[H] 0.000 abstract 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 229920002689 polyvinyl acetate Polymers 0.000 abstract 1
- 239000011118 polyvinyl acetate Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 125000004079 stearyl 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])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])[H] 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Polyphosphate esters useful as lubricant additives are obtainable by a process which comprises heating at a temperature within the range from 90 DEG to 250 DEG C. an hydroxyl-containing phosphate ester having the structure: (RO) (R1O)P(O)(OC2H3R11)xOH, wherein R an R1 respectively are alkyl, haloalkyl, aralkyl, aryl, haloaryl, or alkaryl radicals, R11 is an hydrogen atom or a methyl, ethyl or halomethyl radical, and X is a numerical value from 1 to 10, and removing an alcohol or phenol as it is formed in the heating (see Group IV (b)), the resulting polyphosphate esters having the probable structure <FORM:0812390/III/1> or <FORM:0812390/III/2> wherein R, R1, R11 and x are as defined above and y is a number from 2 to 10. The acylated derivatives of the polyphosphate esters are also stated to be useful as lubricant additives. The polyphosphate esters may be used as additives for synthetic lubricants and the acylated derivatives are soluble in mineral oils.ALSO:Polyphosphate esters suitable as plasticizers for polyvinyl acetate, and vinyl chloride-vinyl acetate copolymers are obtainable by a process which comprises heating at a temperature within the range from 90 DEG to 250 DEG C. an hydroxylcontaining phosphate ester having the structure (RO)(R1O)P(O)(OC2H3R11)xOH wherein R and R1 respectively are alkyl, haloalkyl, aralkyl, aryl, haloaryl, or alkaryl radicals, R11 is a hydrogen atom or a methyl, ethyl or halomethyl radical, and x is a numerical value from 1 to 10, and removing an alcohol or phenol as it is formed in the heating, the resulting polyphosphate esters having the probable structure <FORM:0812390/IV (a)/1> wherein R, R1, R11 and x are as defined above and y is a number from 2 to 10. The hydroxyl-containing phosphate ester used as starting material may be obtained by reacting an oxirane compound of the structure <FORM:0812390/IV (a)/2> with an ester of the formula <FORM:0812390/IV (a)/3> wherein R, R1 and R11 are as defined above. The reaction is effected by adding the oxirane compound slowly to the phosphate diester maintained at from - 20 DEG C. to about 80 DEG C., if desired in the presence of an acidic catalyst, e.g. boron trifluoride or its ethyl ether complex, and of an inert organic solvent free from hydroxyl groups, e.g. an alkyl ether such as ethyl ether, a paraffin or aromatic hydrocarbon such as heptane or benzene or a halohydrocarbon, e.g. ethylene dichloride or chlorobenzene. Specified phosphate diesters are the dimethyl, -ethyl, -butyl, -hexyl, -2-ethylhexyl-octyl, -octadecyl, -2-chloro-ethyl, -2-chloropropyl, -2,3-dichloropropyl, -2-bromoethyl, 2-fluoroethyl, -phenyl, -p-chlorophenyl, 2,4-dichlorophenyl, di-cresyl, and dibenzyl phosphate diesters and specified oxirane compounds are ethylene oxide, propylene oxide, 1,2-epoxybutane, epichlorhydrin and epibromhydrin. The heating of the hydroxyl-containing phosphate ester to form the polyphosphate product is usually conducted under reduced pressure, e.g. 0.5 to 1 mm. of mercury and an acidic catalyst, e.g. boron trifluoride, stannic chloride or other Friedel-Crafts type catalyst may be present. The hydroxyl-containing polyphosphate ester product may be reacted, usually at about 100 DEG to 125 DEG C. with an aliphatic, cycloaliphatic, or aromatic mono- or polycarboxylic acid or acid anhydride. Specified acids are acetic, caproic, capric, stearic, succinic, methylsuccinic, benzoic, toluic, phthalic, cyclobutane carboxylic, 1,2 - cyclobutanedicarboxylic, monochloracetic, 2-bromobutanoic, chlorosuccinic, p-chlorobenzoic, 3 - chlorocyclopentamecarboxylic, tetrachlorophthalic, phenyl acetic, p-phenyl benzoic, methoxyacetic, o-ethoxy benzoic, and 2,4-dichlorophenoxy acetic acids. This further reaction is preferably carried out using the acid anhydride in a proportion of 2 mols. per mol. of hydroxyl present in the polyphosphate and an acid esterification catalyst, e.g. sulphuric, hydrochloric or arylsulphonic acid or boron trifluoride may be present. In examples: (1) the diester ( (C4H9O)2P(O)(OCH2CH2)1.38OH (obtained from ethylene oxide and dibutyl phosphoric acid) is heated at 90 DEG to 130 DEG C. for 13 hours under a pressure of 2 mm. mercury to form a hydroxyl-containing polymeric phosphate ester which is then heated with acetic anhydride to block the terminal hydroxyl group; (2) di-(2-ethylhexyl) 2-hydroxyethyl phosphate is heated at 140-152 DEG C. at 0.5 mm. pressure for 28 hours to form a polymeric phosphate ester, the hydroxyethyl phosphate starting material being obtained by reacting ethylene oxide with di-(2-ethylhexyl) phosphoric acid and having the formula (C8H17O)(OCH2 CH2)1.16OH; (3) an ethylene oxide adduct of diphenyl phosphoric acid of the formula (C6H5O)2O(O)(OCH2CH2)1.75OH is heated at 90-150 DEG C. for 10 hours at 2 mm. pressure to form a polymeric phosphate of molecular weight 2164; (4) an epichlorhydrin adduct of di-(2-ethylhexyl) phosphoric acid having the formula (C8H17O)2P(O)(OC3H5Cl)1.027OH is heated for 24 hours at 150 DEG C. and 0.5 mm. pressure to form a polymeric ester of molecular weight 727; (5) the ethylene oxide adduct of dibutyl phosphoric acid having the formula (C4H9O)2P(O)(OCH2CH2)1.224OH i heated for 24 hours at 150 DEG C. and 1.5 mm. pressure to form a polymeric phosphate product of molecular weight 1198; (6) an ethylene oxide adduct of di-(2-ethylhexyl) phosphoric acid having the formula (C8H17O)2P(O)(OCH2CH2)2.11OH i heated for 16 hours at 150-156 DEG C. at 1 mm. pressure to form a polymeric phosphate of molecular weight 1482; (7) an ethylene oxide adduct of di-(2-chloroethyl) phosphoric acid having the formula (ClCH2CH2O)2P(O)(OCH2 CH2)1.9 6OH is heated at 150 DEG C. and 1 mm. pressure with removal of ethylene chlorohydrin to form a light brown rubber-like solid residue; (8) an ethylene oxide adduct of dicresyl phosphoric acid having the formula (CH3C6H4O)2 P(O)(OCH2CH2)2.21OH is heated for 8 hours at 150 DEG C. and 1 mm. pressure to form a polymeric phosphate ester; (9) an ethylene oxide adduct of di-(2-ethylhexyl) phosphoric acid of the formula (C8H17O)2P(O)(OCH2CH2)4.82OH is heated for 32 hours at 150 DEG C. and 1 mm. pressure to form a polymeric phosphate ester; (10) an ethylene oxide adduct of dimethyl phosphoric acid of the formula (CH3O)2P(O) (OCH2CH2)1.9 6OH is heated for 6 hours at 150 DEG C. and 1 mm. pressure to form a polymeric phosphate ester; (11) a propylene oxide adduct of di-(2-ethylhexyl) phosphoric acid of the formula (C8H17O)2P(O)(OC3H6)1.10OH is heated for 36 hours at 150 DEG C. and 0.5 mm. pressure to force a piymeric phosphate esterol. The polymeric phosphate ester products are stated to be useful as insecticides, and as flame-proofing agents and the products obtained by acylating the end hydroxyl groups of the polymeric phosphate ester as well as the polymeric phosphate ester products themselves are stated to be useful as lubricant additives (see Group III).ALSO:The invention comprises polyphosphate esters obtainable by a process which comprises heating at a temperature within the range from 90 DEG C. to 250 DEG C. an hydroxyl-containing phosphate ester having the structure (RO)(R1O)P(O)(OC2H3R11)xOH wherein R and R1 respectively are alkyl, haloalkyl, aralkyl, aryl, haloaryl, or alkaryl radicals, R11 is a hydrogen atom or a methyl, ethyl or halomethyl radical, and x is a numerical value from 1 to 10, and removing an alcohol or phenol as it is formed in the heating, the resulting polyphosphate esters having the probable structure <FORM:0812390/IV (b)/1> or <FORM:0812390/IV (b)/2> wherein R, R1, R11 and x are as defined above and y is a number from 2 to 10. The hydroxylcontaining phosphate ester used as starting material may be obtained by reacting an oxirane compound of the structure <FORM:0812390/IV (b)/3> with an ester of the formula <FORM:0812390/IV (b)/4> wherein R, R1 and R11 are as defined above. The reaction is effected by adding the oxirane compound slowly to the phosphate diester maintained at from - 20 DEG C. to about 80 DEG C., if desired in the presence of an acidic catalyst, e.g. boron trifluoride or its ethyl ether complex, and of an inert organic solvent free from hydroxyl groups, e.g. an alkyl ether such as ethyl ether, a paraffin or aromatic hydrocarbon such as heptane or benzene or a halohydrocarbon, e.g. ethylene dichloride or chlorobenzene. Specified phosphate diesters are the di-methyl, ethyl, butyl, hexyl, 2-ethylhexyl, octyl, octadecyl, 2-chloro-ethyl, 2-chloropropyl, 2,3-dichloropropyl, 2 - bromoethyl, 2 - fluoroethyl, phenyl, p-chlorophenyl, 2,4 - dichlorophenyl, di - cresyl and dibenzyl phosphate diesters and specified oxirane compounds are ethylene oxide, propylene oxide, 1,2-epoxybutane, epichlorhydrin and epibromhydrin. The heating of the hydroxyl-containing phosphate ester to form the polyphosphate product is usually conducted under reduced pressure, e.g. 0.5 to 1 mm. of mercury and an acidic catalyst, e.g. boron trifluoride, stannic chloride or other Friedel-Crafts type catalyst may be present. The hydroxyl-containing polyphosphate ester product may be reacted, usually at about 100 DEG to 125 DEG C. with an aliphatic, cycloaliphatic, or aromatic mono- or polycarboxylic acid or acid anhydride. Specified acids are acetic, caproic, capric, stearic, succinic, methylsuccinic, benzoic, toluic, phthalic, cyclobutane carboxylic, 1,2 - cyclobutanedicarboxylic, monochloracetic, 2 - bromobutanoic, chlorosuccinic, p - chlorobenzoic, 3 - chlorocyclopentanecarboxylic, tetrachlorophthalic, phenyl acetic, p-phenyl benzoic, methoxyacetic, o-ethoxy benzoic, and 2,4-dichlorophenoxy acetic acids. This further reaction is preferably carried out using the acid anhydride in a proportion of 2 mols. per mol. of hydroxyl present in polyphosphate and an acid esterification catalyst, e.g. sulphuric, hydrochloric or arylsulphonic acid or boron trifluoride may be present. In
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US812390XA | 1955-06-06 | 1955-06-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB812390A true GB812390A (en) | 1959-04-22 |
Family
ID=22162941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB17280/56A Expired GB812390A (en) | 1955-06-06 | 1956-06-05 | Polymeric phosphate esters and their production |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB812390A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4062855A (en) | 1971-09-27 | 1977-12-13 | University Of Washington | Synthetic polymers furnishing controlled release of a biologically active component during degradation |
| US5387655A (en) * | 1991-09-09 | 1995-02-07 | Chemische Fabrik Budenheim | Composition with integral intumescence properties |
| WO1996016969A1 (en) * | 1994-11-29 | 1996-06-06 | Henkel Kommanditgesellschaft Auf Aktien | Phosphoric acid triesters |
| US5864003A (en) * | 1996-07-23 | 1999-01-26 | Georgia-Pacific Resins, Inc. | Thermosetting phenolic resin composition |
| US5962603A (en) * | 1996-07-23 | 1999-10-05 | Georgia-Pacific Resins, Inc. | Intumescent composition and method |
| US6107507A (en) * | 1999-09-10 | 2000-08-22 | Akzo Nobel Nv | Formation of oligomeric organophosphorus compositions with improved color |
| US7087703B2 (en) | 2004-07-26 | 2006-08-08 | Georgia-Pacific Resins, Inc. | Phenolic resin compositions containing etherified hardeners |
-
1956
- 1956-06-05 GB GB17280/56A patent/GB812390A/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4062855A (en) | 1971-09-27 | 1977-12-13 | University Of Washington | Synthetic polymers furnishing controlled release of a biologically active component during degradation |
| US5387655A (en) * | 1991-09-09 | 1995-02-07 | Chemische Fabrik Budenheim | Composition with integral intumescence properties |
| WO1996016969A1 (en) * | 1994-11-29 | 1996-06-06 | Henkel Kommanditgesellschaft Auf Aktien | Phosphoric acid triesters |
| US5864003A (en) * | 1996-07-23 | 1999-01-26 | Georgia-Pacific Resins, Inc. | Thermosetting phenolic resin composition |
| US5962603A (en) * | 1996-07-23 | 1999-10-05 | Georgia-Pacific Resins, Inc. | Intumescent composition and method |
| US6107507A (en) * | 1999-09-10 | 2000-08-22 | Akzo Nobel Nv | Formation of oligomeric organophosphorus compositions with improved color |
| US7087703B2 (en) | 2004-07-26 | 2006-08-08 | Georgia-Pacific Resins, Inc. | Phenolic resin compositions containing etherified hardeners |
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