WO2008073872A1 - Oligomères d'organophosphonate, leurs mélanges et procédés de production d'oligomères d'organophosphonate et de leurs mélanges - Google Patents
Oligomères d'organophosphonate, leurs mélanges et procédés de production d'oligomères d'organophosphonate et de leurs mélanges Download PDFInfo
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- WO2008073872A1 WO2008073872A1 PCT/US2007/086934 US2007086934W WO2008073872A1 WO 2008073872 A1 WO2008073872 A1 WO 2008073872A1 US 2007086934 W US2007086934 W US 2007086934W WO 2008073872 A1 WO2008073872 A1 WO 2008073872A1
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- WIPO (PCT)
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- oligomers
- process according
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 58
- -1 alkyl phosphite Chemical compound 0.000 claims abstract description 48
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 17
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 16
- 125000000746 allylic group Chemical group 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract 7
- 238000006243 chemical reaction Methods 0.000 claims description 136
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000000047 product Substances 0.000 claims description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 239000003039 volatile agent Substances 0.000 claims description 13
- 238000002411 thermogravimetry Methods 0.000 claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 11
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical group COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 11
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 10
- 238000009616 inductively coupled plasma Methods 0.000 claims description 10
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical group IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 2
- 239000010452 phosphate Substances 0.000 claims 2
- 150000001351 alkyl iodides Chemical class 0.000 claims 1
- 238000005809 transesterification reaction Methods 0.000 abstract description 4
- 238000006462 rearrangement reaction Methods 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 description 26
- 239000006227 byproduct Substances 0.000 description 25
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 20
- 238000004679 31P NMR spectroscopy Methods 0.000 description 15
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 239000003063 flame retardant Substances 0.000 description 11
- 239000005297 pyrex Substances 0.000 description 11
- 229920005830 Polyurethane Foam Polymers 0.000 description 10
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 10
- 239000011496 polyurethane foam Substances 0.000 description 10
- 238000009472 formulation Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- 230000003247 decreasing effect Effects 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- LTBRACVJRXLQHC-UHFFFAOYSA-N OP(=O)OCC1=CC=CC=C1 Chemical class OP(=O)OCC1=CC=CC=C1 LTBRACVJRXLQHC-UHFFFAOYSA-N 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZDXGQHXSMPGQRI-UHFFFAOYSA-N 2,6-ditert-butyl-3-[(2,4-ditert-butyl-3-hydroxyphenyl)methyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC=C1CC1=CC=C(C(C)(C)C)C(O)=C1C(C)(C)C ZDXGQHXSMPGQRI-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- PELLYVDRZIFQRF-UHFFFAOYSA-N benzyl dihydrogen phosphite Chemical class OP(O)OCC1=CC=CC=C1 PELLYVDRZIFQRF-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 210000004124 hock Anatomy 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
-
- 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
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
Definitions
- the present invention relates to organophosphonate oligomers, mixtures of organophosphonate oligomers, processes for producing organophosphonate oligomers and mixtures thereof, and the use of such organophosphonate oligomers and mixtures of organophosphonate oligomers.
- Polyurethane foams are used in many applications today. Because of the widespread use of polyurethane foams, much research has been done on providing flame retardancy to such foams. To this end, a myriad of flame retardants have been used and proposed to provide flame retardant properties to flexible polyurethane foams. However, even with the available flame retardants, the polyurethane industry has increasingly requested flame retardants that outperform or have more favorable characteristics than those currently available. Thus, there is a need in the art for flame retardants that are effective in polyurethane foams and methods for forming such flame retardants.
- organophosphonate oligomers can be produced that are capable of providing flame retarded polyurethane foams of very desirable quality.
- the present invention relates to a process comprising: a) bringing together in a reaction vessel (i) at least one trialkyl phosphite, (ii) at least one polyalkylene glycol, (iii) at least one allylic or methylated aromatic alcohol; and (iv) optionally at least one catalyst while maintaining the temperature of the reaction vessel contents at a temperature in the range of about 75 0 C to about 130 0 C thereby forming at least a mixture of alkyl phosphite oligomers; b) adding to said mixture of mixed alkyl phosphite oligomers a catalytic quantity of at least one alkyl halide while maintaining the reaction vessel contents at one or more temperatures in the range of from about 6O 0 C to about 15O 0 C for a period in the range of about 2 hours to about 12 hours thereby converting at least a portion, of said mixture of alkyl phosphite oligomers to
- the process of the present invention can be described as a two step process that can be described as 1) a transesterification reaction of the at least one trialkylphosphite with the at least one polyalkylene glycol and the at least one allylic or methylated aromatic alcohol to produce a mixture of mixed alkyl phosphite oligomer, and step 2) the conversion of at least a portion of the mixture of alkyl phosphite oligomers to a mixture of alkyl polyphosphonate oligomers via Arbuzov Rearrangement reactions catalyzed by the at least one alkyl halide.
- the optional catalyst is used in the processes of the present invention. In some embodiments, the optional catalyst is not used in processes of the present invention.
- the processes of the present invention are conducted in a batch manner, and in other embodiments, a semi-continuous, and in other embodiments, a continuous manner.
- organophosphonate oligomers and organophosphonate oligomer mixtures pursuant to this invention.
- these components are trimethyl phosphite, diethylene glycol, and benzyl alcohol. Similar products made from polypropylene glycol are unsuitable for producing polyurethanes having good properties.
- other processes such as those employing trimethyl phosphite, diethylene glycol, and benzyl chloride generate toxic gaseous methyl chloride.
- the present invention inventors hereof have noted that the processes of the present invention generate substantially no methyl chloride, typically no methyl chloride, and in some preferred embodiments, the processes of the present invention do not generate any gaseous side product.
- organophosphonate oligomer mixtures produced pursuant to this invention have been found capable of providing both polyether polyurethanes and polyester polyurethanes having desirable properties. Also, because of the availability and low cost of diethylene glycol, the practice of this invention is also of economic advantage.
- reaction vessel as used herein is used in its broadest sense and is meant to refer to any vessel, container, etc., which one having ordinary skill in the art would deem acceptable in carrying out the process of the present invention.
- the (i) at least one trialkyl phosphite used herein can be selected from any trialkyl phosphite.
- Non-limiting examples of preferred trialkyl phosphites include trimethyl phopsphite and triethyl phosphite.
- the at least one trialkyl phosphite is trimethyl phosphite.
- the (ii) at least one polyalkylene glycol used herein can be selected from any polyalkylene glycol.
- preferred polyalkylene glycols include triethylene glycol, diethylene glycol, and dipropylene glycol.
- the at least one polyalkylene glycol is diethylene glycol.
- the (iii) at least one allylic or methylated aromatic alcohol used herein can be selected from any allylic or methylated aromatic alcohol.
- the at least one allylic or methylated aromatic alcohol is benzyl alcohol.
- the (iv) at least one optional catalyst be selected from any catalyst effective at catalyzing transesterification reactions.
- catalysts suitable for use herein include alkali alkoxide such as sodium methoxide. It should be noted that it is preferred to operate the processes of the present invention in the absence of the optional catalyst.
- the amount of the (i) at least one trialkyl phosphite and (ii) at least one polyalkylene glycol used in the practice of the present invention is generally a mole ratio of about 0.8 to about 1.5 moles of (i) per mole of (ii), preferably a mole ratio of in the range of from about
- the amount of (iii) at least one allylic or methylated aromatic alcohol used herein is generally in the range of from about 0.05 to about 0.3 moles of (iii) per mole of (ii), preferably a mole ratio of in the range of from about 0.1 to about 0.2 moles of (iii) per mole of (ii).
- (i), (ii), (iii), and optionally (iv), can be combined in any order and in any amount.
- a portion or all of one reactant can be added to a portion or all of another reactant which in turn can be added to a portion or all of the third reactant, the reactants can be co-fed, and so forth.
- at least a portion, preferably substantially all, of (i) is added to the reaction vessel, and (ii) and (iii) are then introduced into the reaction vessel, preferably over time.
- substantially of all of (i) is added to the reaction vessel, then (iii) is added to reaction vessel, preferably over time, more preferably over a period of about 0.5 hours to about 3 hours, more preferably over a period of about 1 hour to about 2 hours, and then (ii) is introduced into the reaction vessel, preferably over time, more preferably over a period of about 2 hours to about 6 hours, most preferably over a period of about 3 hours to about 4 hours.
- (i) be trimethyl phosphite
- (ii) be diethylene glycol
- (iii) be benzyl alcohol.
- the temperature of the contents of the reaction vessel are maintained at one or more temperatures in the range of from about 75 0 C to about 13O 0 C. In preferred embodiments, the contents of the reaction vessel are maintained at one or more temperatures in the range of from about 85 0 C to about 12O 0 C.
- (iii), preferably benzyl alcohol is introduced into the reaction vessel after (i), preferably trimethyl phosphite, but before (ii), preferably diethylene glycol
- (ii) is then introduced while maintaining the temperature of the reaction vessel contents within these ranges. It should be noted that the temperature of the reaction vessel contents can be maintained through any means and method known in the art.
- heating can be applied to the reactor contents to raise the temperature or vacuum pressure applied to reduce the temperature of the boiling mixture.
- vacuum pressure is applied to maintain the reactor vessel temperature
- the vacuum pressure is decreased over time such that the ending pressure of the reaction vessel, i.e. after the introduction of (i), (ii), (iii), and optionally (iv), is in the range of from about 150 to about 330mmHg and the ending temperature of the reactor contents is in the range of from about 9O 0 C to about HO 0 C.
- the choice of reaction temperature and vacuum pressure and reaction time are in accordance with the desired degree of polymerization allowed in the reaction, which can be followed by the amount of methanol generated during the reaction.
- the methanol be removed from the reaction vessel as it is generated from the transesterification reactions of (i) with (ii) and (iii).
- the methanol can be removed from the reaction vessel via any technique known, but it is typically effectively removed by collecting the low boiling volatile components from the reaction vessel, typically as the temperature of the reaction vessel is maintained within the ranges described above, and utilizing distillation techniques to separate the methanol therefrom and return at least a portion, preferably substantially all, of any trimethyl phosphite contained therein to the reaction vessel.
- a catalytic quantity of alkyl halide preferably methyl iodide
- alkyl phosphite oligomers thereby converting at least a portion, preferably substantially all, of said mixture of alkyl phosphite oligomers to a mixture of alkyl phosphonate oligomers.
- catalytic amount of the at least one alkyl halide it is meant in the range of from about 0.1 to about 2.0 wt.%, preferably in the range of from about 0.3 to about 2.0 wt.%, more preferably in the range of from about 0.3 to about 1.0wt.%, all based on the total weight of the mixture of alkyl phosphite oligomers.
- the at least one alkyl halide can be introduced into the reaction vessel containing the mixture of alkyl phosphite oligomers, or the mixture of alkyl phosphite oligomers can be added to a second reaction vessel, optionally containing at least a portion of the at least one alkyl halide, and then the alkyl halide, or remaining alkyl halide, introduced.
- the mixture of alkyl phosphite oligomers is introduced into a second reaction vessel containing a heel of organophosphonate mixture, preferably remaining from a previous run of a process according to the present invention, and additional, if necessary, alkyl halide added to provide for an alkyl halide addition amount within the described ranges.
- the mixture of alkyl phosphite oligomers be fed over a period of time in the range of from about 2 to about 16 hours, preferably in the range of from about 3 to about 10 hours.
- the temperature of the reaction vessel contents be maintained at one or more temperatures in the range of from about 12O 0 C to about 17O 0 C, most preferably from about 12O 0 C to about 15O 0 C.
- At least a portion, preferably substantially all, of any volatiles is then removed from the mixture of alkyl phosphonate oligomers thereby producing an organophosphonate oligomer product.
- the method by which the volatiles are removed from the mixture of alkyl phosphonate oligomers can be selected from any technique known to be capable of removing volatile components from a reaction product mixture. Non-limiting examples of suitable methods include stripping, distilling, or using wipe film evaporators. In some embodiments, a wipe film evaporator is used.
- the organophosphonate oligomer product produced in the practice of the present invention comprises at least one, preferably a mixture of, organophosphonate oligomer(s).
- the organophosphonate oligomer(s) and organophosphonate oligomer mixtures produced by the present invention are copolymeric polyphosphonates having a suitable quantity of hydroxy-terminated end groups, thus enabling them to be utilized as reactive flame retardants in polyurethanes.
- organophosphonate oligomer mixtures produced by the present invention are typically mixtures of individual oligomers, and because these oligomers are mixtures of individual oligomers produced in a series of reactions, a depiction of the products is at best an approximation. Nevertheless, the following depiction will enable a visualization of a presumed general structure of the individual oligomers organophosphonate oligomer mixtures produced by the present invention:
- each Ri is independently selected from methyl, benzyl, or hydroxy terminated alkyl group, branched or straight, preferably branched, having in the range of from 1 to 10 carbon atoms; each Ej is the same or different and is either HOC 2 H 4 OC 2 H 4 - or methyl; and n is a whole or fractional number.
- one Ei is HOC 2 H 4 OC 2 H 4 - and the other Ei is methyl.
- the hydroxy terminated alkyl groups are branched primary or secondary alcohols having in the range of from 2 to 5 carbon atoms.
- each Rj is methyl or benzyl.
- methyl and benzyl are present in a numerical ratio of about 3 methyl groups per each benzyl group to about 10 methyl groups per each benzyl group. In these preferred embodiments, methyl and benzyl are present in a numerical ratio of about 3 methyl groups per each benzyl group to about 8 methyl groups per each benzyl group.
- n is about 20 or less, and preferably, is about 10 or less, and these values can be average values because the products are usually a mixture of oligomers.
- the average value of n is usually in the range of from about 1 to about 10; in some embodiments in the range of from about 1 to about 5; in some embodiments in the range of from about 2 to about 3; in still other embodiments, in the range of from about 5 to about 10.
- at least a portion of EiO contains terminal hydroxyl groups.
- the above formula is not intended to depict any particular stereoisomeric configuration for the oligomer depicted and consequently, the above formula does not constitute any representation, let alone limitation, concerning the geometric configuration of the oligomer.
- the mixtures of organophosphonate oligomers of the present invention further comprise organophosphonate oligomers wherein each Ei of is methyl.
- the hydroxyl number can be determined by a standard analytical procedure.
- the polyphosphonate oligomers produced pursuant to this invention have hydroxyl numbers in the range of about 10 to about 100, but can have hydroxyl numbers in the range of 0 to 100.
- the organophosphonate oligomer mixtures produced by the present invention can be characterized as having at least two, in some embodiments more than two, and in other embodiments all, of i) an average molecular weight, as determined by freeze point depression (“FPD") in the range of from about 400 to about 1200 g per gmol, in some embodiments in the range of from about 500 to about 900 g per gmol; ii) a viscosity at 25 0 C in the range of from about 2,000 to about 30,000 cP, in some embodiments in the range of from about 3,000 to about 9,000 cP; iii) a phosphorous content, as determined by inductively coupled plasma ("ICP"), in the range of from about 15 to about 20 wt.%, in some embodiments in the range of from about 16 to about 18 wt.%; v) an acid value in the range of from about 0.5 to 1.5 mg KOH/g solution; iv) a TGA (thermogravi
- the organophosphonate oligomer mixtures produced by the present invention are useful as flame retardants in a variety of applications.
- the organophosphonate oligomer mixtures produced by the present invention are used as flame retarding agents in polyurethane foams.
- the fundamental components used are isocyanates, polyols, and an organophosphonate oligomer mixtures of the present invention.
- the polyols are polyether polyols or polyester polyols. The reaction readily occurs at room temperature in the presence of a blowing agent such as water, a volatile hydrocarbon, halocarbon, or halohydrocarbon, or mixtures of two or more such materials.
- Catalysts used in effecting the reaction include amine catalysts, tin-based catalysts, bismuth-based catalysts or other organometallic catalysts, and the like.
- Surfactants such as substituted silicone compounds are often used in order to maintain homogeneity of the cells in the polymerization system.
- Hindered phenolic antioxidants e.g., 2,6-di-tert-butyl-para-cresol and methylenebis(2,6-di-tert-butylphenol), can be used to further assist in stabilization against oxidative degradation.
- organophosphonate oligomer mixtures of the present invention in the range of about 4 to about 15 wt% based on the total weight of the polyurethane formulation, are typically used.
- the organophosphonate oligomer products produced by this invention are typically colorless or slightly off-white in color. Light color is advantageous as it simplifies the end- users task of insuring consistency of color in the articles that are flame retarded with the oligomeric products.
- the organophosphonate oligomer mixtures produced by the present invention can also be used as flame retardants in, or in connection with, polyurethane resins and composites, rigid polyurethane foams, phenolic resins, paints, varnishes, and textiles.
- the organophosphonate oligomer mixtures of the present invention may be used as additive flame retardants in formulations with other flammable materials.
- the flammable material may be macromolecular, for example, a cellulosic material or a polymer.
- Illustrative polymers are: olefin polymers, cross-linked and otherwise, for example homopolymers of ethylene, propylene, and butylene; copolymers of two or more of such alkene monomers and copolymers of one or more of such alkene monomers and other copolymerizable monomers, for example, ethylene/propylene copolymers, ethylene/ethyl acrylate copolymers and ethylene/propylene copolymers, ethylene/acrylate copolymers and ethylene/vinyl acetate copolymers; polymers of olefmically unsaturated monomers, for example, polystyrene, e.g.
- polystyrene, and styrene copolymers polyamides; polyimides; polycarbonates; polyethers; acrylic resins; polyesters, especially poly(ethyleneterephthalate) and poly(butyleneterephthalate); thermosets, for example, epoxy resins; elastomers, for example, butadiene/styrene copolymers and butadiene/acrylonitrile copolymers; terpolymers of acrylonitrile, butadiene and styrene; natural rubber; butyl rubber and polysiloxanes.
- the polymer may be, where appropriate, cross-linked by chemical means or by irradiation.
- the organophosphonate oligomer products of this invention also can be used in textile applications, such as in latex-based back coatings.
- the amount of an organophosphonate oligomer mixtures produced by the present invention used in a formulation will be that quantity needed to obtain the flame retardancy sought. It will be apparent to those skilled in the art that for all cases no single precise value for the proportion of the product in the formulation can be given, since this proportion will vary with the particular flammable material, the presence of other additives and the degree of flame retardancy sought in any give application. Further, the proportion necessary to achieve a given flame retardancy in a particular formulation will depend upon the shape of the article into which the formulation is to be made, for example, electrical insulation, tubing, electronic cabinets and film will each behave differently.
- the formulation, and resultant product may contain from about 1 to about 30 wt%, preferably from about 5 to about 25 wt% of an organophosphonate oligomer mixture produced by the present invention.
- thermoplastic formulations Any of several conventional additives used in thermoplastic formulations may be used, in their respective conventional amounts, with the oligomeric flame retardants of this invention, e.g., plasticizers, antioxidants, fillers, pigments, UV stabilizers, etc.
- oligomeric flame retardants of this invention e.g., plasticizers, antioxidants, fillers, pigments, UV stabilizers, etc.
- Thermoplastic articles formed from formulations containing a thermoplastic polymer and an oligomeric product of this invention can be produced conventionally, e.g., by injection molding, extrusion molding, compression molding, and the like. Blow molding may also be appropriate in certain cases.
- TMPi trimethyl phosphite
- BzOH benzyl alcohol
- DEG diethylene glycol
- the reactor temperature was maintained between about 82-92°C and low boiling by-products were collected.
- the reaction mixture was held in the reaction vessel for a period of about 6 hours during which time the pressure of the reaction vessel was decreased gradually from a starting pressure of about 760 torr to an ending pressure of about 164 torr, and low boiling by-products were continuously removed.
- the temperature of the reaction vessel was about 102 0 C when the 164 torr pressure was reached.
- the mixture of alkyl phosphite oligomers in the reaction vessel was analysed by 31 P-NMR and found containing 95.2 mol% methyl and benzyl phosphites, 1.1 mol% H-phosphonates, and 3.3 mol% phosphonates.
- the low boiling by-products removed from the reaction vessel weighed 486.7 g and were found to contain 92.5 wt% methanol ("MeOH")-and 7.5 wt% trimethyl phosphite, both based on the total weight of the low boiling by-products removed.
- Methyl iodide (6.7 g, 0.047 gmol) ("Mel) was added to a second reaction vessel (2- liter Pyrex reaction flask) containing a heel (192 g) from a previous reaction.
- This heel comprised 97.7% phosphonates; 1.8% H-phosphonates; and 0.5% phosphates; and had an acid number of 0.73 mg KOH/g.
- the heel was heated to 130 0 C, and then 1350.5 g of the mixture of alkyl phosphite oligomers was added to the second reaction vessel over a 4 hour period while maintaining the second reaction vessel contents at about 13O 0 C. After a 4-hr post heating at 13O 0 C, 31 P-NMR confirmed the complete conversion of phosphites to phosphonates.
- TGA 5 wt% at 238 0 C, 10 wt% at 263°C.
- a 2-liter round bottom jacketed Pyrex reactor equipped with an overhead stirrer, addition funnel, thermocouple, and a distillation head was charged with TMPi (1014.8 g, 8.18 mol). After the addition of the TMPi, the reactor contents were heated to 95 0 C, and BzOH (127 '.4 g, 1.18 mol) was fed over 1 hour. During the addition of BzOH the temperature of the reaction mixture varied from 95-97°C. Next, DEG (743.9 g, 7.01 mol) was fed into the reactor over 5.5 hours. During the addition of DEG, the reactor temperature was maintained between 85-95 0 C and low boiling by-products were collected.
- reaction contents were held in the reaction vessel for a period of about 7.5 hours during which time the pressure of the reaction vessel was decreased from a starting pressure of about 760 torr to an ending pressure of about 150 torr, and low boiling byproducts were continuously removed.
- the temperature of the reaction vessel was about 112 0 C when the 150 torr pressure was reached.
- mixture of alkyl phosphite oligomers in the reaction vessel was analysed by 31 P-NMR and found containing 94.3 mol.% phosphites, 3.6 mol% phosphonates, 0.5 mol% phosphates, and 1.6 mol% H-phosphonates.
- the low boiling by-products removed from the reaction vessel weighed 48Og and were composed of 95.1 wt% MeOH and 4.7 wt% TMPi,-both based on the total weight of the low boiling by-products removed.
- MeI (6.7 g, 0.047 moles) was added to a second reaction vessel (2-liter round bottom jacketed Pyrex reaction flask) containing 179 g of the heel from Example 1.
- the second reaction vessel contents were heated to 13O 0 C and then 1371 g of the mixture of alkyl phosphite oligomers were added to the second reaction vessel over a 4 hour period while maintaining the second reaction vessel contents at about 13O 0 C.
- TGA 5 wt% at 223 0 C, 10 wt% at 253°C.
- a 2-liter round bottom jacketed Pyrex reactor equipped with an overhead stirrer, addition funnel, thermocouple, and a distillation head was charged with TMPi (1010 g, 8.15 mol). After the addition of the TMPi, the reactor contents were heated to 92°C, and BzOH (128 g, 1.18 mol) was fed over 1.3 hours. During the addition of BzOH the temperature of the reaction mixture varied from 92-99°C. Next, DEG (747.4 g, 7.04 mol) was fed into the reactor over 5.7 hours. During the addition of DEG, the reactor temperature was maintained between 82-100 0 C and low boiling by-products were collected.
- the reaction contents were held in the reaction vessel for a period of about 3 hours during which time the pressure of the reaction vessel was decreased from a starting pressure of about 760 torr to an ending pressure of about 100 torr, and low boiling by-products were continuously removed.
- the temperature of the reaction vessel was about 113 0 C when the 100 torr pressure was reached.
- the mixture of alkyl phosphite oligomers in the reaction vessel was analysed by 31 P-NMR and found containing 98.1 mol.% phosphites, 0.7 mol% phosphonates, 0.57 mol% phosphates, and 0.71 mol% H-phosphonates.
- the low boiling by-products removed from the reaction vessel weighed 496g and were composed of 93.8 wt% MeOH and 5.1 wt% TMPi, both based on the total weight of the low boiling byproducts removed.
- Methyl iodide (6.53 g, 0.046 moles) was added to a second reaction vessel (2-liter round bottom jacketed Pyrex reaction flask) containing 173 g of the heel from Example 2.
- the heel was heated to 13O 0 C and then 1317 g of the mixture of alkyl phosphite oligomers were added to the second reaction vessel over a 4.3 hour period while maintaining the second reaction vessel contents at about 13O 0 C.
- TGA 5 wt% at 24O 0 C, 10 wt% at 261 0 C.
- a 2-liter round bottom jacketed Pyrex reactor equipped with an overhead stirrer, addition funnel, thermocouple, and a distillation head was charged with TMPi (1036 g, 8.35 mol). After the addition of the TMPi, the reactor contents were heated to 94 0 C, and BzOH (141.5 g, 1.31 mol) was fed over 1.3 hours. During the addition of BzOH the temperature of the reaction mixture varied from 94-96 0 C. Next, DEG (822 g, 7.74 mol) was fed into the reactor over 4.3 hours. During the addition of DEG, the reactor temperature was maintained between 81-93°C and low boiling by-products were collected.
- reaction contents were held in the reaction vessel for a period of about 1.3 hours during which time the pressure of the reaction vessel was decreased from a starting pressure of about 760 torr to an ending pressure of about 240 torr, and low boiling byproducts were continuously removed.
- the temperature of the reaction vessel was about 91 0 C when the 240 torr pressure was reached, and the reaction contained about 1544 g of mixture of alkyl phosphite oligomers.
- the low boiling by-products removed from the reaction vessel weighed 456 g and were composed of 93.1 wt% MeOH and 6.8 wt% TMPi, both based on the total weight of the low boiling by-products removed.
- Methyl iodide (7.5 g, 0.053 moles) was added to a second reaction vessel (2-liter round bottom jacketed Pyrex reaction flask) containing 139 g of a heel from a pevious reaction.
- This heel comprised 97.5 mol% phosphonates, 2.2 mol% H-phosphonates, and 0.2 mol% phosphates.
- 1528 g of the mixture of alkyl phosphite oligomers were added to the second reaction vessel over a 4.5 hour period while maintaining the second reaction vessel contents at 125-127 0 C.
- TGA 5 wt% at 219°C, 10 wt% at 246 0 C.
- the reaction contents were held in the reaction vessel for a period of about 1.5 hours during which time the pressure of the reaction vessel was decreased from a starting pressure of about 760 torr to an ending pressure of about 145 torr, and low boiling byproducts were continuously removed.
- the temperature of the reaction vessel was about 101 0 C when the 145 torr pressure was reached.
- the mixture of alkyl phosphite oligomers in the reaction vessel was analysed by 31 P-NMR and found containing 98.0 mol.% phosphites, 0.8 mol% phosphonates, 0.3 mol% phosphates, and 0.8 mol% H-phosphonates.
- the low boiling by-products removed from the reaction vessel weighed 506 g and were composed of 92 wt% MeOH and 7.5 wt% TMPi, both based on the total weight of the low boiling by-products removed.
- Methyl iodide (7.1 g, 0.05 moles) was added to a second reaction vessel (2-liter round bottom jacketed Pyrex reaction flask) containing 228 g of a heel from a previous reaction.
- This heel comprised 98.8 mol% phosphonates, 1.1 mol% H-phosphonates, and 0.2 mol% phosphates.
- the heel was heated to 130 0 C and then 1402 g of the mixture of alkyl phosphite oligomers were added to the second reaction vessel over a 4 hour period while maintaining the second reaction vessel contents at about 13O 0 C.
- TGA 5 wt% at 229 0 C, 10 wt% at 252 0 C.
- a 2-liter round bottom jacketed Pyrex reactor equipped with an overhead stirrer, addition funnel, thermocouple, and a distillation head was charged with TMPi (1000 g, 8.06 mol). After the addition of the TMPi, the reactor contents were heated to 95°C, and BzOH (129.2 g, 1.29 mol) was fed over 1 hour. During the addition of BzOH the temperature of the reaction mixture varied from 95-98°C. After the addition of BzOH, a solution of 25 wt% sodium methoxide (1.45 g) was mixed with the reactor contents. Next, DEG (732 g, 6.9 mol) was fed into the reactor over 4 hours.
- the reactor temperature was maintained between 83-95°C and low boiling by-products were collected.
- the reaction contents were held in the reaction vessel for a period of about 2.5 hours during which time the pressure of the reaction vessel was decreased from a starting pressure of about 760 torr to an ending pressure of about 400 torr, and low boiling by-products were continuously removed.
- the temperature of the reaction vessel was about 99°C when the 400 torr pressure was reached, and the reaction contained about 1470 g of mixture of alkyl phosphite oligomers.
- the low boiling by-products removed from the reaction vessel weighed 394.4 g and were composed of 94.8 wt% MeOH and 5.2 wt% TMPi, both based on the total weight of the low boiling by-products removed.
- a portion (1102 g) of the mixture of alkyl phosphite oligomers were removed.
- Methyl iodide (1.62 g) was added to the rest of the alkyl phosphite oligomers in the reactor.
- the reactor contents were heated at 13O 0 C for 3 hours to create a heel of a mixture of phosphonate oligomers. Then an additional 5.8 g of methyl iodide was added to the heel.
- the 1102 g of the mixture of alkyl phosphite oligomers were subsequently added to the reaction vessel over a 4 hour period while maintaining the reaction vessel contents at 13O 0 C. After a 4-hr posting heating at 130 0 C, 31 P-NMR confirmed the complete conversion of phosphites to phosphonates.
- the resulting mixture of alkyl phosphonate oligomers was first batch stripped to remove 54.3 g of volatiles at an ending condition of 49 torr and 126°C, and then stripped of all the remaining volatiles using a 2" wiped-film evaporator, operating at a vacuum of 0.46 torr, absolute, and at a jacket temperature of 130°C, thereby producing an organophosphonate oligomer product.
- TGA 5 wt% at 212°C, 10 wt% at 238°C.
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Abstract
Cette invention concerne des procédés de production d'oligomères d'organophosphonate et de leurs mélanges à partir de 1) la réaction de transestérification d'au moins un phosphite de trialkyle, d'au moins un polyalkylène glycol, d'au moins un alcool aromatique allylique ou méthylé et éventuellement d'au moins un catalyseur pour former un mélange d'oligomères de phosphite d'alkyle ; 2) la réaction de réarrangement d'Arbuzov des oligomères de phosphite d'alkyle résultants catalysée par une quantité catalytique d'un halogénure d'alkyle en un mélange d'oligomères de phosphonate d'alkyle ; et 3) l'élimination des composants volatiles par vaporisation instantanée.
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US86952306P | 2006-12-11 | 2006-12-11 | |
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US94855207P | 2007-07-09 | 2007-07-09 | |
US60/948,552 | 2007-07-09 |
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WO2018129288A1 (fr) * | 2017-01-05 | 2018-07-12 | Frx Polymers, Inc. | Durcissement de résines époxy avec des oligomères de phosphonate |
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TW201022335A (en) * | 2008-10-21 | 2010-06-16 | Albemarle Corp | Mixed glycol polyphosphonate compounds |
CN104119380A (zh) * | 2014-04-15 | 2014-10-29 | 江苏大明科技有限公司 | 一种无卤低聚膦酸酯阻燃剂及其合成方法 |
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US3092651A (en) * | 1961-08-07 | 1963-06-04 | Weston Chemical Corp | 2-hydroxyalkane phosphonate and polyphosphonate hydroxyalkyl esters |
US3840622A (en) * | 1971-11-11 | 1974-10-08 | Stauffer Chemical Co | Polyalkylene glycol polyphosphorus compounds |
GB1397361A (en) * | 1972-08-21 | 1975-06-11 | Stauffer Chemical Co | Polyalkylene glycol alkyl or haloalkyl polyphosphonates useful as flame retardants |
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DE10247973B4 (de) * | 2002-10-15 | 2005-05-04 | Clariant Gmbh | Halogenreduzierte Flammschutzmittelmischungen zur Herstellung von emissionsstabilen Polyurethanweichschäumen |
RU2276638C1 (ru) * | 2004-12-14 | 2006-05-20 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") | Композиционный материал и изделие, выполненное из него |
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- 2007-12-10 WO PCT/US2007/086934 patent/WO2008073872A1/fr active Application Filing
- 2007-12-10 WO PCT/US2007/086932 patent/WO2008073871A1/fr active Application Filing
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Publication number | Priority date | Publication date | Assignee | Title |
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US3092651A (en) * | 1961-08-07 | 1963-06-04 | Weston Chemical Corp | 2-hydroxyalkane phosphonate and polyphosphonate hydroxyalkyl esters |
US3840622A (en) * | 1971-11-11 | 1974-10-08 | Stauffer Chemical Co | Polyalkylene glycol polyphosphorus compounds |
GB1397361A (en) * | 1972-08-21 | 1975-06-11 | Stauffer Chemical Co | Polyalkylene glycol alkyl or haloalkyl polyphosphonates useful as flame retardants |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2018129288A1 (fr) * | 2017-01-05 | 2018-07-12 | Frx Polymers, Inc. | Durcissement de résines époxy avec des oligomères de phosphonate |
KR20190105036A (ko) * | 2017-01-05 | 2019-09-11 | 에프알엑스 폴리머스, 인코포레이티드 | 포스포네이트 올리고머를 갖는 에폭시 수지의 경화 |
CN110300757A (zh) * | 2017-01-05 | 2019-10-01 | Frx 聚合物股份有限公司 | 用膦酸酯低聚物固化环氧树脂 |
US10717931B2 (en) | 2017-01-05 | 2020-07-21 | Frx Polymers, Inc. | Curing of epoxy resins with phosphonate oligomers |
KR102668113B1 (ko) * | 2017-01-05 | 2024-05-23 | 에프알엑스 폴리머스, 인코포레이티드 | 포스포네이트 올리고머를 갖는 에폭시 수지의 경화 |
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