CA2177059A1 - Bis(pentaerythritol phosphate alcohol) alkylphosphonate - Google Patents
Bis(pentaerythritol phosphate alcohol) alkylphosphonateInfo
- Publication number
- CA2177059A1 CA2177059A1 CA002177059A CA2177059A CA2177059A1 CA 2177059 A1 CA2177059 A1 CA 2177059A1 CA 002177059 A CA002177059 A CA 002177059A CA 2177059 A CA2177059 A CA 2177059A CA 2177059 A1 CA2177059 A1 CA 2177059A1
- Authority
- CA
- Canada
- Prior art keywords
- pentaerythritol phosphate
- phosphate alcohol
- bis
- compound
- alcohol
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
-
- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
Abstract
A bis(pentaerythritol phosphate alcohol) alkylphosphonate compound, such as one comprising an alkyl group of from about one to four carbon atoms, preferably bis(pentaerythritol phosphate alcohol) methylphosphonate, is a flame retardant compound. Such a compound can be prepared by the transesterification of a diphenyl alkyl phosphonate carrying the desired alkyl group with pentaerythritol phosphate alcohol.
An alternative process of preparation comprises the reaction of pentaerythritol phosphate alcohol, a trialkylamine, and an alkylphosphonic dihalide.
An alternative process of preparation comprises the reaction of pentaerythritol phosphate alcohol, a trialkylamine, and an alkylphosphonic dihalide.
Description
WO95/14704 ~ 17 ~ ~ 5 9 PCT~S94/13174 .
BIS(PENTAERYTHRITOL PHOSPHATE
ALCOHOL) ALKYLPHOSPHONATE
BACKGROUND OF THE INVENTION
i Various derivatives of pentaerythritol phosphate are known as flame retardant additives for polymers such as polypropylene. A recent example is provided by U.S.
Patent No. 4,801,625 to W.J. Parr et al. which describes ether, ester and carbonate derivatives of pentaerythritol phosphate. The carbonate version of such compounds can be advantageously prepared by the reaction of pentaerythritol phosphate alcohol with a dihydrocarbyl carbonate as described in U.S. Patent No. 5,235,085.
SUMMARY OF THE PRESENT INVENTION
The present invention relates to novel flame retardant compounds which are bis(pentaerythritol phosphate alcohol) alkylphosphonate compounds.
~ESCRIPTION OF PREFERRED EMBODIMENTS
The present novel bis(pentaerythritol phosphate alcohol) alkylphosphonate compounds are of the formula:
[O=P- O - CH2 -C-CH2O]2P(O)R
where R is alkyl, for example alkyl of from one to four carbon atoms, preferably methyl.
One process for forming the above-described novel compounds is by the transesterification of a diphenyl alkyl phosphonate carrying the desired alkyl group with pentaerythritol phosphate alcohol which has the formula WO95/14704 PCT~S94/13174 2 ~ 7 ~ 2-O=P-- O -- CH2 --C--CH20H
0 ~ CH2 ~r The phosphonate reagent is of the formula (ArO)2P(O)R, where Ar is substituted or unsubstituted phenyl and R is alkyl as previously described. The transesterification reaction is advantageously conducted at elevated temperature (e.g., a temperature of from about 170C to about 200C) in a high boiling organic solvent, such as an aryl phosphate solvent (as described in U.S. Patent No.
5,237,085), using an appropriate transesterification catalyst (e.g., magnesium dichloride, sodium phenoxide, or the like). The reaction mixture will contain the desired crude product with a phenolic by-product. The crude product can be triturated with a solvent such as acetonitrile or methanol to give the desired, purified product.
An alternative way of preparing the novel compounds is by the reaction of pentaerythritol phosphate alcohol, a trialkylamine, such as triethylamine, and an alkylphosphonic dihalide, such as methylphosphonic dichloride, in an appropriate solvent, such as acetonitrile, under cooling at essentially ambient temperature (e.g., 20C to about 30C).
The following Examples further illustrate the present invention.
Wos~/l47o4 2 1 7 ~ PCT~$94/1317 This illustrates preparation of bis(pentaerythritol phosphate alcohol) methylphosphonate.
Pentaerythritol phosphate alcohol (90.1 gm, 0.5 J 5 mole), diphenyl methylphosphonate (62.0 gm, 0.25 mole), magnesium chloride (238 mg, 2.5 mmole, 1.0 mole % on diphenyl methylphosphonate), and 85 mL of isopropyl triarylphosphate (PHOSFLEX 41P brand from Akzo Chemicals Inc.) were charged to a 250 mL, four neck, round bottom flask with mechanical stirrer, thermometer, 3.5 inch Vigreux column, distillation head and receiver with vacuum connection. A vacuum of 60 mm Hg was applied, and the reaction mixture was heated.
Over a period of four hours the flask temperature was raised from room temperature to 193C. About thirty-five minutes thereafter, slow distillation of phenol began at a flask temperature of 185C, distillation head temperature of 97OC, and 35 mm Hg pressure. One hour later, with the flask at 200C, the distillation head at 90C, and 10 mm Hg pressure, the reaction was cooled and 1000 mg of magnesium chloride was added. Then, the reactor was heated for two hours at 195C (down to 5.5 mm Hg pressure) before cooling after no further distillation occurred.
The system was cooled to 100C at which time two phases were observed, one liquid and the other a gummy mass. After further cooling to 80C, 100 ml of methanol was added which dissolved the liquid phase and part of the gummy mass leaving behind a white solid. The solid was removed by filtration and washed three times with 20 ml of methanol. The washed product was dried in an oven overnight at room temperature and 1 mm Hg pressure yielding 12.0 gm of a white powder having a decomposition about 325C.
After the remaining mother liquor was allowed to stand overnight, more solid crystallized and was filtered, WO95/14704 PCT~S94/13174 9 ~
washed twice with 20 ml of methanol, and dried in air to yield 5.8 gm of a white solid.
Both isolated products had structures by 31p nmr in DMSO (+ 34.2 ppm and -6.3 ppm in a 1:2 ratio) which were consistent with bis(pentaerythritol phosphate alcohol) methylphosphonate.
~XAMPLE 2 This illustrates an alternative preparation of bis(pentaerythritol phosphate alcohol) methylphosphonate.
Pentaerythritol phosphate alcohol (63.4 g, 0.36 mole), triethylamine (49.1 mL, 35.6 g, 0.36 mole), and 150 mL of acetonitrile were charged to a 250 mL 4-necked round-bottomed flask with mechanical stirrer, thermometer, nitrogen inlet, and dropping funnel containing methylphosphonic dichloride (23.4 g, 0.18 mole) and 5 mL
acetonitrile. The reactor was stirred and cooled with an ice bath as the methylphosphonic dichloride was added dropwise over fifteen minutes while maintaining a pot temperature of 20C-30C.
The resulting thick slurry was heated to reflux for twelve hours, cooled to 25C, and filtered. The white solid was washed four times with 50 mL of methanol and then dried overnight at 100C/ 2 mm Hg. The white product weighed 61.4 g (81.2 % yield) and had properties substantially identical to the product from Example 1.
WO95/14704 2 1 7 7 ~ ~ 9 PCT~S94/13174 The compound of Example 2, hereinafter abbreviated as "Bis(PEPA)MPI', was evaluated as a flame retardant in polypropylene in the three formulations listed below from i 5 the following ingredients.
-- Weight Percentage --Inqredient l ~ 3 Polypropylene* 71.l 71.l 68.7 Bis(PEPA)MP lo.s l0.9 12.0 APP** 18.0 MPP*** - 18.0 l9.8 * Polypropylene homopolymer powder from Himont (PROFAX
6623PM brand) ** Ammonium polyphosphate from Monsanto (P/40 brand).
*** Melamine phosphate from Akzo Chemicals Inc. (FYROL MP
brand).
All ingredients were preblended prior to compounding in a Brabender mixer bowl. The mixing regime was at a temperature of 164C for approximately five minutes at a rotor rate of 50-75 rpm. The homogenized mixture was then compression molded to a thickness of l/16" in a heated hydraulic press (200C) for three-five minutes and cooled to room temperature. From this molded plaque, UL-94 test specimens were cut and tested for flammability.
The flame retardancy data was as follows:
Result l 2 3 UL-94 Test V-2 V-2 V-o Average Flame Time (sec) 2.l 8.9 l.2 The foregoing Examples, which illustrate certain embodiments of the present invention, should not be construed in a limiting sense for that reason. The scope PCT~S94/13174 ~ 7~ ~5 9 -6-of protection sought is set forth in the claims which follow.
BIS(PENTAERYTHRITOL PHOSPHATE
ALCOHOL) ALKYLPHOSPHONATE
BACKGROUND OF THE INVENTION
i Various derivatives of pentaerythritol phosphate are known as flame retardant additives for polymers such as polypropylene. A recent example is provided by U.S.
Patent No. 4,801,625 to W.J. Parr et al. which describes ether, ester and carbonate derivatives of pentaerythritol phosphate. The carbonate version of such compounds can be advantageously prepared by the reaction of pentaerythritol phosphate alcohol with a dihydrocarbyl carbonate as described in U.S. Patent No. 5,235,085.
SUMMARY OF THE PRESENT INVENTION
The present invention relates to novel flame retardant compounds which are bis(pentaerythritol phosphate alcohol) alkylphosphonate compounds.
~ESCRIPTION OF PREFERRED EMBODIMENTS
The present novel bis(pentaerythritol phosphate alcohol) alkylphosphonate compounds are of the formula:
[O=P- O - CH2 -C-CH2O]2P(O)R
where R is alkyl, for example alkyl of from one to four carbon atoms, preferably methyl.
One process for forming the above-described novel compounds is by the transesterification of a diphenyl alkyl phosphonate carrying the desired alkyl group with pentaerythritol phosphate alcohol which has the formula WO95/14704 PCT~S94/13174 2 ~ 7 ~ 2-O=P-- O -- CH2 --C--CH20H
0 ~ CH2 ~r The phosphonate reagent is of the formula (ArO)2P(O)R, where Ar is substituted or unsubstituted phenyl and R is alkyl as previously described. The transesterification reaction is advantageously conducted at elevated temperature (e.g., a temperature of from about 170C to about 200C) in a high boiling organic solvent, such as an aryl phosphate solvent (as described in U.S. Patent No.
5,237,085), using an appropriate transesterification catalyst (e.g., magnesium dichloride, sodium phenoxide, or the like). The reaction mixture will contain the desired crude product with a phenolic by-product. The crude product can be triturated with a solvent such as acetonitrile or methanol to give the desired, purified product.
An alternative way of preparing the novel compounds is by the reaction of pentaerythritol phosphate alcohol, a trialkylamine, such as triethylamine, and an alkylphosphonic dihalide, such as methylphosphonic dichloride, in an appropriate solvent, such as acetonitrile, under cooling at essentially ambient temperature (e.g., 20C to about 30C).
The following Examples further illustrate the present invention.
Wos~/l47o4 2 1 7 ~ PCT~$94/1317 This illustrates preparation of bis(pentaerythritol phosphate alcohol) methylphosphonate.
Pentaerythritol phosphate alcohol (90.1 gm, 0.5 J 5 mole), diphenyl methylphosphonate (62.0 gm, 0.25 mole), magnesium chloride (238 mg, 2.5 mmole, 1.0 mole % on diphenyl methylphosphonate), and 85 mL of isopropyl triarylphosphate (PHOSFLEX 41P brand from Akzo Chemicals Inc.) were charged to a 250 mL, four neck, round bottom flask with mechanical stirrer, thermometer, 3.5 inch Vigreux column, distillation head and receiver with vacuum connection. A vacuum of 60 mm Hg was applied, and the reaction mixture was heated.
Over a period of four hours the flask temperature was raised from room temperature to 193C. About thirty-five minutes thereafter, slow distillation of phenol began at a flask temperature of 185C, distillation head temperature of 97OC, and 35 mm Hg pressure. One hour later, with the flask at 200C, the distillation head at 90C, and 10 mm Hg pressure, the reaction was cooled and 1000 mg of magnesium chloride was added. Then, the reactor was heated for two hours at 195C (down to 5.5 mm Hg pressure) before cooling after no further distillation occurred.
The system was cooled to 100C at which time two phases were observed, one liquid and the other a gummy mass. After further cooling to 80C, 100 ml of methanol was added which dissolved the liquid phase and part of the gummy mass leaving behind a white solid. The solid was removed by filtration and washed three times with 20 ml of methanol. The washed product was dried in an oven overnight at room temperature and 1 mm Hg pressure yielding 12.0 gm of a white powder having a decomposition about 325C.
After the remaining mother liquor was allowed to stand overnight, more solid crystallized and was filtered, WO95/14704 PCT~S94/13174 9 ~
washed twice with 20 ml of methanol, and dried in air to yield 5.8 gm of a white solid.
Both isolated products had structures by 31p nmr in DMSO (+ 34.2 ppm and -6.3 ppm in a 1:2 ratio) which were consistent with bis(pentaerythritol phosphate alcohol) methylphosphonate.
~XAMPLE 2 This illustrates an alternative preparation of bis(pentaerythritol phosphate alcohol) methylphosphonate.
Pentaerythritol phosphate alcohol (63.4 g, 0.36 mole), triethylamine (49.1 mL, 35.6 g, 0.36 mole), and 150 mL of acetonitrile were charged to a 250 mL 4-necked round-bottomed flask with mechanical stirrer, thermometer, nitrogen inlet, and dropping funnel containing methylphosphonic dichloride (23.4 g, 0.18 mole) and 5 mL
acetonitrile. The reactor was stirred and cooled with an ice bath as the methylphosphonic dichloride was added dropwise over fifteen minutes while maintaining a pot temperature of 20C-30C.
The resulting thick slurry was heated to reflux for twelve hours, cooled to 25C, and filtered. The white solid was washed four times with 50 mL of methanol and then dried overnight at 100C/ 2 mm Hg. The white product weighed 61.4 g (81.2 % yield) and had properties substantially identical to the product from Example 1.
WO95/14704 2 1 7 7 ~ ~ 9 PCT~S94/13174 The compound of Example 2, hereinafter abbreviated as "Bis(PEPA)MPI', was evaluated as a flame retardant in polypropylene in the three formulations listed below from i 5 the following ingredients.
-- Weight Percentage --Inqredient l ~ 3 Polypropylene* 71.l 71.l 68.7 Bis(PEPA)MP lo.s l0.9 12.0 APP** 18.0 MPP*** - 18.0 l9.8 * Polypropylene homopolymer powder from Himont (PROFAX
6623PM brand) ** Ammonium polyphosphate from Monsanto (P/40 brand).
*** Melamine phosphate from Akzo Chemicals Inc. (FYROL MP
brand).
All ingredients were preblended prior to compounding in a Brabender mixer bowl. The mixing regime was at a temperature of 164C for approximately five minutes at a rotor rate of 50-75 rpm. The homogenized mixture was then compression molded to a thickness of l/16" in a heated hydraulic press (200C) for three-five minutes and cooled to room temperature. From this molded plaque, UL-94 test specimens were cut and tested for flammability.
The flame retardancy data was as follows:
Result l 2 3 UL-94 Test V-2 V-2 V-o Average Flame Time (sec) 2.l 8.9 l.2 The foregoing Examples, which illustrate certain embodiments of the present invention, should not be construed in a limiting sense for that reason. The scope PCT~S94/13174 ~ 7~ ~5 9 -6-of protection sought is set forth in the claims which follow.
Claims (9)
1. A bis(pentaerythritol phosphate alcohol) alkyl-phosphonate compound.
2. A compound as claimed in Claim 1 wherein the alkyl contains from about one to four carbon atoms.
3. Bis(pentaerythritol phosphate alcohol) methyl-phosphonate.
4. A process for preparing a compound as claimed in Claim 1 which comprises the transesterification of a diphenyl alkyl phosphonate carrying the desired alkyl group with pentaerythritol phosphate alcohol.
5. A process for preparing a compound as claimed in Claim 2 which comprises the transesterification of a diphenyl alkyl phosphonate carrying the desired alkyl group with pentaerythritol phosphate alcohol.
6. A process for preparing a compound as claimed in Claim 2 which comprises the transesterification of a diphenyl alkyl phosphonate carrying the desired alkyl group with pentaerythritol phosphate alcohol.
7. A process for preparing a compound as claimed in Claim 1 which comprises the reaction of pentaerythritol phosphate alcohol, a trialkylamine, and an alkylphosphonic dihalide.
8. A process for preparing a compound as claimed in Claim 2 which comprises the reaction of pentaerythritol phosphate alcohol, a trialkylamine, and an alkylphosphonic dihalide.
9. A process for preparing a compound as claimed in Claim 3 which comprises the reaction of pentaerythritol phosphate alcohol, a trialkylamine, and an alkylphosphonic dihalide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/155,666 | 1993-11-22 | ||
| US08/155,666 US5362898A (en) | 1993-11-22 | 1993-11-22 | Bis(pentaerythritol phosphate alcohol) alkylphosphonate |
| PCT/US1994/013174 WO1995014704A1 (en) | 1993-11-22 | 1994-11-15 | Bis(pentaerythritol phosphate alcohol) alkylphosphonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2177059A1 true CA2177059A1 (en) | 1995-06-01 |
Family
ID=22556302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002177059A Abandoned CA2177059A1 (en) | 1993-11-22 | 1994-11-15 | Bis(pentaerythritol phosphate alcohol) alkylphosphonate |
Country Status (6)
| Country | Link |
|---|---|
| US (3) | US5362898A (en) |
| EP (1) | EP0730600A4 (en) |
| JP (1) | JPH10500656A (en) |
| CN (1) | CN1135755A (en) |
| CA (1) | CA2177059A1 (en) |
| WO (1) | WO1995014704A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5536862A (en) * | 1995-05-09 | 1996-07-16 | Akzo Nobel N.V. | Pentaerythritol phosphate alcohol-containing phosphonate and phosphite compounds |
| US5536863A (en) * | 1995-05-09 | 1996-07-16 | Akzo Nobel N.V. | (Pentaerythritol phosphate alcohol) (cyclic neopentylene glycol) phosphite and phosphonate |
| US5614081A (en) * | 1995-06-12 | 1997-03-25 | Betzdearborn Inc. | Methods for inhibiting fouling in hydrocarbons |
| US5633301A (en) * | 1996-05-23 | 1997-05-27 | Akzo Nobel Nv | Flame retardant polyketone composition |
| US5858176A (en) * | 1997-04-22 | 1999-01-12 | Betzdearborn Inc. | Compositions and methods for inhibiting fouling of vinyl monomers |
| US6455722B1 (en) * | 2001-06-29 | 2002-09-24 | Pabu Services, Inc. | Process for the production of pentaerythritol phosphate alcohol |
| DE102011002639A1 (en) * | 2011-01-13 | 2012-07-19 | Evonik Oxeno Gmbh | Process for the preparation of biphephos |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA866204A (en) * | 1971-03-16 | Gordon Irving | Ester of phosphorus and method of preparation thereof | |
| US3494986A (en) * | 1963-07-01 | 1970-02-10 | Hooker Chemical Corp | Process for the preparation of triesters of phosphorus |
| US3772414A (en) * | 1971-01-05 | 1973-11-13 | Monsanto Co | Preparation of esters of phosphorus acids |
| US3965220A (en) * | 1971-06-24 | 1976-06-22 | Monsanto Company | Preparation of esters of phosphorus acids |
| US3789091A (en) * | 1971-11-15 | 1974-01-29 | Mobil Oil Corp | Cyclic phosphonate esters and their preparation |
| US3883478A (en) * | 1973-12-07 | 1975-05-13 | Fmc Corp | Flame-Retardant Polyester Fiber Compositions |
| US4152373A (en) * | 1975-09-22 | 1979-05-01 | Stauffer Chemical Company | Process for preparing diaryl methylphosphonate and derivatives thereof |
| US4801625A (en) * | 1987-08-27 | 1989-01-31 | Akzo America Inc. | Bicyclic phosphate ether, ester, and carbonate intumescent flame retardant compositions |
| US5235085A (en) * | 1992-07-10 | 1993-08-10 | Akzo N.V. | Process for forming bis(pentaerythritol phosphate) carbonate |
| US5237085A (en) * | 1992-07-10 | 1993-08-17 | Akzo N V | Process for the formation of pentaerythritol-based phosphorous heterocycles |
-
1993
- 1993-11-22 US US08/155,666 patent/US5362898A/en not_active Expired - Fee Related
-
1994
- 1994-08-30 US US08/298,249 patent/US5486640A/en not_active Expired - Fee Related
- 1994-08-30 US US08/298,250 patent/US5486639A/en not_active Expired - Fee Related
- 1994-11-15 EP EP95902564A patent/EP0730600A4/en not_active Withdrawn
- 1994-11-15 JP JP7515124A patent/JPH10500656A/en active Pending
- 1994-11-15 CN CN94194249.XA patent/CN1135755A/en active Pending
- 1994-11-15 CA CA002177059A patent/CA2177059A1/en not_active Abandoned
- 1994-11-15 WO PCT/US1994/013174 patent/WO1995014704A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1995014704A1 (en) | 1995-06-01 |
| EP0730600A1 (en) | 1996-09-11 |
| US5486640A (en) | 1996-01-23 |
| US5486639A (en) | 1996-01-23 |
| CN1135755A (en) | 1996-11-13 |
| EP0730600A4 (en) | 1997-03-19 |
| US5362898A (en) | 1994-11-08 |
| JPH10500656A (en) | 1998-01-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |