WO1995014704A1 - Bis(pentaerythritol phosphate alcohol) alkylphosphonate - Google Patents

Bis(pentaerythritol phosphate alcohol) alkylphosphonate Download PDF

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Publication number
WO1995014704A1
WO1995014704A1 PCT/US1994/013174 US9413174W WO9514704A1 WO 1995014704 A1 WO1995014704 A1 WO 1995014704A1 US 9413174 W US9413174 W US 9413174W WO 9514704 A1 WO9514704 A1 WO 9514704A1
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Prior art keywords
pentaerythritol phosphate
phosphate alcohol
bis
compound
alcohol
Prior art date
Application number
PCT/US1994/013174
Other languages
French (fr)
Inventor
Jeffrey E. Telschow
Original Assignee
Akzo Nobel N.V.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Priority to CA002177059A priority Critical patent/CA2177059A1/en
Priority to JP7515124A priority patent/JPH10500656A/en
Priority to EP95902564A priority patent/EP0730600A4/en
Publication of WO1995014704A1 publication Critical patent/WO1995014704A1/en

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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

Definitions

  • the present invention relates to novel flame retardant compounds which are bis(pentaerythritol phosphate alcohol) alkylphosphonate compounds.
  • the present novel bis(pentaerythritol phosphate alcohol) alkylphosphonate compounds are of the formula:
  • 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 O - CH 2
  • the phosphonate reagent is of the formula (ArO) 2 P(0)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 170°C to about 200°C) 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.
  • a solvent such as acetonitrile or methanol
  • 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., 20°C to about 30°C) .
  • Pentaerythritol phosphate alcohol (90.1 gm, 0.5 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 4IP 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.
  • the flask temperature was raised from room temperature to 193°C. About thirty-five minutes thereafter, slow distillation of phenol began at a flask temperature of 185°C, distillation head temperature of 97°C, and 35 mm Hg pressure. One hour later, with the flask at 200°C, the distillation head at 90°C, 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 195°C (down to 5.5 mm Hg pressure) before cooling after no further distillation occurred.
  • the system was cooled to 100°C at which time two phases were observed, one liquid and the other a gummy mass. After further cooling to 80°C, 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 325°C.
  • Pentaerythritol phosphate alcohol (63.4 g, 0.36 mole), triethylamine (49.1 mL, 35.6 g, 0.36 mole), and 150 L 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 L 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 20°C-30°C.
  • the resulting thick slurry was heated to reflux for twelve hours, cooled to 25°C, and filtered.
  • the white solid was washed four times with 50 mL of methanol and then dried overnight at 100°C/ 2 mm Hg.
  • the white product weighed 61.4 g (81.2 % yield) and had properties substantially identical to the product from Example 1.
  • Example 2 The compound of Example 2, hereinafter abbreviated as "Bis(PEPA)MP", was evaluated as a flame retardant in polypropylene in the three formulations listed below from the following ingredients.
  • the flame retardancy data was as follows:

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.

Description

BIS(PENTAERYTHRITOL PHOSPHATE ALCOHOL) ALKYLPHOSPHONATE
BACKGROUND OF THE INVENTION
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.
DESCRIPTION OF PREFERRED EMBODIMENTS
The present novel bis(pentaerythritol phosphate alcohol) alkylphosphonate compounds are of the formula:
O - CH2
/ \
[0=P- O - CH2 -C-CH20]2P(0)R
\ /
0 - CH2
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 O - CH2
/ \
0=P- 0 - CH2 -C-CH2OH
\ / O - CH2
The phosphonate reagent is of the formula (ArO)2P(0)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 170°C to about 200°C) 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., 20°C to about 30°C) .
The following Examples further illustrate the present invention.
EXAMPLE 1
This illustrates preparation of bis(pentaerythritol phosphate alcohol) methylphosphonate.
Pentaerythritol phosphate alcohol (90.1 gm, 0.5 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 4IP 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 193°C. About thirty-five minutes thereafter, slow distillation of phenol began at a flask temperature of 185°C, distillation head temperature of 97°C, and 35 mm Hg pressure. One hour later, with the flask at 200°C, the distillation head at 90°C, 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 195°C (down to 5.5 mm Hg pressure) before cooling after no further distillation occurred.
The system was cooled to 100°C at which time two phases were observed, one liquid and the other a gummy mass. After further cooling to 80°C, 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 325°C.
After the remaining mother liquor was allowed to stand overnight, more solid crystallized and was filtered. 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.
EXAMPLE 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 L 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 L 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 20°C-30°C. The resulting thick slurry was heated to reflux for twelve hours, cooled to 25°C, and filtered. The white solid was washed four times with 50 mL of methanol and then dried overnight at 100°C/ 2 mm Hg. The white product weighed 61.4 g (81.2 % yield) and had properties substantially identical to the product from Example 1.
EXAMPLES 3 -5
The compound of Example 2, hereinafter abbreviated as "Bis(PEPA)MP", was evaluated as a flame retardant in polypropylene in the three formulations listed below from the following ingredients.
— Weight Percentage —
Ingredient 1 2 3 Polypropylene* 71.1 71.1 68.7 Bis(PEPA)MP 10.9 10.9 12.0 APP** 18.0 — — MPP*** 18.0 19.8
* 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 164°C for approximately five minutes at a rotor rate of 50-75 rpm. The homogenized mixture was then compression molded to a thickness of 1/16" in a heated hydraulic press (200°C) 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 I 2 2
UL-94 Test V-2 V-2 V-0
Average Flame Time (sec) 2.1 8.9 1.2
The foregoing Examples, which illustrate certain embodiments of the present invention, should not be construed in a limiting sense for that reason. The scope of protection sought is set forth in the claims which follow.

Claims

I Claim :
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.
PCT/US1994/013174 1993-11-22 1994-11-15 Bis(pentaerythritol phosphate alcohol) alkylphosphonate WO1995014704A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002177059A CA2177059A1 (en) 1993-11-22 1994-11-15 Bis(pentaerythritol phosphate alcohol) alkylphosphonate
JP7515124A JPH10500656A (en) 1993-11-22 1994-11-15 Bis (pentaerythritol phosphate alcohol) alkyl phosphonate
EP95902564A EP0730600A4 (en) 1993-11-22 1994-11-15 Bis(pentaerythritol phosphate alcohol) alkylphosphonate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/155,666 US5362898A (en) 1993-11-22 1993-11-22 Bis(pentaerythritol phosphate alcohol) alkylphosphonate
US08/155,666 1993-11-22

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JP (1) JPH10500656A (en)
CN (1) CN1135755A (en)
CA (1) CA2177059A1 (en)
WO (1) WO1995014704A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5536863A (en) * 1995-05-09 1996-07-16 Akzo Nobel N.V. (Pentaerythritol phosphate alcohol) (cyclic neopentylene glycol) phosphite and phosphonate
US5536862A (en) * 1995-05-09 1996-07-16 Akzo Nobel N.V. Pentaerythritol phosphate alcohol-containing phosphonate and phosphite compounds
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

Citations (4)

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Publication number Priority date Publication date Assignee Title
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

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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
US5237085A (en) * 1992-07-10 1993-08-17 Akzo N V Process for the formation of pentaerythritol-based phosphorous heterocycles

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
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

Non-Patent Citations (1)

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Title
See also references of EP0730600A4 *

Also Published As

Publication number Publication date
CA2177059A1 (en) 1995-06-01
US5486639A (en) 1996-01-23
US5486640A (en) 1996-01-23
JPH10500656A (en) 1998-01-20
CN1135755A (en) 1996-11-13
US5362898A (en) 1994-11-08
EP0730600A4 (en) 1997-03-19
EP0730600A1 (en) 1996-09-11

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