WO1996017854A1 - Process for making hydroxy-terminated aromatic oligomeric phosphates - Google Patents

Process for making hydroxy-terminated aromatic oligomeric phosphates Download PDF

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Publication number
WO1996017854A1
WO1996017854A1 PCT/US1995/015868 US9515868W WO9617854A1 WO 1996017854 A1 WO1996017854 A1 WO 1996017854A1 US 9515868 W US9515868 W US 9515868W WO 9617854 A1 WO9617854 A1 WO 9617854A1
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WIPO (PCT)
Prior art keywords
terminated
aromatic
hydroxy
phosphate
resorcinol
Prior art date
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Ceased
Application number
PCT/US1995/015868
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French (fr)
Inventor
Danielle A. Bright
Ronald L. Pirrelli
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Akzo Nobel NV
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Akzo Nobel NV
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Filing date
Publication date
Application filed by Akzo Nobel NV filed Critical Akzo Nobel NV
Priority to JP51774996A priority Critical patent/JP3819425B2/en
Priority to EP95941523A priority patent/EP0796265B1/en
Priority to DE69530317T priority patent/DE69530317T2/en
Publication of WO1996017854A1 publication Critical patent/WO1996017854A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41F—PRINTING MACHINES OR PRESSES
    • B41F13/00—Common details of rotary presses or machines
    • B41F13/54—Auxiliary folding, cutting, collecting or depositing of sheets or webs
    • B41F13/56—Folding or cutting
    • B41F13/58—Folding or cutting lengthwise
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds

Definitions

  • Aromatic oligomeric phosphate compositions which are not hydroxy-terminated are known to persons of ordinary skill in the art with representative examples being described in European Patent Publication Nos. 509,506 and 521,628 and Japanese Patent Publication No. 227,632/1988.
  • a hydroxy-terminated aromatic oligomeric phosphate is depicted as one of the products formed by the processes described in Japanese Patent Publication No. 223,158/1989.
  • the product that is desired is a mixture of 22%-65%, by weight, of a reactive, hydroxy- terminated monophosphate ester, 15%-30% of a non-reactive, non- hydroxy-terminated phosphate ester, and 5%-63% of the hydroxy- terminated oligomeric phosphate ester.
  • 223,158/1989 relies, for example, upon the reaction of a mixture of phenol and aromatic diol (e.g., resorcinol) with phosphorus oxychloride in the presence of a catalyst (e.g., aluminum chloride) .
  • a catalyst e.g., aluminum chloride
  • the present invention is a process for forming hydroxy- terminated aromatic oligomeric phosphates by the initial reaction of a monoaryl dihalophosphate, such as monophenyl dichlorophosphate, with an aromatic diol, such as resorcinol, to form a halo-terminated aromatic oligomeric phosphate and the subsequent reaction of that halo-terminated phosphate with aromatic diol to form the hydroxy-terminated aromatic oligomeric phosphate.
  • the initial and subsequent reactions preferably employ a Lewis acid catalyst, such as magnesium dichloride.
  • the initial process step in the instant process for forming hydroxy-terminated aromatic oligomeric phosphates is the initial reaction of a monophenyl dihalophosphate with an aromatic diol to form a halo-terminated aromatic oligomeric phosphate.
  • the monophenyl dihalophosphate is of the formula ArOP(0)X 2 , where Ar stands for substituted or unsubstituted phenyl and X stands for halo, such as chloro or bromo.
  • a preferred reagent to use is monophenyl dichlorophosphate.
  • the aromatic diol is of the formula HOROH, with R being a hydrocarbyl group such as phenyl, diphenyl, 4,4' -isopropylidenediphenyl, and the like.
  • a particularly preferred diol is resorcinol.
  • Others which can be used include hydroquinone, bisphenol A, bisphenol S, and 4,4-diphenol.
  • This initial reaction step is preferably conducted at an elevated temperature of about 50°C to about 130°C using an effective amount (about 0.1% to about 0.5%, by weight of the dihalophosphate) of a Lewis acid catalyst, such as magnesium dichloride.
  • the resulting halo-terminated product from this reaction is an aromatic oligomeric phosphate of the following formula:
  • This second reaction step is also preferably conducted at an elevated temperature of about 110°C to about 180°C.
  • the resulting product can be used as a reactive flame retardant in forming polycarbonate resin compositions. It can also be used as an additive flame retardant in polycarbonate resin compositions such as described and claimed in copending U.S. Serial No. 350,601, filed on even date herewith.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention is a process for forming hydroxy-terminated aromatic oligomeric phosphates by the initial reaction of a monoaryl dihalophosphate, such as monophenyl dichlorophosphate, with an aromatic diol, such as resorcinol, to form a halo-terminated aromatic oligomeric phosphate and the subsequent reaction of that halo-terminated phosphate with aromatic diol to form the hydroxy-terminated aromatic oligomeric phosphate. The initial and subsequent reactions preferably employ a Lewis acid catalyst, such as magnesium dichloride.

Description

PROCESS FOR MAKING HYDROXY-TERMINATED AROMATIC OLIGOMERIC PHOSPHATES
Background of the Invention
Aromatic oligomeric phosphate compositions which are not hydroxy-terminated are known to persons of ordinary skill in the art with representative examples being described in European Patent Publication Nos. 509,506 and 521,628 and Japanese Patent Publication No. 227,632/1988.
A hydroxy-terminated aromatic oligomeric phosphate is depicted as one of the products formed by the processes described in Japanese Patent Publication No. 223,158/1989. The product that is desired is a mixture of 22%-65%, by weight, of a reactive, hydroxy- terminated monophosphate ester, 15%-30% of a non-reactive, non- hydroxy-terminated phosphate ester, and 5%-63% of the hydroxy- terminated oligomeric phosphate ester. The process used to synthesize the product desired by the patentees of Japanese Patent Publication No. 223,158/1989 relies, for example, upon the reaction of a mixture of phenol and aromatic diol (e.g., resorcinol) with phosphorus oxychloride in the presence of a catalyst (e.g., aluminum chloride) .
Summary of the Invention
The present invention is a process for forming hydroxy- terminated aromatic oligomeric phosphates by the initial reaction of a monoaryl dihalophosphate, such as monophenyl dichlorophosphate, with an aromatic diol, such as resorcinol, to form a halo-terminated aromatic oligomeric phosphate and the subsequent reaction of that halo-terminated phosphate with aromatic diol to form the hydroxy-terminated aromatic oligomeric phosphate. The initial and subsequent reactions preferably employ a Lewis acid catalyst, such as magnesium dichloride.
Df-scriPt-inn of Preferred Embodimen R
The initial process step in the instant process for forming hydroxy-terminated aromatic oligomeric phosphates is the initial reaction of a monophenyl dihalophosphate with an aromatic diol to form a halo-terminated aromatic oligomeric phosphate. The monophenyl dihalophosphate is of the formula ArOP(0)X2, where Ar stands for substituted or unsubstituted phenyl and X stands for halo, such as chloro or bromo. A preferred reagent to use is monophenyl dichlorophosphate. The aromatic diol is of the formula HOROH, with R being a hydrocarbyl group such as phenyl, diphenyl, 4,4' -isopropylidenediphenyl, and the like. A particularly preferred diol is resorcinol. Others which can be used include hydroquinone, bisphenol A, bisphenol S, and 4,4-diphenol. This initial reaction step is preferably conducted at an elevated temperature of about 50°C to about 130°C using an effective amount (about 0.1% to about 0.5%, by weight of the dihalophosphate) of a Lewis acid catalyst, such as magnesium dichloride. The resulting halo-terminated product from this reaction is an aromatic oligomeric phosphate of the following formula:
0 0
X- (P-0-R-0-)„-P-X
OAr OAr
with Ar and X being defined as earlier described and n ranging from 1 to about 10. Mixtures where n is a decimal number are also contemplated. This halo-terminated reaction product is then reacted with additional diol in a subsequent reaction step to substitute the halo-termination with the HO-R-O- group from the diol to yield the desired hydroxy-terminated aromatic oligomeric phosphate product:
Figure imgf000005_0001
HO-R-0- ( P-0-R-0- ) n-P-0-R-OH
I I
OAr OAr
This second reaction step is also preferably conducted at an elevated temperature of about 110°C to about 180°C.
The resulting product can be used as a reactive flame retardant in forming polycarbonate resin compositions. It can also be used as an additive flame retardant in polycarbonate resin compositions such as described and claimed in copending U.S. Serial No. 350,601, filed on even date herewith.
The present invention is further illustrated by the Examples which follow.
EXAMPLE 1
To 1403 g (6.65 moles) of monophenyl dichlorophosphate was added 3.5 g of magnesium chloride and 366 g of resorcinol. The reaction mixture was heated with stirring to 110°C over thirty minutes and kept at this temperature for an additional two hours. At the end of this time all the hydroxy groups were reacted. The reaction mixture was cooled to 50°C and an additional 750 g (6.82 moles) of resorcinol was added to the reaction mixture. The temperature was increased to 110°C, and the mixture became dark purple. The temperature was gradually increased to 150°C over six hours and was kept there for an additional two hours. At the end, the reaction mixture was orange. It was cooled to 70°C and was washed twice with a 5% sodium carbonate solution and three times with water.
After removal of traces of water at 80°C under vacuum, there was left 1380.5 g of an extremely viscous orange oil that did not flow at room temperature. The percent yield was 82%. The material had the following composition:
Figure imgf000006_0001
P.- (0H)2 22%
P2- (OH)2 29%
Pα- <OH)2 14%
P4- (0H)2 9%
P5-(OH)2 5%
P6-(OH)2 to P10(OH)2

Claims

Wf, Claim :
1. A process for forming hydroxy-terminated aromatic oligomeric phosphates which comprises the initial reaction of a monoaryl dihalophosphate with an aromatic diol to form a halo-terminated aromatic oligomeric phosphate and the subsequent reaction of that halo-terminated phosphate with aromatic diol to form the hydroxy-terminated aromatic oligomeric phosphate.
2. A process as claimed in Claim 1 wherein the monoaryl dihalophosphate is monophenyl dichlorophosphate.
3. The process as claimed in Claim 1 wherein the aromatic diol is resorcinol.
4. The process as claimed in Claim l wherein the monoaryl dihalophosphate is monophenyl dichlorophosphate and the aromatic diol is resorcinol.
5. The process as claimed in Claim 1 wherein the initial and subsequent reactions employ a Lewis acid catalyst.
6. A process as claimed in Claim 5 wherein the catalyst is magnesium dichloride.
7. The process as claimed in Claim 5 wherein the monoaryl dihalophosphate is monophenyl dichlorophosphate and the aromatic diol is resorcinol.
8. A process as claimed in Claim 5 wherein the catalyst is magnesium dichloride, the monoaryl dihalophosphate is monophenyl dichlorophosphate, and the aromatic diol is resorcinol.
PCT/US1995/015868 1994-12-07 1995-12-05 Process for making hydroxy-terminated aromatic oligomeric phosphates Ceased WO1996017854A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP51774996A JP3819425B2 (en) 1994-12-07 1995-12-05 Method for producing aromatic oligomeric phosphate having hydroxyl terminal
EP95941523A EP0796265B1 (en) 1994-12-07 1995-12-05 Process for making hydroxy-terminated aromatic oligomeric phosphates
DE69530317T DE69530317T2 (en) 1994-12-07 1995-12-05 METHOD FOR PRODUCING AROMATIC OLIGOMER PHOSPHATES WITH FINAL HYDROXY GROUPS

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/350,911 1994-12-07
US08/350,911 US5508462A (en) 1994-12-07 1994-12-07 Process for making hydroxy-terminated aromatic oligomeric phosphates

Publications (1)

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WO1996017854A1 true WO1996017854A1 (en) 1996-06-13

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US (1) US5508462A (en)
EP (1) EP0796265B1 (en)
JP (1) JP3819425B2 (en)
CA (1) CA2206130A1 (en)
DE (1) DE69530317T2 (en)
ES (1) ES2199258T3 (en)
WO (1) WO1996017854A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5728859A (en) * 1996-10-31 1998-03-17 Akzo Nobel N.V. Process for making monohydroxy-terminated phosphate compositions
US5833886A (en) * 1997-09-17 1998-11-10 Akzo Nobel Nv Thermostability enhancement of polyphosphate flame retardants
CN100432081C (en) * 2001-02-15 2008-11-12 帕布服务公司 Novel hydroxyaryl phosphine oxides,diglycidyl ethers and epoxy compositions, composites and laminates derived therefrom
US6887950B2 (en) * 2001-02-15 2005-05-03 Pabu Services, Inc. Phosphine oxide hydroxyaryl mixtures with novolac resins for co-curing epoxy resins

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2682521A (en) * 1952-09-10 1954-06-29 Eastman Kodak Co Resinous, linear polymeric amidophosphonates
US2952666A (en) * 1957-09-11 1960-09-13 Eastman Kodak Co Phosphoro-polyesters and polyesterurethanes derived from phosphorodichloridates and aliphatic glycols
US5393621A (en) * 1993-10-20 1995-02-28 Valence Technology, Inc. Fire-resistant solid polymer electrolytes

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2520090A (en) * 1947-12-30 1950-08-22 Monsanto Chemicals Polyphosphates of divalent aryl hydrocarbons
US3965220A (en) * 1971-06-24 1976-06-22 Monsanto Company Preparation of esters of phosphorus acids
DE3377138D1 (en) * 1982-09-10 1988-07-28 Bayer Ag Flame-retardant polymer mixtures
US4510101A (en) * 1983-03-18 1985-04-09 The Dow Chemical Company Halogenated phosphorus hydroxy-alkyl and t-alkoxyalkyl esters
JPS63227632A (en) * 1987-03-17 1988-09-21 Daihachi Kagaku Kogyosho:Kk Production of flame retardant
JP2661109B2 (en) * 1988-03-02 1997-10-08 味の素株式会社 Flame retardant phenolic resin composition
JP2552780B2 (en) * 1991-04-16 1996-11-13 大八化学工業株式会社 Method and application for producing aromatic diphosphate
AU655284B2 (en) * 1991-06-14 1994-12-15 Ethyl Corporation Organic phosphates and their preparation
US5457221A (en) * 1993-03-03 1995-10-10 Akzo Nobel N.V. Process for the manufacture of poly (hydrocarbylene aryl phosphate) compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2682521A (en) * 1952-09-10 1954-06-29 Eastman Kodak Co Resinous, linear polymeric amidophosphonates
US2952666A (en) * 1957-09-11 1960-09-13 Eastman Kodak Co Phosphoro-polyesters and polyesterurethanes derived from phosphorodichloridates and aliphatic glycols
US5393621A (en) * 1993-10-20 1995-02-28 Valence Technology, Inc. Fire-resistant solid polymer electrolytes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Volume 92, Abstract No. 24140, issued 1980, PETREUS et al., "Nonflammable Polyesters"; & RO,A,64 218. *
See also references of EP0796265A4 *

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Publication number Publication date
EP0796265A4 (en) 1998-05-06
ES2199258T3 (en) 2004-02-16
US5508462A (en) 1996-04-16
EP0796265A1 (en) 1997-09-24
DE69530317D1 (en) 2003-05-15
EP0796265B1 (en) 2003-04-09
JPH10510269A (en) 1998-10-06
DE69530317T2 (en) 2004-02-19
JP3819425B2 (en) 2006-09-06
CA2206130A1 (en) 1996-06-13

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