WO1996013508A1 - Process for the formation of hydrocarbyl bis(hydrocarbyl phosphate) - Google Patents

Process for the formation of hydrocarbyl bis(hydrocarbyl phosphate) Download PDF

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Publication number
WO1996013508A1
WO1996013508A1 PCT/US1995/013408 US9513408W WO9613508A1 WO 1996013508 A1 WO1996013508 A1 WO 1996013508A1 US 9513408 W US9513408 W US 9513408W WO 9613508 A1 WO9613508 A1 WO 9613508A1
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hydrocarbyl
diol
phosphate
bis
dihydrocarbyl
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French (fr)
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Danielle A. Bright
Ronald L. Pirrelli
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Akzo Nobel NV
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Akzo Nobel NV
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Priority to EP95937516A priority Critical patent/EP0789703B1/en
Priority to DE69530503T priority patent/DE69530503T2/en
Priority to JP8514639A priority patent/JPH10508021A/en
Publication of WO1996013508A1 publication Critical patent/WO1996013508A1/en
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    • 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
    • C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
    • 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

  • the reaction mixture comprising the desired diphosphate compound will generally contain undesired cyclic by-product(s) , such as of the formula
  • the impurity will, for example, be isopropyl phenyl diphenyl phosphate.
  • the unstable nature of such diols in regard to the aforementioned formation of by-product(s) , is due to either intramolecular reaction and rearrangement, such as in the case of the branched neopentyl glycol reagent and/or actual splitting apart of the diol molecule as in the case of bisphenol A which comprises two phenyl groups linked together with an alkylene moiety, namely -C(CH 3 ) 2 -.
  • the terminology "unstable hydrocarbyl-containing" will be used to characterize either type of such diols.
  • the present invention is a process for the synthesis of a hydrocarbyl bis(dihydrocarbyl phosphate), such as a hydrocarbyl bis(diary1 phosphate), which comprises the reaction of an unstable hydrocarbyl-containing diol, such as an alkylene- or alkylene bridged aromatic group-containing diol, with a dihydrocarbyl halophosphate, such as diphenyl chlorophosphate, in the presence of a Lewis acid catalyst, such as magnesium dichloride, in the additional presence of an effective amount (e.g., up to about 100% by weight of diol and halophosphate) of a liquid hydrocarbon, such as an aliphatic hydrocarbon, like heptane, to enhance the removal of hydrogen halide by-product and thereby increase the yield of hydrocarbyl bis(dihydrocarbyl phosphate) while reducing the formation of undesired cyclic by ⁇ products.
  • the present process is one which is intended to synthesize a hydrocarbyl bisphosphate of the formula
  • R can be hydrocarbyl (such as, substituted or unsubstituted aryl) and R' can be either alkylene, such as derived from neopentyl glycol, or alkylene bridged arylene-containing, such as derived from bisphenol A.
  • the dihydrocarbyl halophosphate reactant used in the instant process has the formula
  • R is hydrocarbyl (e.g., substituted or unsubstituted aryl) and X is halogen.
  • Preferred compounds are the diarylchlorophosphates (e.g. , diphenylchlorophosphate) . This reactant is preferably present at about 2:1 (on a molar basis) to the following dihydroxy reaction.
  • the dihydroxy reactant (HOR'OH) is used to form the bridging group R' in the final compounds.
  • the reaction is run at elevated temperature (above about 20°C) but not at temperatures high enough to induce the formation of cyclic by-products and/or trihydrocarbyl phosphate using an effective amount (e.g., about
  • Such catalysts include such transition metal halides as magnesium chloride, aluminum chloride, zinc chloride, titanium tetrachloride and the like.
  • the present invention relies upon the presence of an additional amount of a liquid hydrocarbon, for example, an aliphatic hydrocarbon, such as heptane, or an aromatic solvent, such as toluene, to assist, as a "chaser", in driving off the hydrogen halide by-product.
  • a liquid hydrocarbon for example, an aliphatic hydrocarbon, such as heptane, or an aromatic solvent, such as toluene
  • the amount of solvent that is used will be up to about 100 % by weight of the weight of diol and halophosphate, preferably up to about 50 %, more preferably up to about 20 %.
  • this liquid hydrocarbon allows for a high purity product to be formed at lower temperatures than possible if the liquid hydrocarbon were absent.
  • Diphenyl chlorophosphate (0.5 mole), bisphenol A (0.25 mole), magnesium chloride (2.63 x 10 * mole) and heptane (20 wt%) were heated to reflux (about 99°C) for six hours. The disappearance of the hydroxy functionality was monitored by infrared analysis.
  • Liquid chro atographic analysis (area %) of the reaction mixture showed the following composition: 1.5% triphenyl phosphate; 0.49% isopropenylphenyl diphenylphosphate; 1.7% bisphenol A diphenyl phosphate; 92.3% bisphenol A bis(diphenyl phosphate) , which is referred to as "P 2 " in the Table in Examples 2-5, below, and 2.4% of oligomeric bisphenol A bis(diphenyl phosphate) containing three phosphorus atoms.
  • Neopentyl glycol bis(diphenylphosphate) was made by heating to reflux 1.1 moles (295.5 grams) of diphenylchlorophosphate, 0.5 mole (52.0 grams) of neopentyl glycol, 0.2 gram of magnesium chloride, and 100 ml of a non-polar solvent. Upon reaction completion, the solvent was recovered by vacuum stripping, and the reaction mixture was washed with 2% sulfuric acid aqueous solution, 2% sodium hydroxide aqueous solution, and water. After removal of traces of water the following results were obtained:
  • Dibromoneopentyl glycol bis(diphenylphosphate) was made by heating to reflux (117°C) about 1.1 moles (295.5 grams) of diphenylchlorophosphate, about 0.5 mole (131.0 grams) of dibromoneopentyl glycol, 0.2 grams of magnesium chloride, and 100 ml of ISOPAR E isoparaffin solvent. After fifteen hours at this temperature, the solvent was removed by layer separation. The reaction mixture was washed as described in Examples 6-10. There was left 348 grams of an oil (96% yield) that assayed at 81.5 area % of the desired product by high pressure liquid chromatography. The by-products were triphenylphosphate (8.2% by weight) and cyclic phosphorinane (2.6 area %)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for the synthesis of a hydrocarbyl bis(dihydrocarbyl phosphate), such as a hydrocarbyl bis(diaryl phosphate), comprises the reaction of an unstable hydrocarbyl-containing diol, such as an aromatic group-containing diol, with a dihydrocarbyl halophosphate, such as diphenyl chlorophosphate, in the presence of a Lewis acid catalyst, such as magnesium dichloride, in the additional presence of an effective amount (e.g., up to about 100 % by weight of diol and halophosphate) of a liquid hydrocarbon, such as an aliphatic hydrocarbon, like heptane, or an aromatic hydrocarbon, such as toluene, to enhance the removal of hydrogen halide by-product and thereby increase the yield of hydrocarbyl bis(dihydrocarbyl phosphate).

Description

PROCESS FOR THE FORMATION OF HYDROCARBYL BIS (HYDROCARBYL PHOSPHATES
Background of the Invention
Processes for the synthesis of a hydrocarbyl bis(dihydrocarbyl phosphate) by the reaction of a hydrocarbyl diol with a dihydrocarbyl halophosphate in the presence of a Lewis acid catalyst are known to the prior art. For example, U.S. Patent No. 3,254,973 to J.J. Giammaria et al. illustrates such a general reaction and employs nitrogen gas to sparge the reaction medium and remove hydrogen chloride as by-product. U.S. Patent No. 4,133,846 to J.A. Albright illustrates an analogous reaction but does not show the nitrogen sparge aspect. More recent U.S. Patent No. 4,343,732 to T. Zama et al. shows the reaction of certain diols, phosphorus oxychloride, and certain alcohols and phenols, in the presence of aluminum chloride as a catalyst, indicates (at Col. 4, lines 21-22) that inert solvents, such as toluene and xylene, may be used, but demonstrates no advantage for the use of a solvent.
When the diol used in the aforementioned reaction is alkylene in character, such as neopentylglycol, the reaction mixture comprising the desired diphosphate compound will generally contain undesired cyclic by-product(s) , such as of the formula
/ θ-CH2, C6HsP(0)\ / C< 0-CH2
, along with triphenyl phosphate,which lower the thermal stability of the diphosphate-containing compositions. If the diol which is used contains an alkylene group in association with phenyl moieties, such as in bisphenol A, the impurity will, for example, be isopropyl phenyl diphenyl phosphate. The unstable nature of such diols, in regard to the aforementioned formation of by-product(s) , is due to either intramolecular reaction and rearrangement, such as in the case of the branched neopentyl glycol reagent and/or actual splitting apart of the diol molecule as in the case of bisphenol A which comprises two phenyl groups linked together with an alkylene moiety, namely -C(CH3)2-. The terminology "unstable hydrocarbyl-containing" will be used to characterize either type of such diols.
Summary of the Invention
The present invention is a process for the synthesis of a hydrocarbyl bis(dihydrocarbyl phosphate), such as a hydrocarbyl bis(diary1 phosphate), which comprises the reaction of an unstable hydrocarbyl-containing diol, such as an alkylene- or alkylene bridged aromatic group-containing diol, with a dihydrocarbyl halophosphate, such as diphenyl chlorophosphate, in the presence of a Lewis acid catalyst, such as magnesium dichloride, in the additional presence of an effective amount (e.g., up to about 100% by weight of diol and halophosphate) of a liquid hydrocarbon, such as an aliphatic hydrocarbon, like heptane, to enhance the removal of hydrogen halide by-product and thereby increase the yield of hydrocarbyl bis(dihydrocarbyl phosphate) while reducing the formation of undesired cyclic by¬ products. Detailed Description of the Invention
The present process is one which is intended to synthesize a hydrocarbyl bisphosphate of the formula
RO O O OR
\" "/
POR'OP
/ \ RO OR
where R can be hydrocarbyl (such as, substituted or unsubstituted aryl) and R' can be either alkylene, such as derived from neopentyl glycol, or alkylene bridged arylene-containing, such as derived from bisphenol A.
The dihydrocarbyl halophosphate reactant used in the instant process has the formula
RO O
\" P-X
/ RO
where R is hydrocarbyl (e.g., substituted or unsubstituted aryl) and X is halogen. Preferred compounds are the diarylchlorophosphates (e.g. , diphenylchlorophosphate) . This reactant is preferably present at about 2:1 (on a molar basis) to the following dihydroxy reaction.
The dihydroxy reactant (HOR'OH) is used to form the bridging group R' in the final compounds. The reaction is run at elevated temperature (above about 20°C) but not at temperatures high enough to induce the formation of cyclic by-products and/or trihydrocarbyl phosphate using an effective amount (e.g., about
0.01% to about 1% by weight of the dihydrocarbylhalophosphate) of a Lewis acid catalyst. Such catalysts include such transition metal halides as magnesium chloride, aluminum chloride, zinc chloride, titanium tetrachloride and the like.
The present invention relies upon the presence of an additional amount of a liquid hydrocarbon, for example, an aliphatic hydrocarbon, such as heptane, or an aromatic solvent, such as toluene, to assist, as a "chaser", in driving off the hydrogen halide by-product. Generally speaking, the amount of solvent that is used will be up to about 100 % by weight of the weight of diol and halophosphate, preferably up to about 50 %, more preferably up to about 20 %. The use of this liquid hydrocarbon allows for a high purity product to be formed at lower temperatures than possible if the liquid hydrocarbon were absent. The use of such lower temperature results in a lessened propensity for the formation of undesired by-products such as triphenyl phosphate and isopropenyl diphenyl phosphate in the case of bisphenol A and cyclic phosphates in the case of neopentyl glycol.
The present invention is illustrated by the Examples which follow.
Diphenyl chlorophosphate (0.5 mole), bisphenol A (0.25 mole), magnesium chloride (2.63 x 10* mole) and heptane (20 wt%) were heated to reflux (about 99°C) for six hours. The disappearance of the hydroxy functionality was monitored by infrared analysis. Liquid chro atographic analysis (area %) of the reaction mixture showed the following composition: 1.5% triphenyl phosphate; 0.49% isopropenylphenyl diphenylphosphate; 1.7% bisphenol A diphenyl phosphate; 92.3% bisphenol A bis(diphenyl phosphate) , which is referred to as "P2" in the Table in Examples 2-5, below, and 2.4% of oligomeric bisphenol A bis(diphenyl phosphate) containing three phosphorus atoms.
EXAMPLES 2-5
In these Examples the effects of temperature, nitrogen sparge, and heptane concentration on the purity of the product described in Example 1 was determined (all amounts of product given in the following Table being on the basis of area percent, except for triphenyl phosphate, "TPP", which is based on weight percent) :
Figure imgf000009_0001
10
15
Figure imgf000009_0003
Figure imgf000009_0004
Figure imgf000009_0005
* = "A" is used to identify the isopropenylphenyl diphenylphosphate component.
20
Figure imgf000009_0002
EXAMPLES 6-10
Neopentyl glycol bis(diphenylphosphate) was made by heating to reflux 1.1 moles (295.5 grams) of diphenylchlorophosphate, 0.5 mole (52.0 grams) of neopentyl glycol, 0.2 gram of magnesium chloride, and 100 ml of a non-polar solvent. Upon reaction completion, the solvent was recovered by vacuum stripping, and the reaction mixture was washed with 2% sulfuric acid aqueous solution, 2% sodium hydroxide aqueous solution, and water. After removal of traces of water the following results were obtained:
Figure imgf000010_0001
* ISOPAR E brand from Exxon Company.
In Run No. 9, 50 ml of this solvent was used rather than 100 ml as in Run No. 10.
—High Pressure Liquid Chromatography Analysis—
Triphenyl Cyclic
Bisphosphate Phosphate By-product Run No. (Area %ϊ fWt ■%) (Area %)
6 96.3 1.1
7 93.1 2.5
8 96.7 1.4
9 76.3 3.0
10 62.5 7.4
11 88.6
Figure imgf000010_0002
2.2 EXAMPLE 12
Dibromoneopentyl glycol bis(diphenylphosphate) was made by heating to reflux (117°C) about 1.1 moles (295.5 grams) of diphenylchlorophosphate, about 0.5 mole (131.0 grams) of dibromoneopentyl glycol, 0.2 grams of magnesium chloride, and 100 ml of ISOPAR E isoparaffin solvent. After fifteen hours at this temperature, the solvent was removed by layer separation. The reaction mixture was washed as described in Examples 6-10. There was left 348 grams of an oil (96% yield) that assayed at 81.5 area % of the desired product by high pressure liquid chromatography. The by-products were triphenylphosphate (8.2% by weight) and cyclic phosphorinane (2.6 area %)
The foregoing Examples have been presented to illustrate certain preferred embodiments of the present invention and, for that reason, should not be construed in a limiting sense. The scope of protection sought is set forth in the Claims which follow.

Claims

We Claim:
1. In a process for the synthesis of a hydrocarbyl bis(dihydrocarbyl phosphate) which comprises the reaction of an unstable hydrocarbyl-containing diol with a dihydrocarbyl halophosphate in the presence of a Lewis acid catalyst, wherein the improvement comprises the additional presence of an effective amount of a liquid hydrocarbon to enhance the removal of hydrogen halide by-product and decrease the reaction temperature while increasing the yield and purity of hydrocarbyl bis(dihydrocarbyl phosphate) .
2. A process as claimed in Claim 1 wherein the hydrocarbyl bis(dihydrocarbyl phosphate) is a hydrocarbyl bis(diaryl phosphate) .
3. A process as claimed in Claim 1 wherein the hydrocarbyl diol is selected from the group consisting of an alkylene group- containing diol and an alkylene bridged aromatic group-containing diol.
4. A process as claimed in Claim 1 wherein the hydrocarbyl bis(dihydrocarbyl phosphate) is a hydrocarbyl bis(diaryl phosphate) and the hydrocarbyl diol is an alkylene group- containing diol.
5. A process as claimed in Claim 1 wherein the hydrocarbyl bis(dihydrocarbyl phosphate) is a hydrocarbyl bis(diaryl phosphate) and the hydrocarbyl diol is an alkylene bridged aromatic group-containing diol.
6. A process as claimed in Claim 1 wherein the Lewis acid catalyst is magnesium dichloride.
7. A process as claimed in Claim 1 wherein the hydrocarbyl bis(dihydrocarbyl phosphate) is a hydrocarbyl bis(diaryl phosphate) , the hydrocarbyl diol is selected from the group consisting of an alkylene group-containing diol and an alkylene bridged aromatic group-containing diol, and the Lewis acid catalyst is magnesium dichloride.
8. A process as claimed in Claim 1 wherein the liquid hydrocarbon is an aliphatic hydrocarbon.
9. A process as claimed in Claim 1 wherein the hydrocarbyl bis(dihydrocarbyl phosphate) is a hydrocarbyl bis(diaryl phosphate) , the hydrocarbyl diol is selected from the group consisting of an alkylene group-containing diol and an alkylene bridged aromatic group-containing diol, the Lewis acid catalyst is magnesium dichloride, and the liquid hydrocarbon is an aliphatic hydrocarbon.
10. A process as claimed in Claim 1 wherein the liquid hydrocarbon is present at up to about 50 % of the weight of diol and halophosphate.
11. A process as claimed in Claim 9 wherein the liquid hydrocarbon is present at up to about 50 % of the weight of diol and halophosphate.
12. A process as claimed in Claim 1 wherein the hydrocarbyl bis(dihydrocarbyl phosphate) is a hydrocarbyl bis(diaryl phosphate) , the hydrocarbyl diol is selected from the group consisting of an alkylene group-containing diol and an alkylene bridged aromatic group-containing diol, the Lewis acid catalyst is magnesium dichloride, the liquid hydrocarbon is an aliphatic hydrocarbon, and the process is performed at a temperature of above about 20°C.
PCT/US1995/013408 1994-11-01 1995-10-20 Process for the formation of hydrocarbyl bis(hydrocarbyl phosphate) Ceased WO1996013508A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP95937516A EP0789703B1 (en) 1994-11-01 1995-10-20 Process for the formation of hydrocarbyl bis(hydrocarbyl phosphate)
DE69530503T DE69530503T2 (en) 1994-11-01 1995-10-20 METHOD FOR PRESENTING HYDROCARBYL BIS (HYDROCARBYL PHOSPHATE)
JP8514639A JPH10508021A (en) 1994-11-01 1995-10-20 Method for producing hydrocarbyl bis (hydrocarbyl phosphate)

Applications Claiming Priority (2)

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US08/332,671 1994-11-01
US08/332,671 US6136997A (en) 1994-11-01 1994-11-01 Process for the formation of hydrocarbyl BIS(hydrocarbyl phosphate)

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WO (1) WO1996013508A1 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998004566A1 (en) * 1996-07-29 1998-02-05 Akzo Nobel N.V. Process for the formation of hydrocarbyl bis(dihydrocarbyl phosphate)
US5756798A (en) * 1996-06-13 1998-05-26 Great Lakes Chemical Corporation Process to prepare aryldiphosphoric esters
WO1999005200A1 (en) * 1997-07-25 1999-02-04 Nycomed Imaging As Process for the preparation of polyether phosphates
US6031035A (en) * 1998-02-13 2000-02-29 Great Lakes Chemical Corporation Process for making and using bisaryl diphosphates
WO2002008329A1 (en) * 2000-07-25 2002-01-31 Bayer Aktiengesellschaft Flame-resistant polycarbonate compositions
US6388120B1 (en) 1998-02-13 2002-05-14 Pabu Services, Inc. Continuous process for the manufacture of phosphoric acid esters
US6399685B1 (en) 2000-12-11 2002-06-04 Albemarle Corporation Purification of arylene polyphosphate esters
US6486241B2 (en) 1997-08-29 2002-11-26 General Electric Company Polycarbonate resin composition
US6613820B2 (en) 1997-08-29 2003-09-02 General Electric Company Polycarbonate resin composition
WO2013058690A1 (en) * 2011-10-21 2013-04-25 Perstorp Ab Novel tetraoxaspiro[5.5]undecane based phosphate compounds and their use as flame retardants

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003095463A1 (en) * 2002-05-07 2003-11-20 Akzo Nobel N.V. Neopentylglycol bis (diarylphosphate) esters
JP4011441B2 (en) * 2002-05-10 2007-11-21 ダイハツ工業株式会社 Instrument panel structure of vehicle
CN100362001C (en) * 2005-12-06 2008-01-16 河北工业大学 A kind of polycondensation type phosphoric acid ester and its preparation method and application
US20100137467A1 (en) * 2006-11-20 2010-06-03 Stowell Jeffrey K Polyurethane foam containing flame-retardant mixture
CN110143980A (en) * 2019-06-05 2019-08-20 南京恒桥化学技术材料有限公司 A kind of powder type bisphenol A bis(diphenyl phosphate) and preparation method thereof

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5756798A (en) * 1996-06-13 1998-05-26 Great Lakes Chemical Corporation Process to prepare aryldiphosphoric esters
WO1998004566A1 (en) * 1996-07-29 1998-02-05 Akzo Nobel N.V. Process for the formation of hydrocarbyl bis(dihydrocarbyl phosphate)
WO1999005200A1 (en) * 1997-07-25 1999-02-04 Nycomed Imaging As Process for the preparation of polyether phosphates
US6500917B1 (en) 1997-07-25 2002-12-31 Amersham Health As Process for the preparation of polyether phosphates
US6486241B2 (en) 1997-08-29 2002-11-26 General Electric Company Polycarbonate resin composition
US6613820B2 (en) 1997-08-29 2003-09-02 General Electric Company Polycarbonate resin composition
US6031035A (en) * 1998-02-13 2000-02-29 Great Lakes Chemical Corporation Process for making and using bisaryl diphosphates
US6388120B1 (en) 1998-02-13 2002-05-14 Pabu Services, Inc. Continuous process for the manufacture of phosphoric acid esters
WO2002008329A1 (en) * 2000-07-25 2002-01-31 Bayer Aktiengesellschaft Flame-resistant polycarbonate compositions
US6399685B1 (en) 2000-12-11 2002-06-04 Albemarle Corporation Purification of arylene polyphosphate esters
WO2002048158A1 (en) * 2000-12-11 2002-06-20 Albemarle Corporation Purification of arylene polyphosphate esters
WO2013058690A1 (en) * 2011-10-21 2013-04-25 Perstorp Ab Novel tetraoxaspiro[5.5]undecane based phosphate compounds and their use as flame retardants

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EP0789703A1 (en) 1997-08-20
DE69530503T2 (en) 2004-01-29
DE69530503D1 (en) 2003-05-28
US6136997A (en) 2000-10-24
CN1167488A (en) 1997-12-10
EP0789703A4 (en) 1998-02-25
JPH10508021A (en) 1998-08-04
CN1076354C (en) 2001-12-19
EP0789703B1 (en) 2003-04-23

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