US20010025116A1 - Aluminum salts of phosphinic acids - Google Patents
Aluminum salts of phosphinic acids Download PDFInfo
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- US20010025116A1 US20010025116A1 US09/824,478 US82447801A US2001025116A1 US 20010025116 A1 US20010025116 A1 US 20010025116A1 US 82447801 A US82447801 A US 82447801A US 2001025116 A1 US2001025116 A1 US 2001025116A1
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- aluminum
- acids
- diphosphinic
- phosphinic acids
- aluminum salts
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- UJBMDYCJVYVFMH-UHFFFAOYSA-M COP(C)(=O)CP(C)(=O)OC.COP(C)(C)=O.[V]I Chemical compound COP(C)(=O)CP(C)(=O)OC.COP(C)(C)=O.[V]I UJBMDYCJVYVFMH-UHFFFAOYSA-M 0.000 description 1
- ZUTQXBWIQUUXCW-UHFFFAOYSA-N CP(=O)(O)CP(C)(=O)O.CP(C)(=O)O.II Chemical compound CP(=O)(O)CP(C)(=O)O.CP(C)(=O)O.II ZUTQXBWIQUUXCW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
Definitions
- the invention relates to aluminum salts of phosphinic acids, processes for their preparation and to their use as flameproofing agents.
- Aluminum salts of phosphinic acids are valuable flameproofing agents for polyester and polyamide molding materials. They are prepared from the phosphinic acids in aqueous solution with metal carbonates, metal hydroxides or metal oxides (EP-A2-0699708).
- the aluminum salts of phosphinic acids can be prepared in good yields under pressure from the corresponding esters with water and aluminum hydroxide. Furthermore, it was found that the aluminum salts of phosphinic acids or diphosphinic acids having alkyl and/or aryl substitutes are formed in a novel crystal form at a temperature above 150° C. under pressure. These aluminum salts are defined as a high-temperature modification. The aluminum salts known to date and prepared at temperatures of 80 to 100° C. are defined as a low-temperature modification.
- the invention thus relates to aluminum salts of phosphinic acids or diphosphinic acids having alkyl and/or aryl substituents, obtainable by heating an ester of the corresponding phosphinic acids or diphosphinic acids with aluminum hydroxide at a temperature of more 150° C. under pressure in the presence of water.
- the invention also relates to aluminum salts of phosphinic acids or diphosphinic acids having alkyl and/or aryl substituents, obtainable by heating the corresponding aluminum salts in the low-temperature modification at a temperature of more than 150° C. under pressure in the presence of water.
- Alkyl substituents are preferably C 1 -C 8 -alkyl, in particular C 1 -C 4 -alkyl, linear or branched, for example methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, n-hexyl or n-octyl.
- a preferred aryl substituent is the phenyl group.
- the aluminum salts of the high-temperature modification may also be polymers of the phosphinic acid or disphosphinic acids.
- phosphinic acid and “diphosphinic acid”, accordingly, include monomers, oligomers and polymers.
- the invention furthermore relates to a process for the preparation of aluminum salts of phosphinic acids or diphosphinic acids, esters of the corresponding phosphinic acids or diphosphinic acids being reacted with aluminum hydroxide under pressure at 150 to 350° C. in the presence of water.
- the invention furthermore relates to a process for the preparation of aluminum salts of phosphinic acids or diphosphinic acids of the high-temperature modification, the corresponding aluminum salts in the low-temperature modification being exposed to a temperature in the range of 150 to 350° C. in the presence of water.
- Suitable aluminum salts of phosphinic acids or diphosphinic acids are, for example, compounds according to the formula I or II
- R 1 , R 2 are C 1 -C 8 -alkyl, preferably C 1 -C 4 -alkyl, linear or branched, e.g. methyl, ethyl, n-propyl, isobutyl, n-butyl, n-hexyl, phenyl
- R 3 is C 1 -C 10 -alkylene, linear or branched, e.g. methylene, ethylene, n-propylene, isopropylene, n-butylene, n-decylene,
- an arylene e.g. phenylene, napthylene
- alkylarylene e.g. methylphenylene, ethylphenylene, methylphenylenemethyl
- arylalkylene e.g. phenylmethylene, phenylethylene.
- the aluminum salts according to the formula I or II can be prepared, for example, from phosphinic esters or diphosphinic esters of the formula III or IV
- R 1 , R 2 and R 3 have the abovementioned meaning and R 4 is C 1 -C 8 -alkyl, preferably C 4 -C 6 -alkyl.
- R 4 is C 1 -C 8 -alkyl, preferably C 4 -C 6 -alkyl.
- the compounds according to the formula III or IV are reacted with water and aluminum hydroxide under pressure at 150 to 350° C. and heated for several hours in this temperature range, the corresponding aluminum salts being obtained as the high-temperature modification.
- Particularly suitable starting materials for the preparation of the aluminum salts are: methyl dimethylphosphonate, ethyl ethylmethylphosphonate, isobutyl ethymethyiphosphonate, n-butyl methylpropylphosphonate, amyl isobutylmethylphosphonate, isopropyl hexylmethylphosphonate, n-butyl methyloctylphosphonate, n-butyl methylphenylphosphonate, n-pentyl diphenylphosphonate, di-n-butyl hexane-1,6-di(methylphosphonate) and diisobutyl benzene-1,4-di(methylphosphonate).
- the process for the preparation of the high-temperature modification is carried out in a variant in such a way that phosphinic esters are heated with excess water and stoichiometric amounts of aluminum hydroxide under pressure to 150 to 350° C., preferably 180 to 250° C., expediently with continuous stirring.
- the required reaction times are in general at least 4 and preferably at least 40 hours, in particular 50 to 70 hours.
- the reaction times are dependent on the chain length of the ester group (for example, R 4 in the formulae III and IV).
- Methyl esters hydrolyze, for example, more rapidly than the butyl esters.
- the resulting crystals are isolated and dried.
- the reaction conditions, such as temperature and reaction time can also be varied so that mixtures of low-temperature modification and high-temperature modification are obtained.
- Aluminum salts of the high-temperature modification are gradually transformed at room temperature into the low-temperature modification, but the crystal habit of the high-temperature modification is retained.
- the high-temperature modification consists of acicular crystals which have a fibrous appearance.
- the crystals generally have a width in the range from about 0.2 to 1.5 ⁇ m, in particular 0.2 to 1 ⁇ m.
- the ratio of width to length of the crystal has, as a rule, a value of less than 0.2.
- the ratio of width to length of the crystal is usually about 0.1 or less.
- the crystals usually form agglomerates which have the appearance of felt-like bales.
- the agglomerates are obtained with a diameter in the size range from about 10 to 170 ⁇ m, the main proportion comprising agglomerates having a diameter of about 20 ⁇ m.
- the low-temperature modification consists of cylindrical crystals which as a rule have a width of more than 1.5 ⁇ m, typically 2 to 5 ⁇ m.
- the ratio of width to length of the crystals is usually in the range from 0.6 to 2, typically 2.
- the crystals also form agglomerates which for the most part have a diameter of about 20 ⁇ m.
- the high-temperature modification of the aluminum salts is particularly suitable as flameproofing agents or flame retardants for plastics, in particular for polyester or polyamide.
- the aluminum salts of the high-temperature modification have advantages for use as flameproofing agents for plastics. Investigations have shown that the flame-retardant effect of the salts of the phosphinic acids in the plastic depends on the particle size of the salt and that an optimum particle size results.
- the aluminum salts of the high-temperature modification form directly in the advantageous particle size. Milling of the aluminum salts is therefore not necessary for compounding, which means an economic advantage for the preparation of flameproofed plastics.
- the finer structure of the aluminum salt permits a more homogeneous distribution of the flameproofing agent in the plastic.
- the fibrous structure of the aluminum salt moreover leads to reinforcement of the plastic (fiber reinforcement). The finer structure leads to a larger surface area of the particle and, for example with the use of synergistic agents, such as nitrogen compounds, improves their flameproofing effect.
- 264 g (1.5 mol) of n-butyl ethylmethylphosphonate, 250 ml of water and 39 g (0.5 mol) of aluminum hydroxide are kept at 200° C. in a 1 l autoclave for 50 hours while stirring. Cooling and filtration with suction are then carried out, followed by drying at 100° C. in a vacuum drying oven.
- 157 g of aluminum salt of ethylmethylphosphinic acid having a residual water content of 58 ppm and a mean particle size of 20.03 ⁇ m, are obtained. This corresponds to a yield of 90% of theory.
- the product does not melt up to 360° C.
- the product retains the crystal habit of a high-temperature modification (pseudomorphism).
Abstract
Description
- The invention relates to aluminum salts of phosphinic acids, processes for their preparation and to their use as flameproofing agents.
- Aluminum salts of phosphinic acids are valuable flameproofing agents for polyester and polyamide molding materials. They are prepared from the phosphinic acids in aqueous solution with metal carbonates, metal hydroxides or metal oxides (EP-A2-0699708).
- To date, phosphinic esters have been converted into the corresponding phosphinic acids in good yields on hydrolysis at 180° C. under pressure with excess water only when the alcohol formed is removed as a mixture with water from the gas phase of the autoclave (Houben-Weyl, Methoden der organischen Chemie [Methods of organic chemistry] 1982, Volume E2, page 142; DE-A1-27 45 982).
- It was found that the aluminum salts of phosphinic acids can be prepared in good yields under pressure from the corresponding esters with water and aluminum hydroxide. Furthermore, it was found that the aluminum salts of phosphinic acids or diphosphinic acids having alkyl and/or aryl substitutes are formed in a novel crystal form at a temperature above 150° C. under pressure. These aluminum salts are defined as a high-temperature modification. The aluminum salts known to date and prepared at temperatures of 80 to 100° C. are defined as a low-temperature modification.
- The invention thus relates to aluminum salts of phosphinic acids or diphosphinic acids having alkyl and/or aryl substituents, obtainable by heating an ester of the corresponding phosphinic acids or diphosphinic acids with aluminum hydroxide at a temperature of more 150° C. under pressure in the presence of water.
- The invention also relates to aluminum salts of phosphinic acids or diphosphinic acids having alkyl and/or aryl substituents, obtainable by heating the corresponding aluminum salts in the low-temperature modification at a temperature of more than 150° C. under pressure in the presence of water.
- Alkyl substituents are preferably C1-C8-alkyl, in particular C1-C4-alkyl, linear or branched, for example methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, n-hexyl or n-octyl. A preferred aryl substituent is the phenyl group.
- The aluminum salts of the high-temperature modification may also be polymers of the phosphinic acid or disphosphinic acids. The terms “phosphinic acid” and “diphosphinic acid”, accordingly, include monomers, oligomers and polymers.
- The invention furthermore relates to a process for the preparation of aluminum salts of phosphinic acids or diphosphinic acids, esters of the corresponding phosphinic acids or diphosphinic acids being reacted with aluminum hydroxide under pressure at 150 to 350° C. in the presence of water.
- The invention furthermore relates to a process for the preparation of aluminum salts of phosphinic acids or diphosphinic acids of the high-temperature modification, the corresponding aluminum salts in the low-temperature modification being exposed to a temperature in the range of 150 to 350° C. in the presence of water.
-
- in which
- R1, R2 are C1-C8-alkyl, preferably C1-C4-alkyl, linear or branched, e.g. methyl, ethyl, n-propyl, isobutyl, n-butyl, n-hexyl, phenyl
- R3 is C1-C10-alkylene, linear or branched, e.g. methylene, ethylene, n-propylene, isopropylene, n-butylene, n-decylene,
- an arylene, e.g. phenylene, napthylene;
- alkylarylene, e.g. methylphenylene, ethylphenylene, methylphenylenemethyl;
- arylalkylene, e.g. phenylmethylene, phenylethylene.
-
- in which R1, R2 and R3 have the abovementioned meaning and R4 is C1-C8-alkyl, preferably C4-C6-alkyl. Advantageously, the compounds according to the formula III or IV are reacted with water and aluminum hydroxide under pressure at 150 to 350° C. and heated for several hours in this temperature range, the corresponding aluminum salts being obtained as the high-temperature modification.
- Particularly suitable starting materials for the preparation of the aluminum salts are: methyl dimethylphosphonate, ethyl ethylmethylphosphonate, isobutyl ethymethyiphosphonate, n-butyl methylpropylphosphonate, amyl isobutylmethylphosphonate, isopropyl hexylmethylphosphonate, n-butyl methyloctylphosphonate, n-butyl methylphenylphosphonate, n-pentyl diphenylphosphonate, di-n-butyl hexane-1,6-di(methylphosphonate) and diisobutyl benzene-1,4-di(methylphosphonate).
- The process for the preparation of the high-temperature modification is carried out in a variant in such a way that phosphinic esters are heated with excess water and stoichiometric amounts of aluminum hydroxide under pressure to 150 to 350° C., preferably 180 to 250° C., expediently with continuous stirring. The required reaction times are in general at least 4 and preferably at least 40 hours, in particular 50 to 70 hours. The reaction times are dependent on the chain length of the ester group (for example, R4 in the formulae III and IV). Methyl esters hydrolyze, for example, more rapidly than the butyl esters. After the end of the reaction, the resulting crystals are isolated and dried. The reaction conditions, such as temperature and reaction time, can also be varied so that mixtures of low-temperature modification and high-temperature modification are obtained.
- Aluminum salts of the high-temperature modification are gradually transformed at room temperature into the low-temperature modification, but the crystal habit of the high-temperature modification is retained.
- The high-temperature modification consists of acicular crystals which have a fibrous appearance. The crystals generally have a width in the range from about 0.2 to 1.5 μm, in particular 0.2 to 1 μm. The ratio of width to length of the crystal has, as a rule, a value of less than 0.2. The ratio of width to length of the crystal is usually about 0.1 or less. The crystals usually form agglomerates which have the appearance of felt-like bales. The agglomerates are obtained with a diameter in the size range from about 10 to 170 μm, the main proportion comprising agglomerates having a diameter of about 20 μm.
- The low-temperature modification consists of cylindrical crystals which as a rule have a width of more than 1.5 μm, typically 2 to 5 μm. The ratio of width to length of the crystals is usually in the range from 0.6 to 2, typically 2. The crystals also form agglomerates which for the most part have a diameter of about 20 μm.
- The high-temperature modification of the aluminum salts is particularly suitable as flameproofing agents or flame retardants for plastics, in particular for polyester or polyamide.
- The aluminum salts of the high-temperature modification have advantages for use as flameproofing agents for plastics. Investigations have shown that the flame-retardant effect of the salts of the phosphinic acids in the plastic depends on the particle size of the salt and that an optimum particle size results. The aluminum salts of the high-temperature modification form directly in the advantageous particle size. Milling of the aluminum salts is therefore not necessary for compounding, which means an economic advantage for the preparation of flameproofed plastics. In addition, the finer structure of the aluminum salt permits a more homogeneous distribution of the flameproofing agent in the plastic. The fibrous structure of the aluminum salt moreover leads to reinforcement of the plastic (fiber reinforcement). The finer structure leads to a larger surface area of the particle and, for example with the use of synergistic agents, such as nitrogen compounds, improves their flameproofing effect.
- 308 g (1.75 mol) of n-butyl methyl-n-propylphosphonate, 290 ml of water and 45.5 g (0.583 mol) of aluminum hydroxide are introduced into a 1 l autoclave and kept at 200° C. for 50 hours while stirring. Cooling and filtration with suction are then carried out, followed by drying. 214 g of aluminum salt of methyl-n-propylphosphinic acid are obtained. This corresponds to a yield of 94% of theory. The product does not melt up to 360° C. The product retains the crystal habit of a high-temperature modification (pseudomorphism).
- If the product is prepared according to EP-A2-0699708, it is obtained in the low-temperature modification (in this context, also see the attached tables showing the maxima of X-ray diffraction patterns, Cu—Kα1).
- 264 g (1.5 mol) of n-butyl ethylmethylphosphonate, 250 ml of water and 39 g (0.5 mol) of aluminum hydroxide are kept at 200° C. in a 1 l autoclave for 50 hours while stirring. Cooling and filtration with suction are then carried out, followed by drying at 100° C. in a vacuum drying oven. 157 g of aluminum salt of ethylmethylphosphinic acid, having a residual water content of 58 ppm and a mean particle size of 20.03 μm, are obtained. This corresponds to a yield of 90% of theory. The product does not melt up to 360° C. The product retains the crystal habit of a high-temperature modification (pseudomorphism).
- If the product is prepared according to Patent EP-A2-0699708, it is obtained in the low-temperature modification (in this context, also see the attached tables showing the maxima of X-ray diffraction patterns, Cu—Kα1).
- 213 g (1.2 mol) of amyl ethylmethylphosphonate, 200 ml of water and 31.2 g (0.4 mol) of aluminum hydroxide are kept at 190 to 220° C. in a 1 l autoclave for 50 hours. Filtration with suction and drying are then carried out. 123 g of aluminum salt of ethylmethylphosphinic acid are obtained. This corresponds to a yield of 88.5% of theory. The product is obtained in the crystal habit of a high-temperature modification (in this context, see Example 1).
TABLE 1 X-ray diffraction pattern of aluminum methylpropylphosphonate (Debye-Scherrer beam path, Cu-Kα1, transmission) Low-temperature phase High-temperature phase 2θ [°] rel. int. 2θ [°] rel. int. 8.75 100 8.35 100 14.10 1 15.20 2 14.55 2 16.60 3 20.25 6 20.05 6 20.75 7 22.10 3 22.05 <1 22.50 4 23.90 3 23.40 2 26.85 3 26.30 2 27.30 2 28.70 1 29.65 2 28.95 <1 30.10 2 33.50 1 32.45 <1 -
TABLE 2 X-ray diffraction pattern of aluminum methylmethylphosphonate (Debye-Scherrer beam path, Cu-Kα1, transmission) Low-temperature phase High-temperature phase 2θ [°] rel. int. 2θ [°] rel. int. 9.70 100 9.35 100 19.60 20 18.95 9 19.55 5 25.95 4 25.45 2 27.75 13 26.70 5 27.15 2 32.70 2 31.70 1 34.20 1 32.60 <1 35.45 3 34.20 1 36.95 1 35.50 <1 - 250 g of aluminum salt of ethylmethylphosphinic acid, prepared at 90° C. according to Example 1 in EP-A2-0699708 (low-temperature modification), are heated in 250 g of water for 50 hours at 200° C. The mixture is then allowed to cool to room temperature. The liquid is filtered off with suction and the crystals are dried. 230 g of aluminum salt of ethylmethylphosphinic acid are obtained in the crystal habit of the high-temperature modification.
- 30 g of aluminum salt of ethylmethylphosphinic acid, prepared at 90° C. (low-temperature modification), are stirred under a nitrogen atmosphere for 7 hours at 250° C. There is virtually no transformation into the high-temperature modification.
Claims (9)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/824,478 US6414185B2 (en) | 1996-07-22 | 2001-04-02 | Aluminum salts of phosphinic acids |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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DE19629432 | 1996-07-22 | ||
DE19629432.0 | 1996-07-22 | ||
DE19629432A DE19629432A1 (en) | 1996-07-22 | 1996-07-22 | Aluminum salts of phosphinic acids |
US09/214,473 US6211402B1 (en) | 1996-07-22 | 1997-09-07 | Phosphinic acid aluminum salts |
US09/824,478 US6414185B2 (en) | 1996-07-22 | 2001-04-02 | Aluminum salts of phosphinic acids |
Related Parent Applications (2)
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PCT/EP1997/003631 Division WO1998003515A1 (en) | 1996-07-22 | 1997-07-09 | Phosphinic acid aluminium salts |
US09/214,473 Division US6211402B1 (en) | 1996-07-22 | 1997-09-07 | Phosphinic acid aluminum salts |
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US20010025116A1 true US20010025116A1 (en) | 2001-09-27 |
US6414185B2 US6414185B2 (en) | 2002-07-02 |
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US09/214,473 Expired - Lifetime US6211402B1 (en) | 1996-07-22 | 1997-09-07 | Phosphinic acid aluminum salts |
US09/824,478 Expired - Lifetime US6414185B2 (en) | 1996-07-22 | 2001-04-02 | Aluminum salts of phosphinic acids |
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US09/214,473 Expired - Lifetime US6211402B1 (en) | 1996-07-22 | 1997-09-07 | Phosphinic acid aluminum salts |
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US (2) | US6211402B1 (en) |
EP (1) | EP0923586B1 (en) |
JP (1) | JP4049398B2 (en) |
DE (2) | DE19629432A1 (en) |
WO (1) | WO1998003515A1 (en) |
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WO2008135287A1 (en) * | 2007-05-07 | 2008-11-13 | Martinswerk Gmbh | Flame retarded thermosets |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4810425A (en) * | 1988-03-07 | 1989-03-07 | Ethyl Corporation | Preparation of phosphinic acids |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2745982C2 (en) * | 1977-10-13 | 1991-02-14 | Bayer Ag, 5090 Leverkusen | Process for the production of phosphonic acids and phosphinic acids |
DE4430932A1 (en) * | 1994-08-31 | 1996-03-07 | Hoechst Ag | Flame retardant polyester molding compound |
DE19516025A1 (en) | 1994-12-30 | 1996-10-10 | Delbrouck Franz Gmbh | Plastics crates for transporting and storing goods |
DE19616025C1 (en) * | 1996-04-23 | 1997-04-17 | Hoechst Ag | Simple, direct prepn. of aluminium phosphinate(s) from alkyl ester |
-
1996
- 1996-07-22 DE DE19629432A patent/DE19629432A1/en not_active Withdrawn
-
1997
- 1997-07-09 EP EP97932791A patent/EP0923586B1/en not_active Expired - Lifetime
- 1997-07-09 DE DE59709450T patent/DE59709450D1/en not_active Expired - Lifetime
- 1997-07-09 JP JP50649398A patent/JP4049398B2/en not_active Expired - Lifetime
- 1997-07-09 WO PCT/EP1997/003631 patent/WO1998003515A1/en active IP Right Grant
- 1997-09-07 US US09/214,473 patent/US6211402B1/en not_active Expired - Lifetime
-
2001
- 2001-04-02 US US09/824,478 patent/US6414185B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4810425A (en) * | 1988-03-07 | 1989-03-07 | Ethyl Corporation | Preparation of phosphinic acids |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008135287A1 (en) * | 2007-05-07 | 2008-11-13 | Martinswerk Gmbh | Flame retarded thermosets |
Also Published As
Publication number | Publication date |
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WO1998003515A1 (en) | 1998-01-29 |
JP2000515144A (en) | 2000-11-14 |
EP0923586A1 (en) | 1999-06-23 |
JP4049398B2 (en) | 2008-02-20 |
US6211402B1 (en) | 2001-04-03 |
EP0923586B1 (en) | 2003-03-05 |
DE59709450D1 (en) | 2003-04-10 |
DE19629432A1 (en) | 1998-01-29 |
US6414185B2 (en) | 2002-07-02 |
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