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 Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/50—Organo-phosphines
  • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
• • 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
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/50—Organo-phosphines
  • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
  • C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)

Definitions

• the present invention relates to a process for the production of solid acylphosphine oxides by converting an acylphosphine oxide present as a melt in a continuous phase or dispersed under mechanical stress, shear / internal movement of the melt into the solid state.
• acylphosphine oxides with final purity and as a disperse solid are obtained by removing them from the reaction mixture or a solution, i.e. molecularly present, optionally crystallized by precipitation.
• the solvent contained in the crystallization solution that is organic solvents or mixtures thereof, may already have been present in the reaction, or it is added as a solvent in the workup, in particular in a recrystallization.
• the object of the present invention was to provide a process for acylphosphine oxides which provides solids in a simple and inexpensive manner.
• the object was achieved by a process for the production of acylphosphine oxide solids with melting points above room temperature, in which the acylphosphine oxide present after reaction or workup as a continuous melt phase or disperse melt phase under mechanical stress, shear / internal movement of the melt in the solid state transferred.
• Acylphosphine oxides for the purposes of the present invention are phosphine oxides which carry at least one acyl group, for example mono-, bis- or trisacylphosphines, preferably mono- or bisacylphosphine oxides and particularly preferably monoacylphosphine oxides.
• R ⁇ R 2 and R 3 independently of one another d - C 18 alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C 2 - C 18 alkyl, C 2 - C 18 alkenyl, C 6 - C 12 aryl, C 5 - C 12 cycloalkyl or a five- to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms, where the radicals mentioned are each aryl, alkyl, aryloxy, Alkyloxy, heteroatoms and / or heterocycles can be substituted, and
• Ci - C 18 alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl , 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl , 2-phenylethyl, a, a - dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-
• Methylaminopropyl 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3- Phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl,
• Ci - C 18 alkoxy for example methoxy, ethoxy, n-propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, sec-butyloxy, tert-butyloxy, 6-hydroxy-1, 4- dioxohexyl, 9-hydroxy-1, 4,7-trioxononyl, 12-hydroxy-1, 4,7,10-tetraoxododecyl, 6-methoxy-1, 4-dioxohexyl, 9-methoxy-1, 4,7-trioxononyl, 12-methoxy-1, 4,7,10-tetraoxododecyl, 6-ethoxy-1,4-dioxohexyl, 9-ethoxy-1, 4,7-trioxononyl, 12-ethoxy-1, 4,7,10-tetraoxododecyl, 8-hydroxy-1
• C 2 -C 8 -alkyl optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups C 2 -C 8 -alkyl, for example 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxa- octyl, 11-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 11-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa- pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy- 3,6,9-trioxa-undecyl, 7-
• the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the rest, preferably not more than 4 and very particularly preferably not more than 3.
• Substituted and unsubstituted imino groups can be, for example, imino, methylimino, / so-propylimino, n-butylimino or terf-butylimino.
• aryl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C 6 -C 2 aryl, for example phenyl, tolyl, xylyl, a -naphthyl, ⁇ -naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, Methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chlomaphthy
• C 5 -C 12 cycloalkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example cyclopentyl, cyclohexyl, cycloocytyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexohexyl, Dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbomenyl,
• a five- to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms for example furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrylol, dimethylpyrylol Dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl and Ci to C 4 alkyl, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
• radicals having one to three carbon atoms it is up to 3 substituents, preferably up to 2 and particularly preferably up to one.
• radicals with four to six carbon atoms it is usually up to 4 substituents, preferably up to 3 and particularly preferably up to one.
• radicals with more than seven carbon atoms it is generally up to 6 substituents, preferably up to 4 and particularly preferably up to two.
• EP-A2 184 095 there in particular from page 2, line 4 to page 5, line 26 and the examples,
• DE-A1 2909994 there particularly from page 6, line 4 to page 9, line 14 and the examples, EP-A273413, there particularly from page 1, line 27 to page 3, line 13 and the examples, DE-A1 31 39 984, there particularly from page 4, line 25 to page 5, line 20 and the examples, DE-A1 3020 092, page 5, line 31 to page 9, No. 28 and the examples, EP-B1 7 508, there in particular from p. 1, lines 12 to p. 4. line 65 and the examples, DE-C24231 579, there in particular p.
• R 1 is selected from the group phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl or 2,6-dichlorophenyl,
• R 2 is selected from the group phenyl, 4-methylphenyl, 2,6-dimethylbenzoyl, 2,4,6-trimethylbenzoyl, 2,6-dimethoxybenzoyl or 2,6-dichlorobenzoyl and
• R 3 is selected from the group phenyl, 4-methylphenyl or 2,4,4-trimethylpentyl.
• 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide is very particularly preferred, Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2 > 4,4-trimethylpentylphosphine oxide.
• 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide is particularly preferred.
• the process according to the invention can preferably be used for those acylphosphine oxides whose melting points are above room temperature, i.e. 23 ° C.
• the melting point of the acylphosphine oxides which can be used for the process which can be used according to the invention is preferably at least 40 ° C., particularly preferably at least 50 ° C. and particularly preferably at least 70 ° C.
• a melt is understood here to mean a liquid mixture which contains at least 85, preferably at least 90 and particularly preferably at least 95% by weight of the acylphosphine oxide in question.
• a solution is a molecularly disperse liquid system in which the acylphosphine oxide content is below 85 or below 90 or below 95% by weight.
• the acylphosphine oxide can also be used in disperse form, a molecularly disperse distribution, ie a solution, being expressly excluded.
• dispersed distribution means liquid distribution as a melt in another phase, preferably in the form of an emulsion, the diameter of the droplets being at least 0.1 ⁇ m, preferably at least 1 ⁇ m and particularly preferably at least 5y. m.
• the acylphosphine oxide is very particularly preferably used as a continuous melt phase.
• the other phase which surrounds the acylphosphine oxide droplets, can be a liquid or a gas immiscible or preferably immiscible with the acylphosphine oxide, preferably a liquid.
• the melt can come into contact with already existing, specific or other types of solid before or during the solidification.
• a liquid is used as the surrounding phase, it should not be miscible with the acylphosphine oxide in the concentration and temperature range used.
• acylphosphine oxide in the liquid is less than
• the liquid is less than 10% by weight, preferably less than 5% by weight, particularly preferably less than 2% by weight and very particularly preferably less than 1% by weight. It is additionally preferred if the liquid is less than 10% by weight, preferably less than 5% by weight, particularly preferably less than 2% by weight and very particularly preferably less than 1% by weight soluble in the acylphosphine oxide.
• the melt can be obtained directly as a reaction melt or can emerge from the reaction discharge after suitable work-up steps known per se, such as distillation, rectification, extraction, optionally followed by washing or stripping processes.
• suitable work-up steps known per se such as distillation, rectification, extraction, optionally followed by washing or stripping processes.
• Such a solid formation process is particularly advantageous if no solvent is used in the preceding process steps.
• a melt of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (melting point about 92 ° C.) obtained by reaction of trimethylbenzoyl chloride with ethoxidiphenylphosphine and subsequent multi-stage extraction, which is left in a vessel or allowed to cool in a bowl, is allowed to cool with the cooling of the melt increasingly highly viscous and there is no or only a sluggish, usually only partial, solid formation over many hours to several days.
• Pastilling i.e. the application of drops of melt onto a cooling surface, for example a steel strip or steel plate, on which the drops are to be solidified normally in the range of a few minutes, or
• Desquamation i.e. the task of a melt film on a cooling surface, for example a steel belt or a roller, on which the melt film is to convert to a solid layer in the range of a few minutes, which can then be removed with a knife to produce fragments, the scales,
• melts or dispersions preferably melts or emulsions and particularly preferably melts of acylphosphine oxides can be converted into a solid in a short time and without problems if the melt is subjected to mechanical stress during the solidification and as a result thereof internally flows, shears or is moved internally.
• mechanical stress is understood to mean measures which are present in the continuous or disperse phase
• a melt of acylphosphine oxides can be easily converted into a disperse solid by introducing the melt into a stirred or circulated apparatus (eg DTB (Discotherm-B apparatus) from List, paddle dryer, stirred tank), and starting from the continuous melt phase with stirring and heat dissipation, the melt is processed into a free-flowing solid via the state of a suspension (discontinuous variant).
• a stirred or circulated apparatus eg DTB (Discotherm-B apparatus) from List, paddle dryer, stirred tank
• the mechanical stress on the melt i.e. the force acting on the melt, causes shear or internal movement.
• mechanical stresses include stirring, pumping over, doctoring, scraping, treating with ultrasound or a gas jet, for example through a nozzle or a gap which is passed through the melt or directed onto the surface thereof.
• the melt can be mixed with a solid in an apparatus, for example the melt can be placed on a template or a solid can be added to the melt, and after it has been broken up by mixing / moving the solid and melt particles from a single mixer dispersed melt state can be processed to disperse solid (continuous or discontinuous procedure).
• the original can be of a different type or of a different nature, ie it can be the solid acylphosphine oxide to be cleaned or another solid, for example another acylphosphine oxide.
• a further embodiment is the continuous or discontinuous introduction of the melt into a solid bed, which is not stirred or mixed with mechanical aids, but is mixed / moved by means of a fluid flow and thereby cooled.
• a gas is used as the fluid, so that a fluidized bed is formed.
• the particle size distribution of the solid which arises in the process according to the invention can be controlled by changing the operating conditions of the process and by properties of the apparatus in which the process is carried out.
• Changeable sizes for particle size control are e.g. Type, intensity and duration of stirring / mixing, type of melt feed, for example with or without pre-distribution, e.g. via nozzles, baffle plates or distributors, the presence or type of a solid charge, for example foreign or specific, operating temperatures, for example up to 90 K below the melting point of the phosphine oxide, type of cooling process, for example with a cooling rate of 1 to 100, preferably 5 to 60 K / h and residence time / specific melt throughput from a few minutes to a few hours.
• a particle size that is all the smaller is obtained if an energy input takes place longer and more intensively or with a strong pre-distribution and a broad particle size distribution if no solid charge is used.
• the acylphosphine oxide melt can be mixed with a liquid in which the melt is practically insoluble, so that two liquid phases form.
• Preferred liquids therefor are those which, as stated above, are immiscible and have the stated solubilities of acylphosphine oxide in the liquid and the stated solubilities of the liquid in acylphosphine oxide, for example liquids with an E ⁇ (30) value of more than 50, preferably of more than 56 and particularly preferably ionic liquids (the E ⁇ (30) value is a measure of the polarity and is described by C. Reichardt in Reichardt, Christian Solvent Effects in Organic Chemistry Weinheim: VCH, 1979. - XI, ( Monographs in Modern Chemistry; 3), ISBN 3-527-25793-4 page 241 to page 242.). The solvents listed with Reichardt, op. Cit. On p.
• the acylphosphine oxide can be converted into a dispersed melt state by intensive agitation, for example in a stirred or pumped-over container, and into a disperse solid by heat dissipation. Subsequently, it is generally necessary to separate and dry the solid; the other disadvantages of solids extraction by solution crystallization mentioned are avoided, since the losses of valuable product via the liquid are minimized.
• Processing the melt into a disperse solid means that the initially usually melt is present as a continuous phase during / after introduction into the solidification apparatus (e.g. by emulsification in a liquid or by splitting / mixing into a moving solid bed), and then under mechanical stress / internal movement, triggered by flow forces and / or impact events with particles or internals or walls of the apparatus, the divided melt fractions are solidified as separate particles and / or as melt films drawn onto already existing particles and / or between existing particles to form agglomerates.
• the solidification apparatus e.g. by emulsification in a liquid or by splitting / mixing into a moving solid bed
• the divided melt fractions are solidified as separate particles and / or as melt films drawn onto already existing particles and / or between existing particles to form agglomerates.
• 2,4,6-trimethylbenzoyl-diphenylphosphine oxide with bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide with bis ( 2,6-dimethoxybenzoyl) - 2,4,4-trimethylpentylphosphine oxide can be used to achieve a formulation of different acylphosphine oxides in which one acylphosphine oxide supports the solidification of the other.
• the temperature of the cooling medium used for heat dissipation / the cooling surface used for heat dissipation has only a moderate influence on the solid formation times.
• a temperature up to 90 K below the melting point of the phosphine oxide can generally be used, preferably 5 to 70 K, particularly preferably 20 to 60 K.
• the heat dissipation during the formation of the solid can preferably be carried out by cooling apparatus walls.
• the heat dissipation is particularly preferably effected by indirect cooling via heat exchanger surfaces. All substances and mixtures suitable for this purpose can be used as heat carriers, in particular water, water / methanol or water / glycol mixtures.
• the solid present after solidification according to the invention can be subjected to one or more post-treatments by means of methods known per se in order to change the solid properties as desired. Examples include grinding and / or sieving the solid to influence the particle size distribution. Solid particles with undesirable properties (e.g. particles that are too coarse / fine) that are obtained in these post-treatment steps are preferably melted or also returned unmelted to the solid formation stage. A transfer to another procedural point is also possible.
• washing can be carried out in apparatuses customary for this purpose, such as washing columns, for example as described in DE-A1 10036 881, in which the liquid is separated and washed in one apparatus, in centrifuges which can be operated in one or more stages. or in filter chutes or band filters.
• the washing can be carried out on centrifuges or belt filters in one or more stages, the washing liquid preferably being conducted in countercurrent to the solid.
• the mass ratio of washing liquid to solid is generally in the range from 0.1 to 4, particularly preferably in the range from 0.2 to 1 kg of washing liquid per 1 kg of solid.
• the solidification can take place with at least partial evaporation of these parts in a vacuum.
• the solidification can be carried out in air or under protective gas (inert gas such as nitrogen, noble gases, CO 2 etc.).
• protective gas inert gas such as nitrogen, noble gases, CO 2 etc.
• TPO Trimethylbenzoyl-diphenyl-phosphine oxide
• Example 1 The same melt as in Comparative Example 1 was applied with the same feed temperature to the plate cooled with 30 C C cooling medium as a 3 mm thick film and then slowly stirred / sheared with a spatula. A chunky solid was present after about 7 to 8 minutes.
• a melt of 2,4,6-trimethylbenzoyl obtained by reaction of trimethylbenzoyl chloride with ethoxidiphenylphosphine (reaction at 80-85 ° C. in the presence of dimethylcyclohexylamine) and subsequent extraction twice (first extraction with basic water / soda solution; then with water) diphenylphosphine oxide (content of TPO: 99.1 area% HPLC) was placed at 98 ° C. in a 0.5 l glass flask and cooled to room temperature while at rest.
• Diphenyl-phosphine oxide content of TPO: 99.2 area% HPLC
• the apparatus was operated at a speed of 30 rpm and cooled with a coolant temperature of 62 ° C.
• the melt cooled down, clouded over at a temperature of about 80 ° C. (beginning to form a solid) and then converted into a free-flowing, predominantly fine-grained solid within 14 minutes via the state of a suspension.
• Example 4 The same melt as described in Example 3 was continuously introduced at 105 ° C. at a mass flow of 3 kg / h into a 5 l paddle dryer type laboratory apparatus which was already filled with 1.5 kg of solids before the melt was supplied. The apparatus was operated at a speed of 30 rpm and cooled with a coolant temperature of 20 ° C. The melt was mixed into the solid in the apparatus by the rotating mixing elements and discharged as a free-flowing, granular solid at the end of the apparatus opposite the melt task after an average residence time of about 45 min. The temperature of the discharged solid was 25 ° C.
• the particle size distribution for this type of solid formation was: 9% by weight> 2.8 mm; 50.5% by weight from 0.9 to 2.8 mm; 17.9% by weight from 0.56 to 0.9 mm; Balance ⁇ 0.56 mm.
• a melt of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide obtained by reaction of trimethylbenzoyl chloride with ethoxidiphenylphosphine (content of TPO: 95.8 area% HPLC) was placed at 100 ° C. on a stainless steel cooling plate (cooled with a coolant from 60 ° C) as about 3.5 mm thick melt coating and sheared slowly while cooling with a spatula. After 2 minutes there was a hard, crumbly solid.
• a 2,4,6-trimethyibenzoyl-bis (2,5-dimethylphenyl) phosphine oxide melt with a melting point of 136 ° C. was applied in 3 experiments to 145 ° C. as a 3 mm thick film on a stainless steel cooling plate, on which the melt film then rested.
• the plate was cooled with coolant temperatures of 50, 80 and 10 ° C. In all three cases, no, even partial, solid formation was discernible within 15 minutes. The melt remained on the plate as a supercooled, clear and sticky film.

Landscapes

• 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)
• Crystallography & Structural Chemistry (AREA)
• Inorganic Compounds Of Heavy Metals (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (2)

Family

ID=32981095

Family Applications (1)

Country Status (8)

Families Citing this family (4)

Family Cites Families (16)

• 2003
  • 2003-04-04 DE DE10315671A patent/DE10315671A1/de not_active Withdrawn
• 2004
  • 2004-03-30 CN CNB2004800092154A patent/CN100365004C/zh not_active Expired - Fee Related
  • 2004-03-30 US US10/551,994 patent/US7776109B2/en active Active
  • 2004-03-30 JP JP2006504916A patent/JP5322386B2/ja not_active Expired - Fee Related
  • 2004-03-30 EP EP04724292.0A patent/EP1613638B1/de not_active Expired - Lifetime
  • 2004-03-30 WO PCT/EP2004/003349 patent/WO2004087723A2/de not_active Ceased
  • 2004-03-30 KR KR1020057018684A patent/KR100941658B1/ko not_active Expired - Fee Related
  • 2004-04-01 TW TW093108999A patent/TWI325002B/zh not_active IP Right Cessation
• 2013
  • 2013-03-19 JP JP2013056739A patent/JP2013116922A/ja active Pending

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events