CN1194261A - Method for preparing diaryl ester carbonate using beta diketone - Google Patents

Abstract

Hydroxyaromatic compounds such as phenol are converted to diaryl carbonates by reaction with oxygen and carbon monoxide in the presence of a catalyst package which comprises a Group VIIIB metal, preferably palladium, salt of at least one aliphatic beta -diketone such as 2,4-pentanedione. The catalyst package also preferably comprises an inorganic cocatalyst, an organic cocatalyst and a bromide or chloride, preferably bromide, source such as a hexaalkylguanidinium bromide. The use of the beta -diketone salt confers such advantages as long shelf life under normal storage conditions, high activity upon recycle and capability of carbonylation at relatively low temperatures.

Description

Use beta diketone to prepare the method for diaryl carbonate

The present invention relates to prepare the method for diaryl carbonate by carbonylation.More particularly, relate to storage time and the active innovative approach that is used in the catalyzer in the carbonylation reaction.

Diaryl carbonate be by with melt in the transesterification of bis-phenol prepare the valuable intermediate of polycarbonate.This polycarbonate method than use phosgene (a kind of toxic gas) as reagent and environmentally harmful chlorination aliphatic hydrocrbon for example methylene dichloride have advantage on the environment as the method for solvent.

The whole bag of tricks for preparing diaryl carbonate by the carbonylation reaction of hydroxy aromatic compound and carbon monoxide and oxygen is disclosed.Generally speaking, carbonylation reaction needs quite complicated catalyzer.No. the 4187242nd, reference example such as United States Patent (USP), wherein catalyzer can be a VIIIB family metallic compound, promptly is selected from the metallic compound of ruthenium, rhodium, palladium, osmium, iridium and platinum.

Other progress in carbonylation reaction comprises with promotor such as cobalt pentacoordinate polymerization of olefin using catalyst compound and terpyridyl uses acid chloride (II), is disclosed in United States Patent (USP) the 5231210th, 5284964 and 5399734.These patents also disclose the halogenide part formed as described catalyzer of bromination tetra-n-butyl ammonium for example of using quaternary ammonium Huo Phosphonium.In common unsettled provisional application registration number [RD-25209], disclose use chlorination or bromination six alkyl Guanidinium and replaced quaternary ammonium salt.

Use as the VIIIB family metal-salt of acetate follow with as described in storage time and active some relevant shortcoming of catalyst mixture.In the reactant hydroxy aromatic compound, the described catalyzer that stores as feedstock solution is easily, and described feedstock solution comprises the metal-salt with VIIIB at least a and preferably all other catalyst components family.Yet, the storage time of greatly having limited described feeding liquid in storage because VIIIB family metal precipitates.

Reclaiming described catalyzer after use also is easily.Generally the affixture form with catalyst component remaining in other hydroxy aromatic compound solution and hydroxy aromatic compound reclaims diaryl carbonate.Yet this class solution has very short storage time as mentioned above.

At last, in above-mentioned patent, disclose be used for carbonylation reaction temperature 60-150 ℃ of level.Yet the acetate of generally finding divalence VIIIB family metal for example acid chloride (II) is only exceeding under about 100 ℃ temperature and could provide diaryl carbonate with high yield.Thereby, preferably use in wide temperature range, comprise significantly being lower than the catalyzer that has high activity under 100 ℃ of temperature.

The present invention is based on and find that a series of VIIIB family metallic compound during catalyst component, has this fact of many advantages in being used as carbonylation.These advantages are included under the general condition of storage, even contact down long storage time with reagent with other catalyst component, high reactivity after recovery and use properties at a lower temperature.

At it on the one hand, the present invention relates to prepare the method for diaryl carbonate, it comprises the process that at least a hydroxy aromatic compound and oxygen and carbon monoxide are contacted in the presence of at least a catalytic specie (the VIIIB family metal-salt that comprises at least a aliphatic beta-diketon) of the significant quantity that is used for carbonylation.

Another aspect of the present invention relates to the catalyzer of the stable storing of the VIIIB family metal-salt that comprises at least a aliphatic beta-diketon, inorganic promotor, organic promoter and muriate or bromide source and forms, and described composition is in the solution of at least a hydroxy aromatic compound.

Any hydroxy aromatic compound can be with in the present invention.General preferred monohydroxy aromatic substance is phenol, cresols, xylenol and right-cumylphenol, most preferably phenol for example.Yet the present invention also can use dihydroxy aromatic compounds for example Resorcinol, Resorcinol and 2, and two (4-hydroxy phenyl) propane of 2-i.e. " dihydroxyphenyl propane ", and therefore, its product is a polycarbonate.

The essential reagent of in the methods of the invention other is oxygen and carbon monoxide, and they and phenol reactant form needed diaryl carbonate.

The essential composition of used catalytic specie is the VIIIB family metal-salt of at least a aliphatic beta-diketon according to the present invention.Described " beta-diketon " refers to and contains two ketone carbonyls being separated by a carbon atom (generally but be not to be necessary for CH ₂Bonding scheme) compound.

Suitable beta-diketon comprises 2,4-diacetylmethane, 2,4-hexanedione and 3,5-heptadione.The diketone of preferred divalent metal, most preferably 2, the palladium of 4-diacetylmethane (II) salt.

Preferred catalytic specie is also included within the above-mentioned United States Patent (USP) 5231210 disclosed inorganic promotor type and/or disclosed organic promoter type in above-mentioned United States Patent (USP) 5284964.Preferably not only use inorganic but also use organic promoter.

General inorganic promotor is cobalt (II) salt and coordination compound, the especially coordination compound of pentacoordinate base that can form the organic compound of coordination compound.Illustrative this class organic compound is that nitrogen heterocyclic comprises pyridine, dipyridyl, terpyridyl, quinoline, isoquinoline 99.9 and diquinolyl; Aliphatic polyamines is quadrol and tetraalkyl quadrol for example; Crown ether; Aromatics or aliphatic amidogen ether be kryptofix 222 (cryptanes) for example; And Schiff alkali.Particularly preferred inorganic promotor is and cobalt (II) coordination compound of two [3-(salicylic aldehyde amino) propyl group] methylamine that this coordination compound hereinafter is called " CoSMDPT ".

Suitable organic promoter comprises various terpyridyls, phenanthroline, quinoline and isoquinoline compound, comprises 2,2 ': 6 ', 2 "-terpyridyl, 4 '-methylthio group-2; 2 ': 6 ', 2 "-terpyridyl and 2,2 ': 6 '; 2 "-terpyridyl N-oxide compound, 1,10-phenanthroline, 2,4,7,8-tetramethyl--1,10-phenanthroline, 4,7-phenylbenzene-1,10-phenanthroline and 3,4,7,8-tetramethyl--1,10-phenanthroline.General preferred terpyridyl, particularly 2,2 ': 6 ', 2 "-terpyridyl.

Described catalytic specie is preferred package chloride or bromide also, preferred bromide source.It can be as the disclosed quaternary ammonium of above-mentioned patent or phosphonium salt or as common unsettled provisional application registration number [RD-25209] in disclosed chlorination or bromination six alkyl Guanidinium.General preferred Guanidinium salt; They comprise a, two (five alkyl Guanidinium) the alkane salt of w-.Preferred especially wherein alkyl contains the salt of 2-6 carbon atom, especially bromination Hexaethyl Guanidinium.

An important feature of the present invention is that described catalyzer is formed the stability under condition of storage, and no matter they comprise all still catalyst components of part only.Thereby, the beta diketone of palladium can be stored in the container, with inorganic promotor, organic promoter and muriate or bromide source in the solution of hydroxy aromatic compound.If, generally can accomplish to be no more than two so that independently batch catalyst precursor that storage is different composition is more convenient.

The ratio of used VIIIB family metal-salt is for being enough to provide every 800-10000 mole, the amount of the about 1 grammeatom metal of hydroxy aromatic compound of preferred 2000-5000 mole.With regard to the VIIIB family metal of every grammeatom, general about 0.1-5.0, the cobalt of especially about 0.5-1.5 grammeatom of using; About 0.1-3.0, the organic promoter of preferably about 0.3-1.0 mole and about 5-150, the muriate of preferably about 20-50 mole or bromide source.

Ratio with the carbon monoxide of the oxygen of about 2-50% (mole) and equal amount provides gas to described reaction mixture.Can import gas respectively or import, make total pressure in the atmospheric scope of about 10-250 with the form of mixture.Temperature of reaction is generally in about 60-150 ℃ scope, because the energy utilization that reduces and utilize significantly ability than the gas ratio of low oxygen content, the about 80-110 of Chang Youxuan ℃ temperature range, especially about 90-100 ℃ temperature range.In reaction vessel, siccative can be arranged, be generally molecular sieve.For reaction is as far as possible promptly carried out, according to above-mentioned United States Patent (USP) 5399734, preferably keep described reaction pressure, up to the transformation of finishing described hydroxy aromatic compound.

Can use routine techniques to separate the diaryl carbonate for preparing with the inventive method.As described in United States Patent (USP) 5239106 and 5312955, be preferably formed usually and the affixture of cracking diaryl carbonate and hydroxy aromatic compound on thermodynamics.

Explain the present invention by the following example.Except as otherwise noted, all umbers and ratio are all calculated by weight.The ratio of reagent, to be that perseverance is executed fixed although can be said to for all embodiment, in some cases owing to batch big or small trial and error method changes; Yet the difference on this ratio of empirical evidence is unessential for product yield, transformation efficiency etc.Embodiment 1

With 2,4-diacetylmethane palladium (II) salt (2,4-pentanedionate) (500ppm palladium) and 2,2 ': 6 '; 2 " the phenol solution of-terpyridyl (0.33 equivalent) places the 100ml3 neck round-bottomed flask that has magnetic stirring apparatus, nitrogen inlet tube and serum cap, and the metal alloy stopple coupon that is equivalent to the usual pressure reaction vessel is suspended in wherein in case before carbonylation the analogue reactor condition.Described solution is clarification and orange.In nitrogen, stir, in 60 ℃ of heating 9 days, timing sampling analysis.Do not observe the loss of precipitation or soluble palladium.By contrast, wherein use the acid chloride (II) of equivalent to replace 2,7 days postprecipitations of the reference substance of 4-diacetylmethane palladium (II) lose its palladium of 33%.

Embodiment 2

Except described phenol solution also contains 1 normal CoSMDPT and 10 normal bromination Hexaethyl Guanidinium, repeat the process of embodiment 1.After 21 days, do not observe the loss of precipitation or soluble palladium.By contrast, the 7 days postprecipitations of reference substance that contain acid chloride (II) lose its palladium of 56%.Embodiment 3

With 2 of CoSMDPT, the 23.9mg (0.101mmol) of bromination Hexaethyl Guanidinium, the 124.4mg (0.303mmol) of the phenol of 60.06g (638mmol), 1001mg (3.27mmol), 2 ': 6 '; 2 " 2 of-terpyridyl and 87.4 mg (0.288mmol), 4-diacetylmethane palladium (II) salt (500ppm palladium) place as the constant composition gas-flow reactors of above-mentioned United States Patent (USP) 5399734 disclosed tools system.The 37g molecular sieve placed in the porous Teflon basket on the stirrer shaft that is installed in described reactor.

Seal described reactor and be heated to 110 ℃, stir simultaneously, with flow velocity and the about 44 atmospheric pressure of 344ml/min, the mixture of the carbon monoxide of the oxygen and 87.2% (mole) of importing 12.8% (mole).Make air-flow continue 2 hours, thereafter, take out a part of reaction mixture, analyze with high pressure liquid chromatography.

Use 2,4-diacetylmethane palladium (II)-three piperidines composition (as described in example 1 above, having stored 9 days) repeats described reaction.In contrast, use and to use freshly prepd respectively and store the reaction mixture of 7 days acid chloride (II) as described in example 1 above.It the results are shown in the table 1.

Table 1

Pd (II) salt dipheryl carbonate base ester yield %

2,4-diacetylmethane salt, new system 42.9

2,4-diacetylmethane salt stores 35.4

Acetate, new system 43.3

Acetate stores 14.0

The result of table 1 shows 2 of new system, and 4-diacetylmethane salt is provided at the dipheryl carbonate base ester that the yield aspect can be comparable with the acetate of new system.Yet, make described palladium salt aging after, 2, the yield that 4-diacetylmethane salt provides is significantly higher than control group.Embodiment 4

Use is diluted to the catalyzer of the embodiment 2 of catalyst component concentration described in the embodiment 3 to be formed through phenol, repeats the process of embodiment 3.The yield of dipheryl carbonate base ester is 38.4%.Thereby obvious catalyzer of the present invention consists of stable storing.Embodiment 5

By the catalyst component described in the embodiment 3 is added in the mixture of 42 portions of diphenyl carbonates and 58 parts of phenol preparation mimic carbonylation reaction mixture with same ratio (being the 500ppm palladium).The uniform mixture of generate is transferred in the crystallizer that remains on 35 ℃ of stirrings.Behind the several hrs, this crystalline mixture in 35 ℃ of affixtures that enter in the B by the described diphenyl carbonate-phenol of filtering separation, and is washed with 10: 90 uniform mixtures of diphenyl carbonate-phenol.

Dilute its mother liquor with phenol and produce the mixture that contains the 500ppm palladium again, and as described in the embodiment 3 with this mixture carbonylation, just its gas feed contains the oxygen of 9.1% (mole).After 2 hours, the yield of dipheryl carbonate base ester is 51.5%, as a comparison, contains 2 of new system, and the catalyzer of 4-diacetylmethane palladium (II) salt is 51.7%.

Is in the comparative examples of 12.8% (mole) using acid chloride (II) as catalyst component and oxygen concn, use the catalyzer of new system obtain can with use 2, the comparable yield of 4-diacetylmethane palladium (II) salt.Yet, behind separation diphenyl carbonate-phenol affixture, use the yield that reclaims catalyzer to be reduced to 42.4%.Thereby, after obviously reclaiming, 2,4-diacetylmethane palladium (II) salt catalyst mixture is higher than the activity of acid chloride (II) mixture.Embodiment 6

Make and use 2,4-diacetylmethane palladium (II) salt and acid chloride (II) with differing temps and oxygen concn, repeat the process of embodiment 3 as catalyst component.It the results are shown in the Table II.

Table II

Diphenyl carbonate

Yield %Pd (II) salt temperature. ℃ oxygen % (mole) 2,4-diacetylmethane salt ate 110 12.8 42.9

＂ 100 9.1 44.4

＂ 90 9.1 35.4

＂ 80 9.1 27.2 acetates 110 12.8 43.3

＂ 90 9.1 18.9

Obviously, be lower than under 100 ℃ in temperature, 2,4-diacetylmethane salt is the catalyzer higher than acetate activity.

Claims (20)

1. the method for preparing diaryl carbonate, it is included in be used for the carbonylation significant quantity at least a contains under the existence of catalytic specie of VIIIB family metal-salt of at least a aliphatic beta-diketon, and at least a hydroxy aromatic compound is contacted with carbon monoxide with oxygen.

2. according to the process of claim 1 wherein that described VIIIB family metal is a palladium.

3. according to the method for claim 2, wherein said palladium (II) salt is 2,4-diacetylmethane palladium (II) salt.

4. according to the method for claim 3, wherein said hydroxy aromatic compound is a phenol.

5. according to the method for claim 2, wherein said catalytic specie also comprises and cobalt (II) salt that can form the organic compound of pentacoordinate polymerization of olefin using catalyst compound.

6. according to the method for claim 5, wherein said organic compound is two-[3-(salicylic aldehyde amino) propyl group] methylamine.

7. according to the method for claim 2, wherein said catalytic specie comprises that also terpyridyl, phenanthroline, quinoline or isoquinoline compound are as organic promoter.

8. according to the method for claim 7, wherein said organic catalyst is 2,2 ': 6 ', 2 "-terpyridyl.

9. according to the method for claim 2, wherein said catalytic specie also comprises muriate or bromide source.

10. according to the method for claim 9, wherein said muriate or bromide source are bromination quaternary ammonium salt, bromination quaternary phosphine or bromination six alkyl Guanidinium.

11. according to the method for claim 10, wherein said bromide source is bromination C _2-6Six alkyl Guanidinium.

12. according to the method for claim 11, wherein said bromination six alkyl Guanidinium are bromination Hexaethyl Guanidinium.

13. according to the method for claim 2, the ratio of wherein said oxygen and carbon monoxide is the oxygen of about 2-50% (mole), and the carbon monoxide of equal amount.

14. according to the method for claim 2, the ratio of wherein said palladium is the hydroxy aromatic compound of every 2000-5000 mole, about 1 grammeatom.

15. according to the method for claim 2, wherein every grammeatom palladium uses the halogenation six alkyl Guanidinium of about 0.5-1.5 grammeatom cobalt, about 0.3-1.0 mole organic promoter and about 20-50 mole.

16. the composition of stable storing, it contains the VIIIB family metal-salt of at least a aliphatic beta-diketon, inorganic promotor, organic promoter and muriate or bromide source, and described composition is in the solution of at least a hydroxy aromatic compound.

17. according to the composition of claim 16, wherein said aliphatic beta-diketon is 2, the 4-diacetylmethane.

18. according to the composition of claim 17, wherein said inorganic promotor is cobalt (II) coordination compound with two [3-(salicylic aldehyde amino) propyl group] methylamine.

19. according to the composition of claim 17, wherein said organic promoter is 2,2 ': 6 ', 2 "-terpyridyl.

20. according to the composition of claim 17, wherein said muriate or bromide source are bromination Hexaethyl Guanidinium.