CN102295533A - Preparation method of alpha, alpha-dimethyl benzyl alcohol - Google Patents
Preparation method of alpha, alpha-dimethyl benzyl alcohol Download PDFInfo
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Abstract
The invention relates to a preparation method of alpha, alpha-dimethyl benzyl alcohol, mainly solving the problems of production of a large amount of sulfur-containing wastewater, serious pollution, poor product quality, high energy consumption, low production efficiency, and high labor intensity in the prior art. According to the preparation method, olefin and cumene hydroperoxide used as raw materials react for 0.1-24 hours to prepare alpha, alpha-dimethyl benzyl alcohol under the conditions that nonpolar organic compound inert to a reaction system is used as a solvent, the reaction temperature is 0-150 DGE C and reaction pressure is 0.1-10.0MPa, the molar ratio of olefin to cumene hydroperoxide is (0.1-20):1, the weight ratio of cumene hydroperoxide to the solvent is (0.01-9):1 and the amount of a catalyst is 0.01-200% of the weight of cumene hydroperoxide, wherein the catalyst is at least one of Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-KIT-1, Ti-TUD-1 or amorphous Ti/SiO2; and the titanium content of the catalyst is 0.1-20% of weight of the catalyst. The problems in the prior art can be well solved by using the technical scheme; and the preparation method provided by the invention can be used in industrial production of alpha, alpha-dimethyl benzyl.
Description
Technical field
The present invention relates to a kind of α, the preparation method of alpha-alpha-dimethyl benzylalcohol.
Background technology
α, alpha-alpha-dimethyl benzylalcohol are the important source material of preparation dicumyl peroxide (DCP).DCP is considered to industrial monosodium glutamate, and it can make polymkeric substance have three-dimensional structure as linking agent, improves rerum natura greatly; Be used for poly polymerization, its product can be used as the outer dress of cable; Be used for the EVA crosslinked foam, can produce foam materials with fine pores; Be used for the crosslinked of EPM, EPDM, can improve insulativity, processibility and the thermotolerance of product.It also is the excellent vulcanizing agent of natural rubber, synthetic rubber and polyvinyl resin.
Present industrialized α, alpha-alpha-dimethyl benzylalcohol are under 60～65 ℃, use Na
2SO
3Or Na
2The S aqueous solution is that reductive agent reduction hydrogen phosphide cumene (CHP) prepares.This technology produces a large amount of waste water, and 1 ton of DCP of every production will produce 2.5 tons of reductive sulfur-containing waste waters, and COD also will produce a large amount of unpleasant deleterious hydrogen sulfide up to 3.4 ten thousand mg/L in last handling process.Along with the pay attention to day by day of country to " energy-saving and emission-reduction " work, the shortcoming of this technology is more obvious.And, fully being reduced in order to ensure hydrogen phosphide cumene, the consumption of sodium sulphite often will surpass theoretical consumption, and the α of Sheng Chaning like this, the alpha-alpha-dimethyl benzylalcohol product thing that usually can cure pollutes, thereby follow-up use is had a negative impact.Shortcoming such as produce a large amount of sulfur-containing waste waters, seriously polluted, poor product quality, energy consumption height during so prior art exist to be produced, production efficiency is low, labour intensity is big.
Titaniferous porous silica material has good catalytic activity to the selective oxidation of hydro carbons, can be used as the catalyzer that the alkene selective oxidation prepares epoxide.
It is catalyzer that document US 3923843 and US 4367342 disclose with titaniferous amorphous silica, and hydrogen peroxide ethylbenzene (EBHP) can be propylene oxide and by-product α-Jia Jibianchun with Selective Oxidation of Propylene.This patent is just reacted hydrogen peroxide ethylbenzene and propylene and is produced propylene oxide, and the α-Jia Jibianchun of by-product does not mention with the hydrogen phosphide cumene being that oxygenant reacts with propylene or other alkene through further dehydration preparation vinylbenzene.
It is oxygenant that document CN1500004A and CN 1248579A disclose with hydrogen phosphide cumene (CHP) or hydrogen peroxide ethylbenzene (EBHP), prepares the technology of propylene oxide with a kind of titanium-containing catalyst catalytic oxidation propylene of preparation process complexity.But this patent does not relate to α, and the preparation technology of alpha-alpha-dimethyl benzylalcohol and other alkene and hydrogen phosphide cumene react and prepare α, the process of alpha-alpha-dimethyl benzylalcohol.
Summary of the invention
Technical problem to be solved by this invention is exist to produce a large amount of sulfur-containing waste waters, seriously polluted, poor product quality, energy consumption height, production efficiency is low, labour intensity is big problem in the prior art, provides a kind of new α, the preparation method of alpha-alpha-dimethyl benzylalcohol.It is good that this method has selectivity, and the reaction conditions gentleness is pollution-free, the characteristics that good product quality and production cost are low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of α, the preparation method of alpha-alpha-dimethyl benzylalcohol, with alkene and hydrogen phosphide cumene is raw material, reaction system is the inert nonpolar organic compound is solvent, in temperature of reaction is 0～150 ℃, reaction pressure is 0.1～10.0MPa, the mol ratio of alkene and hydrogen phosphide cumene is 0.1～20: 1, the weight ratio of hydrogen phosphide cumene and solvent is 0.01～9: 1, catalyst levels is to react under 0.01～200% condition of hydrogen phosphide cumene weight to obtain described α, alpha-alpha-dimethyl benzylalcohol in 0.1～24 hour; Wherein, described catalyzer is selected from Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-KIT-1, Ti-TUD-1 or unformed Ti/SiO
2In at least a; Wherein titanium content is 0.1～20% of a catalyst weight in the catalyzer.
In the technique scheme, described catalyzer preferred version is for being selected from Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15 or unformed Ti/SiO
2In at least a, more preferably scheme is for being selected from Ti-HMS, Ti-MCM-41 or unformed Ti/SiO
2In at least a.The titanium content preferable range is 0.2～10% of a catalyst weight in the catalyzer, and more preferably scope is 0.5～5%.Before catalyzer uses, be 0～400 ℃ with being dissolved in the organic silicon solution in the organic solvent or using organosilicon steam treatment, silanization temperature preferable range down in gas phase condition preferably, more preferably scope is 50～350 ℃; Silanization treatment time preferable range is 0.5～48 hour, and more preferably scope is 1～24 hour.The organosilicon preferred version is to be selected from least a in halosilanes, silazane or the silylamine; Wherein said halosilanes preferred version is to be selected from least a in trimethylchlorosilane, chlorotriethyl silane, tripropyl chlorosilane, tributyl chlorosilane, chlorodimethyl silane, dimethyldichlorosilane(DMCS), 3,5-dimethylphenyl chlorosilane, dimethyl ethyl chlorosilane, dimethyl n propyl chloride silane, dimethyl isopropyl chloride silane, normal-butyl dimethylchlorosilane or the aminomethyl phenyl chlorosilane, and more preferably scheme is for being selected from trimethylchlorosilane; Described silazane preferred version is for being selected from hexamethyldisilazane, 1,1,3,3-tetramethyl-disilazane, 1,3-two (chloromethyl) tetramethyl-disilazane, 1,3-divinyl-1,1,3,3-tetramethyl-disilazane or 1, at least a in the 3-phenylbenzene tetramethyl-disilazane, more preferably scheme is for being selected from hexamethyldisilazane or 1,1,3, at least a in the 3-tetramethyl-disilazane; Described silylamine is selected from least a in N-trimethyl-silyl-imidazole, N-t-butyldimethylsilyl imidazoles, N-dimethylethylsilyl imidazoles, N-dimethyl n propyl group silyl imidazoles, N-dimethyl sec.-propyl silyl imidazoles, N-trimethyl silyl dimethyl amine or the N-trimethyl silyl diethylamide.The organosilicon consumption is preferably 0.1～100% of catalyst weight, and more preferably scope is 1～50%.
In the technique scheme, described alkene preferred version is for being selected from alkene, cycloolefin, fragrant alkene, chloro-alkenes or hydroxyl alkene; Wherein said alkene preferred version is for being selected from ethene, propylene, butylene, amylene or hexene; Described cycloolefin preferred version is for being selected from cyclopentenes, tetrahydrobenzene, cyclooctene or cyclododecene; Described fragrant alkene preferred version is for being selected from vinylbenzene or alpha-methyl styrene; Described chloro-alkenes preferred version is for being selected from propenyl chloride; Hydroxyl alkene preferred version is for being selected from vinyl carbinol.Described reaction system is inert non-polar organic solvent preferred version is to be selected from least a in benzene,toluene,xylene, ethylbenzene, diethylbenzene, isopropyl benzene, diisopropylbenzene(DIPB), normal butane, Trimethylmethane, pentane, normal hexane, hexanaphthene, heptane, octane, nonane, decane, undecane hydrocarbon or the dodecane hydrocarbon, and more preferably scheme is for being selected from isopropyl benzene.The reaction conditions preferable range is: 40～130 ℃ of temperature of reaction, reaction pressure 0.1～6.0MPa, the mol ratio 0.5～15: 1 of alkene and hydrogen phosphide cumene, the weight ratio 0.1～4: 1 of hydrogen phosphide cumene and solvent, catalyst levels is 0.1～100% of a hydrogen phosphide cumene weight, 0.2～5 hour reaction times.
The catalyzer that is adopted among the present invention is a titaniferous porous silica catalyzer, can be selected from Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-KIT-1, Ti-TUD-1 or unformed Ti/SiO
2In at least a, wherein the content of titanium is 0.1～20% of catalyst weight in the catalyzer.This titaniferous porous silica catalyzer is synthetic for carrying titanium by direct synthetic or back grafting, has the meso-hole structure feature, as Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-KIT-1, Ti-TUD-1, or has the macroporous structure feature, as unformed Ti/SiO
2This titaniferous porous silica catalyzer is at 960 ± 10cm of infrared absorpting light spectra
-1All have charateristic avsorption band with the 210 ± 10nm place at uv-visible absorption spectra figure, this indicates that titanium has been grafted in the silicon dioxide skeleton and has formed the active titanium species with four-coordination structure.
The present invention can prepare α according to hydrogen phosphide cumene through the reductive agent reduction, the reaction mechanism of alpha-alpha-dimethyl benzylalcohol, on highly active titaniferous porous silica catalyzer, make hydrogen phosphide cumene and alkene generation redox reaction, hydrogen phosphide cumene is reduced to α, alpha-alpha-dimethyl benzylalcohol, the reaction conditions gentleness, selectivity is good.Preferred catalyst of the present invention carries out silanization and handles before use, and the hydroxyl that its surface is existed is converted into the alkyl siloxy, strengthens hydrophobicity, reduces acid.The hydrophobic raising of catalyzer can reduce the absorption of polarity oxidation products at catalyst surface, also can avoid the loss of active constituent titanium on the catalyzer.Adopt the inventive method, than using Na
2SO
3Or Na
2S does that the reductive agent selectivity is the highest to improve 15%.The present invention adopts alkene rather than adopts Na
2SO
3Or Na
2S makes reductive agent, so there is not sulfur-containing waste water to produce, does not have problem of environmental pollution, need not handle waste water, and production cost is low.In addition, because the catalyzer that is adopted is a kind of typical heterogeneous catalyst, so, adopting the α that this method produced, not containing catalyzer in the alpha-alpha-dimethyl benzylalcohol reaction solution, product is not subjected to catalyst contamination, and good product quality has been obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
In room temperature with under stirring, the 15.0g cetylamine joined contain 80ml H
2In the mixing solutions of O, 60ml ethanol and 5ml (1mol/L) hydrochloric acid, be stirred to solution and be a phase.The 4.0g tetrabutyl titanate that will be dissolved in the 65.0g tetraethoxy in the 30ml ethanol and be dissolved in the 10ml ethanol joins in the above-mentioned mixing solutions simultaneously, crystallization 24h behind the stirring 30min.Filter the gained decorating film then, wash with water.Material after the washing behind 110 ℃ of oven dry 12h, at 600 ℃ of roasting 4h, is promptly got the Ti-HMS catalyst Precursors.
In the there-necked flask of a 100ml, add the 50ml cumene solution that contains the 4.0g hexamethyldisilazane, the catalyst Precursors of the above-mentioned preparation of 10.0g is joined in the flask, under stirring fast and refluxing, elevated temperature to 150 ℃, and under this temperature, react 4h.Under this temperature, the hexamethyldisilazane of evaporated in vacuo remnants and isopropyl benzene solvent promptly make the Ti-HMS catalyzer finished product of handling through silanization then.XRD, N
2Absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows that this material has typical HMS constitutional features and Ti has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 2.2%.
[embodiment 2]
Method by [embodiment 1] makes the Ti-HMS catalyst Precursors, and it is carried out silanization handle, and just silylating reagent is a trimethylchlorosilane.XRD, N
2Absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows that this material has typical HMS constitutional features and Ti has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 2.1%.
[embodiment 3]
Method by [embodiment 1] makes the Ti-HMS catalyst Precursors, just it is not carried out silanization and handles.XRD, N
2Absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows that this material has typical HMS constitutional features and Ti has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 2.3%.
[embodiment 4]
In room temperature with under stirring, the 15.0g cetylamine joined contain 80ml H
2In the mixing solutions of O, 60ml ethanol and 5ml (1mol/L) hydrochloric acid, be stirred to solution and be a phase.The 65.0g tetraethoxy that will be dissolved in the 30ml ethanol joins in the above-mentioned mixing solutions, crystallization 24h behind the stirring 30min.Filter the gained decorating film then, wash with water.Material after the washing behind 110 ℃ of oven dry 12h, at 600 ℃ of roasting 4h, is promptly got the support of the catalyst with HMS constitutional features.In the there-necked flask of a 100ml, add and contain 4.0gTiCl
4The 50ml cumene solution, the support of the catalyst of above-mentioned preparation is joined in the flask, under stirring fast and refluxing, elevated temperature to 150 ℃, and under this temperature, react 4h.Then under this temperature, the TiCl of evaporated in vacuo remnants
4With the isopropyl benzene solvent.Add distilled water 30ml after being cooled to 90 ℃ and stir 10min, elevated temperature to 110 ℃ evaporating water promptly makes the Ti-HMS catalyst Precursors then.
In the there-necked flask of a 100ml, add the 50ml cumene solution that contains the 3.5g hexamethyldisilazane, the catalyst Precursors of the above-mentioned preparation of 10.0g is joined in the flask, under stirring fast and refluxing, elevated temperature to 150 ℃, and under this temperature, react 4h.Under this temperature, the hexamethyldisilazane of evaporated in vacuo remnants and isopropyl benzene solvent promptly make the Ti-HMS catalyzer of handling through silanization then.XRD, N
2Absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows that this material has typical HMS constitutional features and Ti has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.4%.
[embodiment 5]
Method by [embodiment 4] makes the Ti-HMS catalyst Precursors, and it is carried out silanization handle, and just silylating reagent is a dimethyldichlorosilane(DMCS).XRD, N
2Absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows that this material has typical HMS constitutional features and Ti has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.5%
[embodiment 6]
The 15.0g aerosil is joined in the tetramethylammonium hydroxide aqueous solution of 24.0g 25wt%, and continuously stirring 30min forms solution.Under agitation above-mentioned solution is joined in the 60.0ml aqueous solution that contains the 23.0g cetyl trimethylammonium bromide subsequently and form clear solution.Above-mentioned mixing solutions is moved in the stainless steel autoclave of the poly-tetrafluoro liner of band in 100 ℃ of static crystallization 3 days.Product after the crystallization is after washing, filtering, and in 100 ℃ of oven dry 24h, 550 ℃ of roasting 6h promptly get the support of the catalyst with MCM-41 constitutional features.In the there-necked flask of a 100ml, add and contain 4.0gTiCl
4The 50ml cumene solution, the support of the catalyst of above-mentioned preparation is joined in the flask, under stirring fast and refluxing, elevated temperature to 150 ℃, and under this temperature, react 4h.Then under this temperature, the TiCl of evaporated in vacuo remnants
4With the isopropyl benzene solvent.Add distilled water 30ml after being cooled to 90 ℃ and stir 10min, elevated temperature to 110 ℃ evaporating water promptly makes the Ti-MCM-41 catalyst Precursors then.
By the method for [embodiment 4] the Ti-MCM-41 catalyst Precursors that makes is carried out silanization and handle, promptly make final Ti-MCM-41 catalyzer finished product.XRD, N
2Absorption, FT-IR and UV-Vis characterize and analytical results shows that this material has typical MCM-41 constitutional features and Ti has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 3.0%.
[embodiment 7]
Method by [embodiment 6] makes the Ti-MCM-41 catalyst Precursors, and it is carried out silanization handle, and just silylating reagent is a dimethyldichlorosilane(DMCS).XRD, N
2Absorption, FT-IR and UV-Vis characterize and analytical results shows that this material has typical MCM-41 constitutional features and Ti has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 2.9%.
[embodiment 8]
The 15.0g aerosil is joined in the tetramethylammonium hydroxide aqueous solution of 24.0g 25wt%, and continuously stirring 30min forms solution.Under agitation above-mentioned solution is joined in the 60.0ml aqueous solution that contains the 23.0g cetyl trimethylammonium bromide subsequently and form clear solution.Slowly be added drop-wise in the above-mentioned mixing solutions and continuation stirring 30min at following 2.4g tetrabutyl titanate of quick stirring.Above-mentioned siliceous and mixing solutions titanium is moved in the stainless steel autoclave of the poly-tetrafluoro liner of band in 100 ℃ of static crystallization 3 days, promptly makes the Ti-MCM-41 catalyst Precursors.
By the method for [embodiment 4] the Ti-MCM-41 catalyst Precursors that makes is carried out silanization and handle, promptly make final Ti-MCM-41 catalyzer finished product.XRD, N
2Absorption, FT-IR and UV-Vis characterize and analytical results shows that this material has typical MCM-41 constitutional features and Ti has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.9%.
[embodiment 9]
Method by [embodiment 8] makes the Ti-MCM-41 catalyst Precursors, just it is not carried out silanization and handles.XRD, N
2Absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows that this material has typical MCM-41 constitutional features and Ti has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 2.1%.
[embodiment 10]
62.4g tetraethoxy and 2.04g tetrabutyl titanate joined in the 20ml dehydrated alcohol form mixing solutions, under agitation 47.5g trolamine and 20ml distilled water successively are added drop-wise in the above-mentioned mixing solutions, and 2.0h is stirred in continuation, then 35.5g tetraethyl ammonium hydroxide (25% the aqueous solution) is added drop-wise in the above-mentioned solution and continues to stir 1h and form colourless transparent solution, at room temperature aging subsequently 24h, in 700 ℃ of roasting 12h, promptly get the Ti-TUD-1 catalyst Precursors behind 100 ℃ of aging 24h.
By the method for [embodiment 4] the Ti-TUD-1 catalyst Precursors that makes is carried out silanization and handle, promptly make final Ti-TUD-1 catalyzer finished product.XRD, N
2Absorption, FT-IR and UV-Vis characterize and analytical results shows that this material has typical TUD-1 constitutional features, and Ti entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.3%.
[embodiment 11]
Method by [embodiment 10] makes the Ti-TUD-1 catalyst Precursors, just adopts the N-trimethyl-silyl-imidazole as silylating reagent it to be carried out silanization and handles.XRD, N
2Absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows that this material has typical TUD-1 constitutional features, and Ti entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.4%.
[embodiment 12]
At 40 ℃, 24.0g segmented copolymer (P123) is dissolved in the hydrochloric acid soln that 1L concentration is 2mol/L, under agitation the 68.0g tetraethoxy is joined in the above-mentioned solution and continues and stir 24h, then it is transferred in the stainless steel cauldron that has poly-tetrafluoro liner in 100 ℃ of crystallization 48h.Product after the crystallization is filtered, washs, after the drying, promptly gets support of the catalyst SBA-15 in 550 ℃ of roasting 6h.In the there-necked flask of a 100ml, add and contain 4.0gTiCl
4The 50ml cumene solution, the support of the catalyst of above-mentioned preparation is joined in the flask, under stirring fast and refluxing, elevated temperature to 150 ℃, and under this temperature, react 4h.Then under this temperature, the TiCl of evaporated in vacuo remnants
4With the isopropyl benzene solvent.Add distilled water 30ml after being cooled to 90 ℃ and stir 10min, elevated temperature to 110 ℃ evaporating water promptly makes the Ti-SBA-15 catalyst Precursors then.
By the method for [embodiment 4] the Ti-SBA-15 catalyst Precursors that makes is carried out silanization and handle, promptly make final Ti-SBA-15 catalyzer finished product.XRD, N
2Absorption, FT-IR and UV-Vis characterize and results of elemental analyses shows that this material has typical SBA-15 constitutional features, and Ti entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 3.4%.
[embodiment 13]
Method by [embodiment 12] makes the Ti-SBA-15 catalyst Precursors, just adopts the aminomethyl phenyl chlorosilane as silylating reagent it to be carried out silanization and handles.XRD, N
2Absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows that this material has typical SBA-15 constitutional features, and Ti entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 3.1%.
[embodiment 14]
With tetraethoxy, cetyl trimethylammonium bromide, EDTA and H
2O 1: 0.25: 1 in molar ratio: 60 ratio mix and stir after be transferred in the stainless steel cauldron of the poly-tetrafluoro liner of band, at 100 ℃ of constant temperature 24h, the re-adjustments pH value is about 10.5, behind the constant temperature secondary, product is taken out, and to be washed with distilled water to pH value be about 7.0, the oven dry back prior in the nitrogen atmosphere 550 ℃ of roastings 1 hour, roasting 6h promptly gets the KIT-1 support of the catalyst in air atmosphere again.In the there-necked flask of a 100ml, add and contain 4.0gTiCl
4The 50ml cumene solution, the support of the catalyst 20.0g of above-mentioned preparation is joined in the flask, under stirring fast and refluxing, elevated temperature to 150 ℃, and under this temperature, react 4h.Then under this temperature, the TiCl of evaporated in vacuo remnants
4With the isopropyl benzene solvent.Add distilled water 30ml after being cooled to 90 ℃ and stir 10min, elevated temperature to 110 ℃ evaporating water promptly makes the Ti-KIT-1 catalyst Precursors then.
By the method for [embodiment 4] the Ti-KIT-1 catalyst Precursors that makes is carried out silanization and handle, promptly make final Ti-KIT-1 catalyzer finished product.XRD, N
2Absorption, FT-IR and UV-Vis characterize and results of elemental analyses shows that this material has typical KIT-1 constitutional features and Ti has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 2.8%.
[embodiment 15]
Method by [embodiment 14] makes the Ti-KIT-1 catalyst Precursors, just adopts the aminomethyl phenyl chlorosilane as silylating reagent it to be carried out silanization and handles.XRD, N
2Absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows that this material has typical KIT-1 constitutional features and Ti has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 3.1%.
[embodiment 16]
In room temperature with under stirring, the 4.3g tetrabutyl titanate is joined the ethanolic soln that forms tetrabutyl titanate in the 20ml ethanol, commercially available silica gel (80-120 order, specific surface area 340m that the 20.0g drying treatment is crossed
2/ g, pore volume 0.71cm
3/ g, mean pore size
) join in the 60ml ethanol.Then under nitrogen atmosphere, the ethanolic soln of tetrabutyl titanate is added drop-wise in the ethanolic soln that contains commercially available silica gel, at room temperature stir this mixture 2h after-filtration, with washing with alcohol filtrate three times.Solid 12h in air atmosphere after 110 ℃ of above-mentioned filtrations of oven dry at 600 ℃ of roasting 4h, promptly gets the unformed Ti/SiO of catalyst Precursors
2
In one 100 milliliters there-necked flask, add the 50ml cumene solution contain the 4.0g hexamethyldisilazane, the catalyst Precursors of the above-mentioned preparation of 10.0g is joined in the flask, under stirring and refluxing, elevated temperature to 150 ℃, and under this temperature, react 4h.Under this temperature, the hexamethyldisilazane of evaporated in vacuo remnants and isopropyl benzene solvent promptly make the unformed Ti/SiO that handles through silanization then
2The catalyzer finished product.FT-IR and UV-Vis characterize and results of elemental analyses shows that titanium has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.0%.
[embodiment 17]
Commercially available silica gel (80-120 order, specific surface area 340m that the 20.0g drying was handled
2/ g, pore volume 0.71cm
3/ g, mean pore size
) be immersed in the 60ml octane solvent.Under stirring and nitrogen atmosphere, will be dissolved with 2.4g TiCl
420ml octane mixture be added drop-wise in the above-mentioned paste mixture, be warming up to 100 ℃ after constant temperature stirring and refluxing 2h, elevated temperature to 150 ℃ solvent evaporated under vacuum condition then.
The sample of above-mentioned acquisition is put in the quartz tube reactor, in nitrogen atmosphere, elevated temperature to 700 ℃, and at this roasting temperature 2h, reduce the temperature to 300 ℃ after, nitrogen purging 2h.Further reduce temperature to 220 ℃, the nitrogen that will contain 6.0g trimethylchlorosilane saturation steam under this temperature is used nitrogen purging 2h then by beds, promptly makes the unformed Ti/SiO that handles through silanization
2The catalyzer finished product.FT-IR and UV-Vis characterize and results of elemental analyses shows that titanium has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.2%.
[embodiment 18]
Method by [embodiment 17] makes unformed Ti/SiO
2Catalyst Precursors does not just carry out silanization to it and handles.FT-IR, UV-Vis characterize and results of elemental analyses shows that titanium has entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.3%.
[embodiment 19～36]
Propylene catalytic reduction hydrogen phosphide cumene prepares α, alpha-alpha-dimethyl benzylalcohol (DMBA)
The catalyzer 2.0g of [embodiment 1～18] joined fill 55.0g 30.0 (weight) % hydrogen phosphide cumene (CHP, isopropyl benzene is a solvent) the 300ml stainless steel autoclave in, behind the elevated temperature to 90 ℃, charge into the 45.0g propylene, system pressure is 1.5MPa, stirring reaction 2h, reaction result sees Table 1.
Table 1
[embodiment 37～54]
Tetrahydrobenzene catalytic reduction hydrogen phosphide cumene prepares α, alpha-alpha-dimethyl benzylalcohol (DMBA)
The catalyzer 2.0g of [embodiment 1～18] joined fill 55.0g gram 30 (weight) % hydrogen phosphide cumene (CHP, isopropyl benzene is a solvent) 100ml have in the there-necked flask of reflux condensation mode, behind the elevated temperature to 80 ℃, add the 18.0g tetrahydrobenzene, system pressure is 0.1MPa, stirring reaction 2h, reaction result sees Table 2.
Table 2
[embodiment 55～72]
Cyclooctene catalytic reduction hydrogen phosphide cumene prepares α, alpha-alpha-dimethyl benzylalcohol (DMBA)
The catalyzer 2.0g of [embodiment 1～18] joined fill 55.0g 30.0 (weight) % hydrogen phosphide cumene (CHP, isopropyl benzene is a solvent) 100 milliliters of there-necked flasks that have a reflux condensation mode in, behind the elevated temperature to 80 ℃, add the 24.0g cyclooctene, system pressure is 0.1MPa, under agitation react 2h, reaction result sees Table 3.
Table 3
[comparative example 1]
The hydrogen phosphide cumene solution (CHP, isopropyl benzene are solvent) that takes by weighing 60.8g 50 (weight) % joins 200ml and takes back in three mouthfuls of glass flask of stream prolong, during elevated temperature to 65 ℃, starts magnetic agitation, slowly with the Na of 14.5g 30 (weight) %
2The S aqueous solution is added drop-wise in the flask, treats Na
2After the S aqueous solution dropwises, continue stirring reaction 30min, can think that reaction finishes.Take out reaction product and analyze, draw the α of generation by analysis, the weight of alpha-alpha-dimethyl benzylalcohol (DMBA) is 20.6g, produces simultaneously to contain 7.5gNa
2SO
4And Na
2The about 18.0g of the waste water of S.The transformation efficiency of hydrogen phosphide cumene and α, the selectivity of alpha-alpha-dimethyl benzylalcohol (DMBA) sees Table 4.
[comparative example 2]
The hydrogen phosphide cumene solution (CHP, solvent are isopropyl benzene) that takes by weighing 60.8g 50 (weight) % joins 200ml and takes back in three mouthfuls of glass flask of stream prolong, during elevated temperature to 65 ℃, starts magnetic agitation, slowly with the Na of 104g25%
2SO
3The aqueous solution is added drop-wise in the flask, treats Na
2SO
3After the aqueous solution dropwises, continue stirring reaction 30min, can think that reaction finishes.Take out the oil phase reaction product and carry out chromatogram and iodometric titrationiodimetry titration analysis, draw the α of generation by analysis, the weight of alpha-alpha-dimethyl benzylalcohol (DMBA) is 20.2g, and generation simultaneously contains 29.3g and contains Na
2SO
4And Na
2SO
3Waste water 108.0g.The transformation efficiency of hydrogen phosphide cumene and α, the selectivity of alpha-alpha-dimethyl benzylalcohol (DMBA) sees Table 4.
Table 4
Claims (9)
1. α, the preparation method of alpha-alpha-dimethyl benzylalcohol, with alkene and hydrogen phosphide cumene is raw material, reaction system is the inert nonpolar organic compound is solvent, in temperature of reaction is 0～150 ℃, reaction pressure is 0.1～10.0MPa, the mol ratio of alkene and hydrogen phosphide cumene is 0.1～20: 1, the weight ratio of hydrogen phosphide cumene and solvent is 0.01～9: 1, catalyst levels is to react under 0.01～200% condition of hydrogen phosphide cumene weight to obtain described α, alpha-alpha-dimethyl benzylalcohol in 0.1～24 hour;
Wherein, described catalyzer is selected from Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-KIT-1, Ti-TUD-1 or unformed Ti/SiO
2In at least a; Wherein titanium content is 0.1～20% of a catalyst weight in the catalyzer.
2. according to the described α of claim 1, the preparation method of alpha-alpha-dimethyl benzylalcohol is characterized in that described catalyzer is selected from Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15 or unformed Ti/SiO
2In at least a; Wherein titanium content is 0.2～10% of a catalyst weight in the catalyzer.
3. according to the described α of claim 2, the preparation method of alpha-alpha-dimethyl benzylalcohol is characterized in that described catalyzer is selected from Ti-HMS, Ti-MCM-41 or unformed Ti/SiO
2In at least a; Wherein titanium content is 0.5～5% of a catalyst weight in the catalyzer.
4. according to the described α of claim 1, the preparation method of alpha-alpha-dimethyl benzylalcohol, before it is characterized in that catalyzer uses, handled 0.5～48 hour with the organic silicon solution that is dissolved in the organic solvent, or under gas phase condition, use organosilicon steam treatment 0.5～48 hour at 0～400 ℃ at 0～400 ℃; Wherein organosilicon is selected from least a in halosilanes, silazane or the silylamine, and the organosilicon consumption is 0.1～100% of a catalyst weight.
5. according to the described α of claim 4, the preparation method of alpha-alpha-dimethyl benzylalcohol, before it is characterized in that catalyzer uses, handled 1～24 hour with the organic silicon solution that is dissolved in the organic solvent at 50～350 ℃, or 50～350 ℃ under gas phase condition with organosilicon steam treatment 1～24 hour, the organosilicon consumption is 1～50% of a catalyst weight;
Described halosilanes is selected from least a in trimethylchlorosilane, chlorotriethyl silane, tripropyl chlorosilane, tributyl chlorosilane, chlorodimethyl silane, dimethyldichlorosilane(DMCS), 3,5-dimethylphenyl chlorosilane, dimethyl ethyl chlorosilane, dimethyl n propyl chloride silane, dimethyl isopropyl chloride silane, normal-butyl dimethylchlorosilane or the aminomethyl phenyl chlorosilane;
Described silazane is selected from hexamethyldisilazane, 1,1,3,3-tetramethyl-disilazane, 1,3-two (chloromethyl) tetramethyl-disilazane, 1,3-divinyl-1,1,3,3-tetramethyl-disilazane or 1, at least a in the 3-phenylbenzene tetramethyl-disilazane;
Described silylamine is selected from least a in N-trimethyl-silyl-imidazole, N-t-butyldimethylsilyl imidazoles, N-dimethylethylsilyl imidazoles, N-dimethyl n propyl group silyl imidazoles, N-dimethyl sec.-propyl silyl imidazoles, N-trimethyl silyl dimethyl amine or the N-trimethyl silyl diethylamide.
6. according to the described α of claim 5, the preparation method of alpha-alpha-dimethyl benzylalcohol is characterized in that described halosilanes is selected from trimethylchlorosilane, and described silazane is selected from hexamethyldisilazane or 1,1,3, at least a in the 3-tetramethyl-disilazane.
7. according to the described α of claim 1, the preparation method of alpha-alpha-dimethyl benzylalcohol is characterized in that described alkene is selected from alkene, cycloolefin, fragrant alkene, chloro-alkenes or hydroxyl alkene; Describedly reaction system is the inert non-polar organic solvent is selected from least a in benzene,toluene,xylene, ethylbenzene, diethylbenzene, isopropyl benzene, diisopropylbenzene(DIPB), normal butane, Trimethylmethane, pentane, normal hexane, hexanaphthene, heptane, octane, nonane, decane, undecane hydrocarbon or the dodecane hydrocarbon.
8. according to the described α of claim 7, the preparation method of alpha-alpha-dimethyl benzylalcohol is characterized in that described alkene is selected from ethene, propylene, butylene, amylene or hexene; Described cycloolefin is selected from cyclopentenes, tetrahydrobenzene, cyclooctene or cyclododecene; Described fragrant alkene is selected from vinylbenzene or alpha-methyl styrene; Described chloro-alkenes is selected from propenyl chloride; Hydroxyl alkene is selected from vinyl carbinol; Describedly reaction system is the inert non-polar organic solvent is selected from isopropyl benzene.
9. according to the described α of claim 1, the preparation method of alpha-alpha-dimethyl benzylalcohol, it is characterized in that temperature of reaction is 40～130 ℃, reaction pressure is 0.1～6.0MPa, the mol ratio of alkene and hydrogen phosphide cumene is 0.5～15: 1, the weight ratio of hydrogen phosphide cumene and solvent is 0.1～4: 1, and catalyst levels is 0.1～100% of a hydrogen phosphide cumene weight, and the reaction times is 0.2～5 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230856A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Production method of epoxybutane |
| CN105272945A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Production method for epichlorohydrin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3923843A (en) * | 1972-03-13 | 1975-12-02 | Shell Oil Co | Epoxidation process with improved heterogeneous catalyst |
| US4367342A (en) * | 1969-04-02 | 1983-01-04 | Shell Oil Company | Olefin epoxidation |
| CN1248579A (en) * | 1998-08-04 | 2000-03-29 | 住友化学工业株式会社 | Process for preparing propylene oxide |
| CN1500004A (en) * | 2001-01-31 | 2004-05-26 | ס�ѻ�ѧ��ҵ��ʽ���� | Process for prodn. of titanium-contg. silicon oxide catalysts |
| CN101307039A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Method for producing epoxide |
-
2010
- 2010-06-24 CN CN2010102081537A patent/CN102295533B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367342A (en) * | 1969-04-02 | 1983-01-04 | Shell Oil Company | Olefin epoxidation |
| US3923843A (en) * | 1972-03-13 | 1975-12-02 | Shell Oil Co | Epoxidation process with improved heterogeneous catalyst |
| CN1248579A (en) * | 1998-08-04 | 2000-03-29 | 住友化学工业株式会社 | Process for preparing propylene oxide |
| CN1500004A (en) * | 2001-01-31 | 2004-05-26 | ס�ѻ�ѧ��ҵ��ʽ���� | Process for prodn. of titanium-contg. silicon oxide catalysts |
| CN101307039A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Method for producing epoxide |
Non-Patent Citations (1)
| Title |
|---|
| 李学峰等: "硅烷化对Ti/HMS分子筛催化性能的影响", 《催化学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230856A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Production method of epoxybutane |
| CN104230856B (en) * | 2013-06-17 | 2016-06-08 | 中国石油化工股份有限公司 | The production method of butylene oxide ring |
| CN105272945A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Production method for epichlorohydrin |
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