CN110143871A - A kind of preparation method of dicarboxylic acids diol ester - Google Patents
A kind of preparation method of dicarboxylic acids diol ester Download PDFInfo
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- CN110143871A CN110143871A CN201810143937.2A CN201810143937A CN110143871A CN 110143871 A CN110143871 A CN 110143871A CN 201810143937 A CN201810143937 A CN 201810143937A CN 110143871 A CN110143871 A CN 110143871A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
Abstract
The present invention relates to a kind of preparation methods of dicarboxylic acids diol ester, comprising: in the presence of a catalyst, by aliphatic dicarboxylic acid and monohydric alcohol haptoreaction, while except the water of dereaction generation；The catalyst is the bulk phase catalyst of siliceous, tin and oxygen and contains Sn-O-Si key.The conversion ratio and selectivity of the method for the present invention are high, and recycle stock is few, and Atom economy is stronger.
Description
Technical field
The present invention relates to a kind of preparation methods of dicarboxylic acids diol ester, and in particular to a kind of fat that can be used as plasticizer
The preparation method of race's dicarboxylic acids diol ester.
Background technique
Plasticizer is in the high molecular materials such as a kind of addition plastics, resin, elastomer, for improve they processability,
The auxiliary agent of plasticity, flexibility, draftability.Plasticizer can be divided into primary plasticizer and extender plasticizer.Aliphatic dibasic acid ester
Plasticizer has unique cryogenic property, is commonly used as improving the extender plasticizer of material cold resistance.
CN107188803A discloses a kind of production method of cold resistant plasticizer dodecanedicarboxylic acid diester, and this method uses
Titanate esters are catalyst, and molar ratio of alcohol to acid is 2.6:1~2.9:1.CN1618847A disclose a kind of dibasic acid ester plasticizer and
Its manufacturing method, alcohol used in this method contain ehter bond.CN104592015A proposes that with decanedioic acid, 2-Ethylhexyl Alcohol be original
Material, using stannous oxide as catalyst preparation dioctyl sebacate, after the reaction was completed plus alkali carries out neutralization washing, and vacuum distillation is lived
Property charcoal adsorption filtration after obtain purified product.
Esterification is one of most important organic reaction, and product is widely used in the every field of chemical industry.Ester
Change reaction to generally require using catalyst, catalyst used can be divided into acidic catalyst and non-acidic catalyst.Acidic catalyst
Agent is some inorganic acids and organic acid, and major defect is that reaction selectivity is poor, additionally, there may be burn into pollution, catalyst cannot
The problems such as recycling is reused, product post-processing is difficult.Non-acidic catalyst is mainly aluminium, titanium, zirconium, tin, zinc, magnesium, antimony, bismuth etc.
The compound of metal, these compounds can be used alone, and can also be made composite catalyst, typically no corrosivity, and
And the selectivity of reaction is relatively high.Titanate esters are a kind of nonacid homogeneous catalysts, although catalytic activity is higher, need from
It is decomposed in reaction product and removes catalyst, cause difficulty to the post-processing of product.As esterification catalyst, the catalysis of stannous oxide
It is active high, but stannous oxide, when catalytic hydroxy acid esterifying reacts, catalyst is easy refinement and inactivation is very fast, is unfavorable for continuous esterification
The long-term operation of technique and the catalyst of batch esterification technique are reused.
CN1760339A, CN1740277A disclose stannous supported catalyst, and are used for high-acid crude oil or evaporate
Divide the esterification decarboxylation of oil.US3520915 also discloses that stannous supported catalyst, catalyst be used to prepare unsaturated lipid
Fat nitrile.Wenlei Xie etc. discloses stannic supported catalyst, and catalyst is used for the ester exchange reaction of soybean oil
(Silica-Supported Tin Oxides as Heterogeneous Acid Catalysts for
Transesterification of Soybean Oil with Methanol, Ind.Eng.Chem.Res.2012,51,
225–231).These catalyst not can be well solved refinement and the deactivation prob of catalyst.Vinicius etc. discloses aluminium
With stannous composite oxides, and it is used for the esterification of soya fatty acid, the results showed that " with stannous oxide phase
Than the catalytic activity of composite oxides lowers " (Metal oxides as heterogeneous catalysts for
Esterification of fatty acids obtained from soybean oil, Fuel Processing
Technology, 2011,92,53-57).
Summary of the invention
The present invention provides a kind of preparation methods of dicarboxylic acids diol ester, and the method use a kind of new catalyzing esterifications
Thus agent has higher catalytic activity and selectivity, and the catalyst is easy to separate with reaction product, and can be repeated several times makes
With.
Specifically, the invention mainly comprises the following contents:
1. a kind of preparation method of dicarboxylic acids diol ester, comprising: in the presence of a catalyst, by aliphatic dicarboxylic acid
With monohydric alcohol haptoreaction, while except dereaction generate water；The catalyst is the bulk phase catalyst of siliceous, tin and oxygen and contains
There is Sn-O-Si key；The monohydric alcohol has structure shown in formula R-OH, and wherein R is the alkane of unsubstituted alkyl or ether-containing key
Base.
2. according to preparation method described in 1, which is characterized in that the monohydric alcohol is one of the alkanol of C6~C14
Or it is several.
3. according to aforementioned any preparation method, which is characterized in that the monohydric alcohol be n-butanol, n-hexyl alcohol, n-octyl alcohol,
Isooctanol, Decanol, isodecanol, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol propyl ether, butyl, diethyl
Glycol ethyl butyl ether, dipropylene glycol methyl ether or dipropylene glycol t-butyl ether.
4. according to aforementioned any preparation method, which is characterized in that the aliphatic dicarboxylic acid is the binary of C6~C14
One or more of carboxylic acid (preferably 1,6- adipic acid, 1,8- suberic acid, 1,9- azelaic acid or 1,10- decanedioic acid).
5. according to aforementioned any preparation method, which is characterized in that while reaction, be passed through inert gas (preferably nitrogen
Gas).
6. according to aforementioned any preparation method, which is characterized in that under reflux state, reaction 2h~10h (preferably 3h~
5h)。
7. according to aforementioned any preparation method, which is characterized in that alcohol and acid molar ratio be 2:1~4:1 (preferably
2.4:1~3:1).
8. according to aforementioned any preparation method, which is characterized in that the dosage of catalyst is the 0.1% of reactant gross mass
~10% (preferably 0.5%~2%).
9. according to aforementioned any preparation method, which is characterized in that further include: after reaction, vacuum distillation removing is light
The step of the step of component and decoloration.
10. according to aforementioned any preparation method, which is characterized in that the catalyst is the body being made of silicon, tin and oxygen
Phase catalyst.
11. according to aforementioned any preparation method, which is characterized in that in the catalyst, the molar ratio of silicon and tin is 0.8
~6 (preferably 1.5~5).
12. according to aforementioned any preparation method, which is characterized in that in the catalyst, the mass fraction of tin is 23%
~65% (preferably 26%~53%).
13. according to aforementioned any preparation method, which is characterized in that in the catalyst, the valence state of tin is divalent or four
Valence.
14. according to aforementioned any preparation method, which is characterized in that in the Raman spectrum of the catalyst, in 237cm-1
Nearby there are a characteristic peaks.
15. according to aforementioned any preparation method, which is characterized in that in the Raman spectrum of the catalyst, in 110cm-1
Neighbouring and 211cm-1There is no vibration peak nearby or there are the lesser characteristic peaks of relative intensity.
16. according to aforementioned any preparation method, which is characterized in that in the XRD spectrum of the catalyst, the not no oxygen of tin
The characteristic peak of compound crystal.
17. according to aforementioned any preparation method, which is characterized in that the catalyst is unformed solid.
18. according to aforementioned any preparation method, which is characterized in that after reaction, isolate catalyst, and this is urged
Agent is recycled and reused for the method.
19. a kind of processing method of plastics, which is characterized in that dicarboxylic acids two made from using any one of 1~18
Alcohol ester is as plasticizer.
In the prior art, stannous oxide is preferable nonacid esterification catalyst, but the catalyst has inactivation faster
Problem, more seriously, the catalyst are easy refinement, cause to be difficult to separate catalyst with reaction product, give actual production band
Carry out very big difficulty, the prior art can not be solved these problems ideally by loading or metal composite oxide being made.This hair
Bright people has been surprisingly found that in test, is co-precipitated with silicate and pink salt, and active higher, selectivity can be made more preferably and do not send out
The high temperature esterification catalyst of raw refinement；Also unexpectedly, the tetravalence tin catalyst that the method obtains also have good work
Property, selectivity and thermal stability.Due to this discovery, the present inventor proposes and completes the present invention.
The invention has the following advantages that being combined more in used catalyst containing new tin species and silicon, tin, between oxygen
Securely, to make reaction that there is higher conversion ratio and selectivity；And catalyst is easy to separate with reaction product and can be more
Secondary reuse；When stoichiometric ratio of the reactant dosage close to reaction, very high conversion ratio and selectivity still can reach,
Recycle stock is seldom, and Atom economy is stronger.In addition, method of the invention does not need to include washing step (alkali cleaning and washing).
Other features and advantages of the present invention will be further described in specific embodiment part.
Detailed description of the invention
Fig. 1 is the XPS photoelectron spectroscopy of stannous oxide and stannic oxide.
Fig. 2 is the photoelectron spectroscopy for preparing the catalyst A in embodiment 1 and the catalyst G in preparation comparative example 1.
Fig. 3 is the Raman light for preparing the catalyst A in embodiment 1, the catalyst G in preparation comparative example 1 and stannous oxide
Spectrum.
Fig. 4 is the scanning electron microscope (SEM) photograph of stannous oxide.
Fig. 5 is the scanning electron microscope (SEM) photograph for preparing the catalyst A in embodiment 1.
Fig. 6 is the scanning electron microscope (SEM) photograph for preparing the catalyst G in comparative example 1.
Fig. 7 is the XRD spectrum of stannous oxide.
Fig. 8 is the XRD spectrum for preparing the catalyst J in comparative example 4.
Fig. 9 is the XRD spectrum for preparing the catalyst E in embodiment 5.
Specific embodiment
Below in conjunction with the specific embodiment detailed description present invention, but it should be noted that, protection scope of the present invention is not by these
The limitation that specific embodiment and principle are explained, but determined by claims.
In the present invention, other than the content clearly stated, any matters or item that do not mention are directly applicable in ability
Without carrying out any change those of known to domain.Moreover, any embodiment described herein can with it is described herein
One or more other embodiments freely combine, and the technical solution or technical idea being consequently formed are accordingly to be regarded as the original public affairs of the present invention
It opens or a part of original description, and is not considered as the new content for not disclosing or being expected herein, unless this field skill
Art personnel think that the combination is obvious unreasonable.
All features disclosed in this invention can in any combination, these combinations should be understood presently disclosed or note
The content of load, unless those skilled in the art think that the combination is obviously unreasonable, such as in the present invention, " silicon and tin molar ratio
The combination of any range " and " any ranges of Theil indices in catalyst " should all be considered as specifically being disclosed and being remembered by the present invention
It carries.Numerical point disclosed in this specification includes not only specifically disclosed numerical point in embodiment, further includes each number in specification
It is worth the endpoint of range, the range of these numerical point institute any combination is regarded as the range that the present invention is disclosed or recorded.
Technical and scientific term in the present invention, provide definition be subject to its definition, do not provide definition then by ability
The common meaning in domain understands.
In the present invention, " optional " is meant that, including or does not include that for example " optional A " refers to including A or do not include A.
In the present invention, inert gas refers to the gas having no adverse effect to catalyst performance.
In catalyst of the invention, the sum of each component content is 100%.
The present invention provides a kind of preparation methods of dicarboxylic acids diol ester, comprising: in the presence of a catalyst, will be fatty
Race's dicarboxylic acids and monohydric alcohol haptoreaction, while except the water of dereaction generation；The catalyst is the body phase of siliceous, tin and oxygen
Catalyst and contain Sn-O-Si key；The monohydric alcohol have formula R-OH shown in structure, wherein R be unsubstituted alkyl or
The alkyl of ether-containing key.
According to the present invention, the monohydric alcohol can be the alkanol of C6~C14, preferably n-butanol, n-hexyl alcohol, just pungent
Alcohol, isooctanol, Decanol, isodecanol, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol propyl ether, butyl,
Diethylene glycol ethyl butyl ether, dipropylene glycol methyl ether or dipropylene glycol t-butyl ether.
According to the present invention, the aliphatic dicarboxylic acid can be one or more of the dicarboxylic acids of C6~C14, excellent
It is selected as 1,6- adipic acid, 1,8- suberic acid, 1,9- azelaic acid or 1,10- decanedioic acid.
According to the present invention, the dicarboxylic acids diol ester is preferably diisodecyl adipate (DIDA), dioctyl azelate, the last of the ten Heavenly stems two
Dibutyl phthalate, dioctyl sebacate or Plexol 201.
According to the present invention, 2h~10h is generally reacted at reflux, preferably reaction 3h~5h.
According to the present invention, the molar ratio of acid and alcohol is (1:2)~(1:4), preferably (1:2.4)~(1:3).
According to the present invention, as a kind of means for adjusting regurgitant volume and/or a kind of measure for protecting reaction system, Ke Yi
While reaction, it is passed through inert gas into reactor, for example is passed through nitrogen or argon gas.
According to the present invention, if reaction raw materials alcohol azeotrope with water, can not additionally be added water entrainer, but use reaction raw materials
Alcohol itself is used as water entrainer.
According to the present invention, if necessary to use water entrainer, water entrainer can be benzene,toluene,xylene, hexamethylene, methyl
Hexamethylene, petroleum ether or di-n-butyl ether.The dosage of the water entrainer can be the 10%~50% of reactant gross mass, preferably
It is the 20%~30% of reactant gross mass.
According to the present invention, the dosage of the catalyst be reactant gross mass 0.1%~10%, preferably 0.5%~
2%.
According to the present invention, the method also includes: after the completion of reaction, isolate catalyst, and the catalyst is repeated
For the method.
According to the present invention, the method also includes: after the completion of reaction, by vacuum distillation remove light component the step of and
The step of decoloration.In the decolorization process, it is preferred to use the mode of activated carbon adsorption, adsorption temp can be 90 DEG C~120 DEG C,
Preferably 100 DEG C~110 DEG C；Adsorption time can be 1h~4h, preferably 2h~3h.
According to the present invention, the catalyst is the bulk phase catalyst of siliceous, tin and oxygen and contains Sn-O-Si key, preferably
The bulk phase catalyst that be made of silicon, tin and oxygen and contains Sn-O-Si key.
According to the present invention, in the catalyst, as optional component, the other elements other than tin can be contained.The present invention
These elements are not particularly limited, as long as these elements do not adversely affect to catalyst performance or have others significantly
Benefit, so that it may these elements are introduced when preparing the catalyst, these elements include but is not limited to aluminium, titanium, zirconium, tin, zinc,
One or more of magnesium, antimony and bismuth.
According to the present invention, in the catalyst, impurity can be contained, as long as its type and content does not significantly reduce catalyst
Performance.In general, in catalyst of the invention, in terms of sodium oxide molybdena, the mass fraction of sodium is lower than 0.03%.
Unlike the prior art, the catalyst is bulk phase catalyst.The analysis of XPS the result shows that, body phase is made
Catalyst causes new tin species to generate, and hence improves the performance of tin catalyst.Due to not using tradition in bulk phase catalyst
Carrier, therefore can break through the load capacity of supported catalyst and the limitation of Active components distribution, there is the catalyst can more
Low silicon tin molar ratio, still improves the catalytic activity, selectivity and stability of tin catalyst at this time, and make catalyst be easy with
Reaction product separation；The catalyst can also have high silicon tin molar ratio (1~22), and catalyst has more preferably stable at this time
Property, and be easier to separate with reaction product.The present invention is not particularly limited the molar ratio of silicon and tin, in the teachings of the present invention
Under, those skilled in the art easily choose suitable silicon tin molar ratio.
According to the present invention, in the catalyst, the molar ratio of silicon and tin can be 0.5~22, preferably 0.8~6, more excellent
It is selected as 1~5, further preferred 1.5~5.
According to the present invention, in the catalyst, the mass fraction of tin can be 8%~72%, preferably 23%~65%,
More preferably 26%~61%, further preferred 26%~53%.
According to the present invention, in the catalyst, the valence state of tin can be divalent and/or tetravalence, preferably divalent.
, according to the invention it is preferred in the XRD spectrum of the catalyst, the not no characteristic peak of the oxide crystal of tin, i.e.,
There is no the characteristic peak of tin oxide crystal and stannous oxide crystal.The catalyst roasts 3h at 500 DEG C under nitrogen protection
Afterwards, in XRD spectrum, there is no sharp crystal characteristic peak between 5 °~70 °；And existing silica gel load tin catalyst,
After handling under similarity condition, then occurs sharp crystal characteristic peak within this range.
According to the present invention, by the XRD spectrum of the catalyst it is found that the catalyst is unformed solid.
Under nitrogen protection, after the catalyst roasts 3h at 300 DEG C, in Raman spectrum, in 237cm-1Nearby deposit
In a characteristic peak；And the tin catalyst of existing silica gel load, it is after being handled under similarity condition, then special without this nearby herein
Levy peak or there is with 110cm-1Neighbouring characteristic peak and 211cm-1The neighbouring characteristic peak feature all small compared to relative intensity
Peak.Wherein, the relative intensity of two characteristic peaks is compared with the peak area size of the two, peak area big characteristic peak relative intensity
Larger, the relative intensity of the small characteristic peak of peak area is smaller.
, according to the invention it is preferred in the Raman spectrum of the catalyst, in 110cm-1Neighbouring and 211cm-1Do not have nearby
Characteristic peak.
In a kind of situation, after the catalyst roasts 3h at 300 DEG C under nitrogen protection, in Raman spectrum,
110cm-1Neighbouring and 211cm-1Nearby without characteristic peak；And the tin catalyst of existing silica gel load, it is handled under similarity condition
Afterwards, then in 110cm-1Neighbouring and 211cm-1Nearby respectively there is an apparent characteristic peak.
In another case, after the catalyst roasts 3h at 300 DEG C under nitrogen protection, in Raman spectrum,
110cm-1Neighbouring and 211cm-1Nearby there is characteristic peak, but existing characteristic peak and 237cm-1Neighbouring characteristic peak is compared, phase
All small to intensity (such as in 110cm-1Neighbouring and 211cm-1Nearby respectively have a characteristic peak, any characteristic peak with
237cm-11/2) peak area ratio of neighbouring characteristic peak is both less than；And the tin catalyst of existing silica gel load, under similarity condition
After processing, if in 237cm-1Nearby there is characteristic peaks, then in 110cm-1Neighbouring and 211cm-1Any feature nearby occurred
Peak, relative intensity is all very big by comparison, and the ratio between peak area is much larger than 1.
The present invention provides the preparation methods of the catalyst, including being co-precipitated to the pink salt and silicate that are dissolved in water
The step of；In the water, dissolved with or not dissolved with sour (preferably inorganic acid, such as hydrochloric acid, sulfuric acid or nitric acid)；In the water, dissolved with
Or not dissolved with other metal salts other than tin.
In the preparation method of the catalyst, the mode of co-precipitation is not particularly limited, existing suitable mode is all
It can be used.For example the aqueous solution of pink salt can be both added in aqueous silicate solution, aqueous silicate solution can also be added
Into the aqueous solution of pink salt, the two can also directly be mixed or be mixed in a manner of being added dropwise simultaneously, then be allowed to precipitate
Entirely.If acid is added, preferable mode is that acid is charged first in tin salt aqueous solution, then again by tin salt aqueous solution and silicate
Aqueous solution mixing；If other metal salts are added, preferable mode is also that other metal salts are charged first in tin salt aqueous solution,
Then tin salt aqueous solution is mixed with aqueous silicate solution again；If acid and other metal salts are added simultaneously, preferable mode is
Acid and other metal salts are all added in tin salt aqueous solution, then use tin salt aqueous solution impregnated carrier again.
In the preparation method of the catalyst, the silicate is generally one or more of sodium metasilicate and potassium silicate.
In the preparation method of the catalyst, the pink salt is generally stannous chloride (including anhydrous stannous chloride or two water
Stannous chloride), one or more of tin tetrachloride (including anhydrous stannic chloride or stannic chloride pentahydrate) and stannous sulfate.
In the preparation method of the catalyst, the molar ratio silicon of silicon and tin can be 0.5~22, preferably 0.8~6, more
Preferably 1~5, further preferably 1.5~5.
The dosage of the preparation method of the catalyst, silicate and pink salt is respectively with the mole of silicon atom and tin atom
Meter, sour dosage preferably satisfy following relationship with the molar amount of releasable proton, the dosage of silicate, pink salt and acid: MSi-
MSn=2 × MProton。
In the preparation method of the catalyst, the type and dosage of other metal salts are not particularly limited, only
Not adversely affect or have other benefits significantly to catalyst performance, so that it may introduce when preparing the catalyst suitable
Other metal salts of equivalent.Other described metal salts are preferably selected from aluminium salt, titanium salt, zirconates, pink salt, zinc salt, magnesium salts, antimonic salt and bismuth
One or more of salt.
In the preparation method of the catalyst, the temperature of co-precipitation is generally at room temperature (such as 25 DEG C~40 DEG C).
In the preparation method of the catalyst, this method further includes, and after mixing reactant, adjusts the behaviour of aqueous pH values
Make.The general pH value for adjusting water phase is 2~12, preferably 4~8, more preferable 4~7.The present invention exchange section aqueous pH values medicament and
Mode is not particularly limited, and is adjusted with common aqueous alkali, such as with NaOH aqueous solution, KOH aqueous solution or ammonium hydroxide
Solution carrys out the pH value of regulation system.
In the preparation method of the catalyst, after co-precipitation, preferably precipitating is kept a period of time in water, it is general to keep
0.1h~8h can (preferably 0.5h~5h)；The temperature kept in water is generally 25 DEG C~70 DEG C, temperature when preferably precipitating
Degree.
In the preparation method of the catalyst, by filtering, easily the precipitating can be separated from water phase.
In the preparation method of the catalyst, the precipitating (is generally washed) preferably through washing, heat treatment, then
To catalyst of the invention.
In the preparation method of the catalyst, the temperature of the heat treatment is generally 80 DEG C~600 DEG C, preferably 200 DEG C~
500 DEG C, more preferable 250 DEG C~350 DEG C.The heat treatment, is preferably handled under inert gas protection, such as in nitrogen
Or it is carried out under the protection of argon gas.The time of the heat treatment is generally 2h~5h, preferably 3h~5h.
Embodiment part
The present invention will be described in detail by the following examples, and however, the present invention is not limited to these examples.
In the context of the present specification, all medicaments and raw material both can be commercially available, can also know according to having
Know manufacture.In embodiment below and comparative example, unless otherwise specified, used reagent is that analysis is pure.
In the context of the present specification, it is included in embodiment below and comparative example, the oxidation in test and analysis
Stannous then passes through the processing of " under nitrogen protection, roasting 3 hours at 200 DEG C " unless otherwise instructed；Oxygen in test and analysis
Change tin unless otherwise instructed, then passes through the processing of " under nitrogen protection, roasting 3 hours at 500 DEG C ".
In the context of the present specification, it is included in embodiment below and comparative example, X-ray photoelectron spectroscopic analysis
(XPS) using the ESCALab220i-XL type x-ray photoelectron spectroscopy of VG Scientific company production.(test condition:
Excitation light source is monochromatization Al K α X-ray, and power 300W, base vacuum is 3 × 10-9Mbar, electron binding energy simple substance carbon
The peak C1s correction.).
In the context of the present specification, it is included in embodiment below and comparative example, X-ray fluorescence spectra analysis
(XRF) using the 3271E type Xray fluorescence spectrometer of Rigaku electric machine industry Co., Ltd. production, with scintillation counter and
Proportional counter detects the intensity of spectral line, carries out quantitative and semi-quantitative analysis (test condition: powder pressure to constituent content with external standard method
Sheetmolding, rhodium palladium, excitation voltage 50kV, excitation current 50mA).
In the context of the present specification, it is included in embodiment below and comparative example, Atomic Emission Spectrometer AES (ICP-
AES) (test condition: catalyst is dissolved in using the measurement of 16 type inductively coupled plasma atomic emission of U.S. Atom Scan
HCl and HF volume ratio are to be cleared up in the solution of 50:1 using the microwave dissolver of U.S. CE M production.).
In the context of the present specification, it is included in embodiment below and comparative example, Raman spectrum uses France JY
Company LAM-800 laser co-focusing Raman spectrometer (test condition: incident light 532nm, resolution ratio 4cm-1, scanning range
For 100~1200cm-1)。
In the context of the present specification, it is included in embodiment below and comparative example, scanning electron microscope (SEM)
Using FEI Co. production Quanta 200F type scanning electron microscope (test condition: sample drying processing after, be evaporated in vacuo metal spraying,
To increase electric conductivity and contrast effect, analytic electron microscope accelerating potential 20.0KV, amplification factor is 1~30k).
In the context of the present specification, it is included in embodiment below and comparative example, X-ray powder diffraction (XRD)
Using the D5005 type X-ray diffractometer (test condition: Cu target, K α radiation, Ni filter plate, pipe electricity of Siemens production
Press 35kV, tube current 45mA, 2 θ=5~70 ° of scanning range).
In the context of the present specification, it is included in embodiment below and comparative example, the calculation method of esterification yield is
It is as follows:
The measurement of acid value is using method specified in GB-1668-2008-T in above-mentioned esterification yield calculation method.
In the context of the present specification, it is included in embodiment below and comparative example, esterification selectively uses
U.S.'s Agilent 7890A gas chromatograph, chromatographic condition: capillary column (50m × 0.2mm × 0.5 μm), fid detector, inspection
280 DEG C of room temperature are surveyed, column temperature, to 260 DEG C, is gasified 280 DEG C of room temperature, hydrogen flowing quantity 30mL/min by 60 DEG C of temperature programmings, air
Flow 400mL/min, nitrogen pressure 10MPa.
Calculation method is as follows:
Prepare embodiment 1
Take 2.26g stannous chloride dihydrate (SnCl2·2H2O it) is dissolved in 10ml deionized water, takes Na2O·SiO2·9H2O
It is dissolved in deionized water.Two kinds of solution are added in flask simultaneously at 30 DEG C, the Si/Sn ratio that feeds intake is 1, and ammonia spirit is added
Adjusting pH value is 6, after precipitating is complete, continues to be kept for 2 hours at 50 DEG C, and filtering, washing are dried at 80 DEG C, then in nitrogen
3 hours are roasted to get tin catalyst of the invention, number A in 300 DEG C under gas shielded.
Through XRF analysis, the Si/Sn molar ratio of catalyst is 0.96.
Through XPS analysis, on catalyst surface, tin atom mass fraction is 5.12%；Through icp analysis, in catalyst, tin
Mass fraction is 63.5%.
Prepare embodiment 2
Take 2.26g stannous chloride dihydrate (SnCl2·2H2O it) is dissolved in the aqueous hydrochloric acid solution that 80ml concentration is 1mol/L,
Take Na2O·SiO2·9H2O is dissolved in deionized water.Two kinds of solution are added in flask simultaneously at 30 DEG C, feed intake Si/Sn
Than being 5, it is 7 that ammonia spirit, which is added, and adjusts pH value, after precipitating is complete, continues to be kept for 2 hours at 30 DEG C, be filtered, washed, 80
It is dried at DEG C, then roasts 4 hours in 250 DEG C under nitrogen protection to get tin catalyst of the invention, number B.
Through icp analysis, in catalyst, the mass fraction of tin is 27.2%.
Prepare embodiment 3
It takes 2.15g stannous sulfate to be dissolved in 10ml deionized water, takes Na2O·SiO2·9H2O is dissolved in deionized water.
Two kinds of solution are added in flask simultaneously at 30 DEG C, the Si/Sn ratio that feeds intake is 1, and it is 7 that ammonia spirit, which is added, and adjusts pH value, is sunk
After forming sediment completely, continues to be kept for 4 hours at 30 DEG C, be filtered, washed, dried at 80 DEG C, then under nitrogen protection in 300 DEG C
Roasting 3 hours to get tin catalyst of the invention, number C.
Through XRF analysis, the Si/Sn molar ratio of catalyst is 0.99.
Through icp analysis, in catalyst, the mass fraction of tin is 61.2%.
Prepare embodiment 4
It takes 2.15g stannous sulfate to be dissolved in the aqueous hydrochloric acid solution that 40ml concentration is 1mol/L, takes K2O·SiO2It is dissolved in
Deionized water.Two kinds of solution are added in flask simultaneously at 30 DEG C, the Si/Sn ratio that feeds intake is 3, and ammonia spirit is added and adjusts pH
Value is 7, after precipitating is complete, continues to be kept for 2 hours at 30 DEG C, is filtered, washed, dries at 80 DEG C, then in nitrogen protection
Under in 250 DEG C roast 4 hours to get tin catalyst of the invention, number D.
Through XRF analysis, the Si/Sn molar ratio of catalyst is 3.02.
Through icp analysis, in catalyst, the mass fraction of tin is 37.3%.
Prepare embodiment 5
Take 2.26g stannous chloride dihydrate (SnCl2·2H2O it) is dissolved in the aqueous hydrochloric acid solution that 80ml concentration is 1mol/L,
Take K2O·SiO2It is dissolved in deionized water.Two kinds of solution are added in flask simultaneously at 30 DEG C, the Si/Sn ratio that feeds intake is 5, is added
Entering ammonia spirit to adjust pH value is 7, after precipitating is complete, continues to be kept for 4 hours at 30 DEG C, is filtered, washed, dries at 80 DEG C
It is dry, then 3 hours are roasted to get tin catalyst of the invention, number E in 500 DEG C under nitrogen protection.
Through icp analysis, in catalyst, the mass fraction of tin is 27.1%.
Prepare embodiment 6
Take 3.51g stannic chloride pentahydrate (SnCl4·5H2O it) is dissolved in 10ml deionized water, takes Na2O·SiO2·9H2O
It is dissolved in deionized water.Two kinds of solution are added in flask simultaneously at 30 DEG C, the Si/Sn ratio that feeds intake is 2, and it is molten that ammonium hydroxide is added
It is 7 that liquid, which adjusts pH value, after precipitating is complete, continues to be kept for 0.5 hour at 50 DEG C, is filtered, washed, dries at 80 DEG C, then
3 hours are roasted in 200 DEG C under nitrogen protection to get tin catalyst of the invention, number F.
Through icp analysis, in catalyst, the mass fraction of tin is 44.0%.
Prepare comparative example 1
Take 5g stannous chloride dihydrate (SnCl2·2H2O) it is configured to SnCl2The aqueous solution that mass fraction is 10%, thereto
10g silica gel is added, stirs 10h, then the ammonia spirit that mass fraction is 20% is added thereto, stirs evenly, washs, filtering,
Drying roasts 3 hours tin catalysts to get comparison, number G in 300 DEG C under nitrogen protection.
Through icp analysis, in catalyst, the mass fraction of tin is 20.1%.
Prepare comparative example 2
Catalyst is prepared using method identical with preparation comparative example 1, the difference is that only: stannous chloride dihydrate
(SnCl2·2H2O dosage) is 4g.Catalyst number is H.
Through icp analysis, in catalyst, the mass fraction of tin is 16.4%.
Prepare comparative example 3
Catalyst is prepared using method identical with preparation comparative example 1, the difference is that only: stannous chloride dihydrate
(SnCl2·2H2O dosage) is 7g.Catalyst number is I.
Through icp analysis, in catalyst, the mass fraction of tin is 25.3%.
Prepare comparative example 4
Prepare catalyst using with the identical method of preparation comparative example 1, the difference is that only: under nitrogen protection in
500 DEG C roast 3 hours.Catalyst number is J.
Through icp analysis, in catalyst, the mass fraction of tin is 20.1%.
React embodiment 1
This example demonstrates that preparing the effect of Di-n-butyl Adipate using adipic acid and n-butanol as raw material.
In reaction system, the molar ratio of adipic acid and n-butanol is 1:3, adds the catalysis of reactant gross mass 1.5%
Agent.It is passed through nitrogen, is warming up to reflux, reflux water-dividing while reaction is stirred to react 3 hours.After reaction, stop stirring,
10 minutes are stood, sampling, observation upper phase separate liquid product and catalyst.Liquid product send analysis, calculate esterification yield and
Selectivity.
Reaction result is shown in Table 1.
React embodiment 2
The reuse effect of the present embodiment catalyst of the invention for comparative illustration, the catalyst of load and stannous oxide
Fruit.
It is carried out according to the method for reaction embodiment 1, unlike: except first set reaction is sub- using catalyst A, G and oxidation
Outside tin, the catalyst of later each reaction reuses the catalyst of upper secondary response recycling；Wherein, the campaign of catalyst A
The mode for being all made of filtering recycles, the campaign of catalyst G and stannous oxide, due to the original of filtration difficulty and catalyst loss
Cause, the mode for being all made of centrifugation recycle catalyst.
Reaction result is shown in Table 2.
React embodiment 3
Carry out, the difference is that only according to the method for reaction embodiment 1: the molar ratio of adipic acid and n-butanol is 1:
2.6, the reaction time is 5 hours.After reaction, it separates liquid product and catalyst, liquid product send analysis.By analysis result
It calculates, the esterification yield of reaction is 99.45%, and the selectivity of reaction is 98.59%.
Liquid product removes excessive alcohol by vacuum distillation, then uses active carbon stirring and adsorbing 2 hours at 100 DEG C
(decoloration) filters to obtain transparent oily liquid product.
React embodiment 4
Carry out, the difference is that only according to the method for reaction embodiment 1: the molar ratio of adipic acid and n-butanol is 1:3,
Catalyst amount is the 1% of reactant gross mass, and the reaction time is 5 hours.After reaction, liquid product and catalysis are separated
Agent, liquid product send analysis.By Analysis result calculation, the esterification yield of reaction is 99.50%, and the selectivity of reaction is 98.87%.
Liquid product removes excessive alcohol by vacuum distillation, then uses active carbon stirring and adsorbing 2 hours at 100 DEG C
(decoloration) filters to obtain transparent oily liquid product.
React embodiment 5
It carries out, the difference is that only according to the method for reaction embodiment 1: preparing the last of the ten Heavenly stems using decanedioic acid and n-butanol as raw material
The molar ratio of diacid di-n-butyl, decanedioic acid and n-butanol is 1:3, and catalyst amount is the 1.5% of reactant gross mass, reaction
Time is 4 hours.After reaction, it separates liquid product and catalyst, liquid product send analysis.By Analysis result calculation, instead
The esterification yield answered is 99.56%, and the selectivity of reaction is 99.23%.
Liquid product removes excessive alcohol by vacuum distillation, then uses active carbon stirring and adsorbing 2 hours at 100 DEG C
(decoloration) filters to obtain transparent oily liquid product.
Table 1
| Catalyst | Esterification yield/% | Selectivity/% | Upper phase |
| A | 99.80 | 99.77 | It is limpid |
| B | 99.62 | 99.40 | It is limpid |
| C | 99.70 | 99.42 | It is limpid |
| D | 99.73 | 99.64 | It is limpid |
| E | 98.58 | 99.21 | It is limpid |
| F | 98.96 | 98.32 | It is limpid |
| G | 99.45 | 99.23 | It is slightly cloudy |
| H | 99.11 | 98.83 | It is slightly cloudy |
| I | 99.21 | 99.03 | It is slightly cloudy |
| J | 98.66 | 98.31 | It is slightly cloudy |
| Stannous oxide | 99.42 | 99.45 | It is more muddy |
Table 2
As seen from Figure 1, it is the combination energy of tin in stannous oxide at 486.31ev, is tin in stannic oxide at 486.53ev
Combination energy.From Figure 2 it can be seen that for using silica as the combination energy of tin in the supported catalyst of carrier at 487.89ev,
It is the combination energy of tin in catalyst of the present invention at 488.31.By Fig. 1 and Fig. 2 it is found that the combination of tin can be most in catalyst of the present invention
It is high.
As seen from Figure 3, in 110cm-1Neighbouring and 211cm-1Near, supported catalyst and stannous oxide have consistent two
Characteristic peak, and the two no characteristic peaks of catalyst of the invention, on the contrary in 237cm-1Near, there are one for catalyst of the invention
A supported catalyst and the no strong characteristic peak of stannous oxide.
From fig. 4, it can be seen that the stannous oxide cuboid particle single for pattern (unprocessed after purchase).As seen from Figure 5, originally
The catalyst of invention is the uniform substance of appearance together without clearly profile, cluster.As seen from Figure 6, loaded catalyst
In, hence it is evident that visible carrier is the inhomogenous substance of appearance.
By Fig. 7, Fig. 8 and Fig. 9 as it can be seen that existing load tin catalyst (under nitrogen protection, 500 DEG C are roasted 3 hours) and oxygen
Changing stannous, there are multiple sharp crystal characteristic peaks between 5 °~70 °, and catalyst of the invention does not have between 5 °~70 °
Sharp crystal characteristic peak.
Claims (17)
1. a kind of preparation method of dicarboxylic acids diol ester, comprising: in the presence of a catalyst, by aliphatic dicarboxylic acid and one
First alcohol haptoreaction, while except the water of dereaction generation；The catalyst is the bulk phase catalyst of siliceous, tin and oxygen and contains
Sn-O-Si key；The monohydric alcohol has structure shown in formula R-OH, and wherein R is the alkyl of unsubstituted alkyl or ether-containing key.
2. according to preparation method described in 1, which is characterized in that the aliphatic dicarboxylic acid is in the dicarboxylic acids of C6~C14
One or more (preferably 1,6- adipic acid, 1,8- suberic acid, 1,9- azelaic acid or 1,10- decanedioic acid).
3. preparation method described in accordance with the claim 1, which is characterized in that the monohydric alcohol is n-butanol, n-hexyl alcohol, just pungent
Alcohol, isooctanol, Decanol, isodecanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol
Monobutyl ether, diethylene glycol mono-ethyl butyl ether, dipropylene glycol monomethyl ether or the tertiary butyl ether of dipropylene glycol list.
4. preparation method described in accordance with the claim 1, which is characterized in that at reflux, react 3h~5h.
5. preparation method described in accordance with the claim 1, which is characterized in that the molar ratio of alcohol and acid is 2.4:1~3:1.
6. preparation method described in accordance with the claim 1, which is characterized in that the dosage of catalyst is reactant gross mass
0.5%~2%.
7. preparation method described in accordance with the claim 1, which is characterized in that further include: after reaction, vacuum distillation removing is light
The step of the step of component and decoloration.
8. preparation method described in accordance with the claim 1, which is characterized in that the catalyst is the body being made of silicon, tin and oxygen
Phase catalyst.
9. preparation method described in accordance with the claim 1, which is characterized in that in the catalyst, the molar ratio of silicon and tin is 0.8
~6 (preferably 1.5~5).
10. preparation method described in accordance with the claim 1, which is characterized in that in the catalyst, the mass fraction of tin is 23%
~65%.
11. preparation method described in accordance with the claim 1, which is characterized in that in the catalyst, the valence state of tin is divalent or four
Valence.
12. preparation method described in accordance with the claim 1, which is characterized in that in the Raman spectrum of the catalyst, in 237cm-1
Nearby there are a characteristic peaks.
13. preparation method described in accordance with the claim 1, which is characterized in that in the Raman spectrum of the catalyst, in 110cm-1
Neighbouring and 211cm-1There is no vibration peak nearby or there are the lesser characteristic peaks of relative intensity.
14. preparation method described in accordance with the claim 1, which is characterized in that in the XRD spectrum of the catalyst, not no tin
The characteristic peak of oxide crystal.
15. preparation method described in accordance with the claim 1, which is characterized in that the catalyst is unformed solid.
16. preparation method described in accordance with the claim 1, which is characterized in that after reaction, isolate catalyst, and should
Catalyst is recycled and reused for the method.
17. a kind of processing method of plastics, which is characterized in that use binary carboxylic made from any one of claim 1~16
Sour diol ester is as plasticizer.
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