CN103374126B - The method for preparing erythritol polymer - Google Patents
The method for preparing erythritol polymer Download PDFInfo
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- CN103374126B CN103374126B CN201210122798.8A CN201210122798A CN103374126B CN 103374126 B CN103374126 B CN 103374126B CN 201210122798 A CN201210122798 A CN 201210122798A CN 103374126 B CN103374126 B CN 103374126B
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Abstract
The invention provides a kind of method for preparing erythritol polymer, this method comprises the following steps：Under the catalysis of activated carbon supported base catalyst so that polymerisation occurs for antierythrite monomer, so that erythritol polymer is made, wherein the base catalyst is selected from hydroxide, carbonate, alkoxide or its combination of alkali metal.
Description
Technical field
The present invention relates to polymerisation field, more particularly, the present invention relates to the method for preparing red polymers of sugar alcohols.
Background technology
Antierythrite also known as erythritol, are a kind of polyol sweeteners shown in its structure such as formula (1), naturally occurring
In marine alga, mushroom, muskmelon, grape and fermented foodstuff, it is also present in human eyeball, serum.Due to its it is edible after can not be by
Enzyme degrade, can only through kidney from blood be transferred to urine in discharge, be not involved in glycometabolism and change of blood sugar, be highly suitable as sugar
Urinate the replacement sweetener of patient.In addition, antierythrite does not result in fermentation in colon, digestive discomfort, Er Qieshi can be avoided
A kind of sweetener low in calories, does not result in carious tooth.Due to the above advantage, antierythrite is widely used in various foods
In product.Main fermented by Candida lipolytica (Candida lipolytica) of antierythrite in the market is made.
Formula (1)
Erythritol polymer can be made by occurring polymerisation in antierythrite.The erythritol polymer is one
Golden yellow thick liquid is planted, with the stability under splendid low-temperature pliability and acid, alkali and hot conditions, and volatility is very
Low, adhesiveness is larger, is splendid food gelling agent.
Gelling agent in current jam, jelly isogel based food is mainly agar, gelatin, carragheen, pectin etc. and eaten
Glue, belongs to dietary fiber class, edible excessively to influence the absorption and utilization of the trace element such as fat, albumen and iron zinc, therefore seeks
Looking for its substitute or reducing its consumption in food turns into urgent problem to be solved at this stage.Erythritol polymer molecule it
Between interior, molecule and between hydrone, substantial amounts of hydrogen bond, in solid-state and fluidised form food, erythritol polymer are formed
System is interconnected into huge associated molecule with hydrogen bond, and is interacted with the albumen in food, dietary fiber and starch, makes it
Entirety as a stable homogeneous.Therefore, erythritol polymer is except keeping the refrigerant mouthfeel of monomer antierythrite, low-heat
Measure, do not result in beyond the advantage that digestive discomfort and diabetic group use, also with very strong gelling characteristic, Ke Yiqu
It is used in for foodstuff glues such as agar, gelatin, carragheen, pectin, xanthans, konjac glucomannans in jelly, jam isogel based food, with this
Strengthen the stability of food, promote it to be molded.
(the Appl Microbiol Biotechnol, volume 2010,86 such as Hee-Jung：The 1017-1025 pages),
(the Journal of Thermal Analysis and Calorimetry, volume 2009,95 such as B.Tong：The 469-475 pages)
The production of antierythrite, performance, macroscopic property and application are studied.In U.S. Patent No. US2003/0017132
Erythritol polymer and its fatty acid ester or aliphatic ether are disclosed, can be former as surfactant, emulsifying agent, cosmetics
Material, cleaning agent, defoamer, dispersant, solubilizer, preservative etc., and combinations thereof or raw material.But in these documents without exception
By the way of base catalyst is directly added into antierythrite monomer is polymerize, need to make after polymerization was complete
Catalyst is removed with anion-cation exchange resin post, complex operation takes time and effort, and treating capacity is small, it is high to prepare cost, to red
The industrialization of moss polymers of sugar alcohols preparation technology causes very big obstacle.People are in the urgent need to a kind of quick, easy, cheap
Alternative techniques.
For problem above, the invention provides a kind of preparation method using novel load type catalyst system, make
Need not carry out anion-cation exchange resin column operation after polymerisation, enormously simplify operating procedure, reduce and be prepared into
This.
The content of the invention
The invention provides a kind of method for preparing erythritol polymer, this method comprises the following steps：In activated carbon
Under the catalysis of the base catalyst of load so that polymerisation occurs for antierythrite monomer, so that antierythrite polymerization is made
Thing, wherein the base catalyst is selected from hydroxide, carbonate, alkoxide or its combination, preferably potassium carbonate, carbonic acid of alkali metal
Sodium, potassium hydroxide, sodium hydroxide, potassium methoxide, sodium methoxide or its combination, more preferably potassium carbonate.
In one preferred embodiment, methods described is additionally included in before the polymerisation, will be activated carbon supported
Base catalyst add molten condition antierythrite monomer in step.Another preferred embodiment in, it is described
Method is further comprising the steps of：After polymerization, water is added into reaction system to dissolve the obtained antierythrite
Polymer, then by filter operation by the obtained erythritol polymer and the activated carbon supported base catalyst
Separation.It is preferred that obtained antierythrite catalyst and activated carbon supported base catalyst are divided by filter operation
From after, erythritol polymer product can be directly obtained by removing moisture, without to erythritol polymer or its
The aqueous solution carries out any further purifying of such as chromatogram purification etc.
Embodiment
In the present invention, unless otherwise indicated, all percentage and ratio be in mass.In addition, present invention description
All number ranges include end value and can include by the upper and lower bound of scope of disclosure mutually any combination obtain
New number range.If for example, the weight/mass percentage composition for disclosing certain component is 10~30 mass %, preferably 15~25
Quality %, more preferably 20~23 mass %, then equivalent to also disclosing following number range：10~15 mass %, 10~
25 mass %, 10~20 mass %, 10~23 mass %, 15~30 mass %, 15~20 mass %, 15~23 mass %, 20
~25 mass %, 23~25 mass %.
The base catalyst of the present invention is carbonate, hydroxide, alkoxide and the combinations thereof of alkali metal.It is specific next
Say, the base catalyst be potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium methoxide, sodium methoxide or combinations thereof,
Most preferably potassium carbonate.
In the present invention, the base catalyst is loaded on the activated carbon by infusion process, so as to keep catalysis to live
While property catalyst is easily removed by filtration method after the reaction.Specifically, the loaded catalyst
Prepared approximately by the following manner：The carbonate, hydroxide and alkoxide of alkali metal is soluble in water, by a certain amount of warp
Cross and wash and be dried under vacuum to the granular active high-area carbon of constant weight and be placed in time of infusion in the aqueous solution, be then separated by filtration
And be dried in vacuo.Activated carbon of the present invention is not particularly limited, preferably used public purchased from Holland Nuo Ruite (Norit)
The Norit CA of departmentTMActivated carbon, its surface area is 1800m2/ g, wherein the particle diameter of more than 90% activated carbon granule is micro- less than 40
Rice.But those skilled in the art can be apparent from, the homemade work of other commodity or laboratory can also be used
Property charcoal implements embodiments of the invention and obtains similar technique effect.
The amount of the base catalyst to load on the activated carbon carries out quantitatively characterizing in the following manner：Take a certain amount of work
Property charcoal, and measure its quality for M1, after being loaded to the activated carbon, weigh the mass M 2 of the supported catalyst of drying,
The mass ratio of catalytic component and activated carbon is (M2-M1)/M1.
According to the specific needs of reaction, obtained activated carbon can be controlled to bear by adjusting the concentration of aqueous catalyst solution
Carry the mass ratio of catalytic component and activated carbon in base catalyst.According to a preferred embodiment of the present invention, for making
The concentration of the alkaline catalyst solution of standby activated carbon supported type catalyst is 0.1~5 mol/L, preferably 0.3~3 mole/
Rise, most preferably 1~2 mol/L.Dip time of the activated carbon in this aqueous solution is 30 minutes to 3 days, preferably 2 hours to 2
My god, most preferably 20~36 hours.In obtained loaded catalyst, the quality of carrier active carbon and basic catalyst component
Than for 1: 20 to 1: 3, preferably 1: 15 to 1: 3.5, more preferably 1: 10 to 1: 4, most preferably 1: 6 to 1: 4.
In the polymerisation of antierythrite, the temperature of reaction system is heated to slightly above antierythrite monomer first
Fusing point (about 122 DEG C) so that antierythrite monomer is all melted, then by a certain proportion of above-mentioned activated carbon supported base catalysis
Agent is added thereto, and is vacuumized rapidly so that pressure in reaction system is 5-60 millimetress of mercury, preferably 10-50 millimetress of mercury,
More preferably 20-40 millimetress of mercury, then raise temperature, are reacted at 180-260 DEG C, preferably 200-240 DEG C, at this temperature instead
Answer 3-10 hours, preferably 4-8 hours, more preferably 5-6 hours, so as to carry out polymerisation.Pass through controlling reaction temperature and time
To control the degree of polymerization of obtained erythritol polymer.On the basis of the antierythrite monomer gross mass for adding reaction system
Meter, the consumption of the loaded catalyst is 1-10 mass %, preferably 2-6 mass %.
After reaction terminates, appropriate water is added into reaction system so that erythritol polymer is completely dissolved, filtered
Activated carbon supported catalyst is removed, rotary evaporation removes the moisture in filtrate, and required erythritol polymer is made.
The antierythrite monomer is the polyalcohol with four hydroxyls, at reaction conditions, the hydroxyl of different monomers molecule
Base occurs condensation reaction and forms ehter bond, shown in reaction equation (2) specific as follows：
Formula (2)
Wherein n is 0-16 integer, and in other words, the degree of polymerization is 2-18.
After reading the foregoing specification, within the scope of those skilled in the art can be covered in this area to
The upper embodiment carries out a certain degree of improvement, substitutes and combine, so as to implement the present invention and obtain similar technology effect
Really.All these improvement, replacement and combination are also included within the scope of the present invention.
The preferred embodiment of the present invention is discussed in further detail with reference to specific embodiment, in order to people
More grok the present invention.It should be noted however that following specific embodiment is only used for illustrating
Bright purpose, will not constitute any limitation, the scope of the present invention is only limited only by the appended claims to protection scope of the present invention.
Embodiment
Embodiment 1：Antierythrite polymerization is carried out using activated carbon supported catalyst
A. the preparation of catalyst
The activated carbon that the present embodiment is used is available from the Norit CA of Dutch Nuo Ruite (Norit) companyTMGranular active carbon.
Take 240 grams of activated carbons to be placed in the container comprising 1000 milliliters of water, be stirred overnight on magnetic stirring apparatus.Then vacuum is carried out to take out
Filter, is placed in vacuum drying oven and is dried at a temperature of 90 DEG C to constant weight.By 40 grams thus treated of activated carbon respectively in 300 millis
Rise concentration be respectively the potassium carbonate of 1.2 mol/Ls, the sodium carbonate of 1.3 mol/Ls, 1.5 mol/L potassium hydroxide, 1.6 moles/
Stir 24 hours, drained with Buchner funnel in the aqueous solution of the sodium hydroxide risen, it is small then to dry 5 in 80 DEG C in vacuum drying oven
When, take out after cooling, it is respectively 1: 3.93,1: 3.96,1: 3.99,1 to weigh and measure the mass ratio of catalyst and activated carbon:
4.02, it is then transferred into stand-by in drier.
B. the preparation of erythritol polymer
500 grams of antierythrites (being purchased from Cargill Inc.) are weighed in three-necked flask, 130 DEG C are heated to so that antierythrite
All after fusing, 4% (i.e. 20 grams) activated carbon supported K manufactured in the present embodiment is separately added into2CO3/Na2CO3/ KOH/NaOH,
It is rapid to be evacuated to pressure and reach 35 millimetress of mercury or so, and raise temperature and be stirred to 210 DEG C, and to reaction system,
Reacted 6 hours at a temperature of this.
After reaction terminates, room temperature is cooled to, add 450 milli liter of water products, the activated carbon supported catalyst of filtering and removing,
It is 7.06 to measure pH value, revolving water removal, erythritol polymer is obtained, with GB3143-1982 liquid chemical products colour measurement side
Method (Hazen units-platinum-cobalt color number) analysis product color and luster, with measure erythritol polymer quality divided by the red moss of raw material
The quality of sugar alcohol monomer is to obtain product yield.
Using the molecular weight of gel permeation chromatography gpc measurement erythritol polymer, analysis condition is as described below：
Post：Asahipak GF-510HQ gel columns (are purchased from Shanghai ANPEL Scientific Instrument Co., Ltd.)
Temperature：30℃
Elutriant：Water/acetonitrile=90/10
Sample concentration：1.0g/L
Flow：1.0mL/min
Injection rate：5μL
Analysis time：15min
The structure of the erythritol polymer is by infrared spectrum characterization：A small amount of erythritol polymer is taken to be coated in KBr pressures
On piece, then infrared scan is carried out with Shimadzu IR Prestige-21 infrared spectrometers, product is removed in 3400cm-1There is hydroxyl suction in place
Receive outside peak, separately in 1050cm-1There is ehter bond absworption peak in place, it was demonstrated that erythritol polymer is generated.
Embodiment 2 (comparative example of embodiment 1)：Antierythrite polymerization is carried out using unsupported catalyst
Catalyst K is weighed by the 2 mass % (10 grams) of antierythrite (being purchased from Cargill Inc.) addition2CO3/Na2CO3/
KOH/NaOH, adding 30 grams of distilled water makes it all dissolve, standby.
Weigh 500 grams of antierythrites to be placed in three-necked flask, be heated approximately at 130 DEG C, after antierythrite is completely melt,
Aqueous catalyst solution is poured into antierythrite rapidly, because the temperature in reaction system is higher than the boiling point of water, it is observed that
The violent explosive evaporation of water, after the water evaporating completely of solvent, is evacuated to rapidly pressure and reaches 35 millimetress of mercury or so,
Temperature is raised to 210 DEG C, reaction system is stirred, and is reacted 6 hours at this temperature.
After reaction terminates, room temperature is cooled to, 450 milli liter of water products are added, and decolourized by activated carbon and carclazyte.
The aqueous solution is purified followed by ion-exchange process.The ion-exchange process, which is used, is purchased from Anhui
201 × 7 anion exchange resin and 001 × 7 cationic ion-exchange resin of Samsung resin Science and Technology Ltd., these resins are first
It is swelled 24 hours in 40 DEG C of deionized water, then successively with alkali and acid soak 4 hours, and is washed with deionized water to neutrality,
Cyclic washing 3 times, dress post is stand-by.The pillar that the ion-exchange process is used is normal pressure in common chromatographic column, post, internal diameter 35mm,
Length 60cm, purchased from Shanghai Sha Mei biochemical technologies Development Co., Ltd.Four root chromatogram columns, anionic and cation are loaded altogether
Each two of type.
The product aqueous solution after decolouring is passed sequentially through through above-mentioned pretreated four according to the order of male-female-male-female
Ion exchange resin column, the pH value for measuring final product is 7.06, it was demonstrated that alkalescence is fully eliminated by ion-exchange treatment and is urged
Agent.
Revolving water removal is carried out to the aqueous solution for carrying out ion-exchange treatment, erythritol polymer is obtained, with GB3143-
1982 liquid chemical product colour measurement methods (Hazen units-platinum-cobalt color number) analysis product color and luster, calculates product yield.
The measure of erythritol polymer molecular weight is carried out using GPC, analysis condition is as described below：
Post：Asahipak GF-510HQ gel columns (are purchased from Shanghai ANPEL Scientific Instrument Co., Ltd.)
Temperature：30℃
Elutriant：Water/acetonitrile=90/10
Sample concentration：1.0g/L
Flow：1.0mL/min
Injection rate：5μL
Analysis time：15min
The structure of the erythritol polymer is by infrared spectrum characterization：A small amount of erythritol polymer is taken to be coated in KBr pressures
On piece, then infrared scan is carried out with Shimadzu IR Prestige-21 infrared spectrometers, product is removed in 3400cm-1There is hydroxyl suction in place
Receive outside peak, separately in 1050cm-1There is ehter bond absworption peak in place, it was demonstrated that erythritol polymer is generated.
Embodiment 3 (comparative example of embodiment 1)：Antierythrite polymerization is carried out using gama-alumina supported catalyst
A. the preparation of the catalyst of gama-alumina load
The gama-alumina that the present embodiment is used is available from the AR level gama-aluminas of Chemical Reagent Co., Ltd., Sinopharm Group.
Take 240 grams of gama-aluminas to be placed in the container comprising 1000 milliliters of water, be stirred overnight on magnetic stirring apparatus.Then carry out true
Empty suction filtration, is placed in vacuum drying oven and is dried at a temperature of 90 DEG C to constant weight.Thus 40 grams treated of aluminum oxide is existed respectively
300 milliliters of concentration be respectively the potassium carbonate of 2.6 mol/Ls, the sodium carbonate of 2.7 mol/Ls, the potassium hydroxide of 2.9 mol/Ls,
Stir 24 hours, drained with Buchner funnel, then in 80 in vacuum drying oven in the aqueous solution of the sodium hydroxide of 3.0 mol/Ls
DEG C dry 5 hours, take out after cooling, weighing measures the mass ratio of catalyst and aluminum oxide and be each about 1: 4.01,1: 4.03,1:
3.98,1: 3.96, it is then transferred into stand-by in drier.
B. the preparation of erythritol polymer
500 grams of antierythrites (being purchased from Cargill Inc.) are weighed in three-necked flask, 130 DEG C are heated to so that antierythrite
All after fusing, the K of 4% (i.e. 20 grams) gama-alumina load manufactured in the present embodiment is separately added into2CO3/Na2CO3/KOH/
NaOH, is evacuated to rapidly pressure and reaches 35 millimetress of mercury or so, and raise temperature and stirred to 210 DEG C, and to reaction system
Mix, react 6 hours at this temperature.
After reaction terminates, room temperature is cooled to, 450 milli liter of water products, filtering and removing gama-alumina supported catalyst are added
Agent, it is 7.42 to measure pH value, revolving water removal, erythritol polymer is obtained, with GB3143-1982 liquid chemical product colour measurements
Method (Hazen units-platinum-cobalt color number) analysis product color and luster, with measure erythritol polymer quality divided by raw material it is red
The quality of moss sugar alcohol monomer is to obtain product yield.
By carrying out the measure of GPC erythritol polymer molecular weight, analysis condition is as described below：
Post：Asahipak GF-510HQ gel columns (are purchased from Shanghai ANPEL Scientific Instrument Co., Ltd.)
Temperature：30℃
Elutriant：Water/acetonitrile=90/10
Sample concentration：1.0g/L
Flow：1.0mL/min
Injection rate：5μL
Analysis time：15min
The structure of the erythritol polymer is by infrared spectrum characterization：A small amount of erythritol polymer is taken to be coated in KBr pressures
On piece, then infrared scan is carried out with Shimadzu IR Prestige-21 infrared spectrometers, product is removed in 3400cm-1There is hydroxyl suction in place
Receive outside peak, separately in 1050cm-1There is ehter bond absworption peak in place, it was demonstrated that erythritol polymer is generated.
Embodiment 4 (comparative example of embodiment 1)：Antierythrite polymerization is carried out using molecular sieve carried catalyst
A. the preparation of molecular sieve carried catalyst
The molecular sieve that the present embodiment is used is available from the 4A molecular sieves of Chemical Reagent Co., Ltd., Sinopharm Group.Take 240 grams
Molecular sieve is placed in the container comprising 1000 milliliters of water, is stirred overnight on magnetic stirring apparatus.Then it is filtered by vacuum, is placed in
Dried in vacuum drying oven at a temperature of 90 DEG C to constant weight.By 40 grams thus treated of molecular sieve respectively in 300 milliliters of concentration
The respectively potassium carbonate of 4.2 mol/Ls, the sodium carbonate of 4.4 mol/Ls, the potassium hydroxide of 4.5 mol/Ls, 4.6 mol/Ls
Stir 24 hours, drained with Buchner funnel in the aqueous solution of sodium hydroxide, then dried 5 hours in 80 DEG C in vacuum drying oven,
Take out after cooling, weighing measures the mass ratio of catalyst and molecular sieve and be each about 1: 3.92,1: 3.98,1: 4.06,1: 3.95, so
After be transferred to it is stand-by in drier.
B. the preparation of erythritol polymer
500 grams of antierythrites (being purchased from Cargill Inc.) are weighed in three-necked flask, 130 DEG C are heated to so that antierythrite
All after fusing, 4% (i.e. 20 grams) molecular sieve carried K manufactured in the present embodiment is separately added into2CO3/Na2CO3/ KOH/NaOH,
It is rapid to be evacuated to pressure and reach 35 millimetress of mercury or so, and raise temperature and be stirred to 210 DEG C, and to reaction system,
Reacted 6 hours at a temperature of this.
After reaction terminates, room temperature is cooled to, 450 milli liter of water products, filtering and removing gama-alumina supported catalyst are added
Agent, it is 7.65 to measure pH value, revolving water removal, erythritol polymer is obtained, with GB3143-1982 liquid chemical product colour measurements
Method (Hazen units-platinum-cobalt color number) analysis product color and luster, with measure erythritol polymer quality divided by raw material it is red
The quality of moss sugar alcohol monomer is to obtain product yield.
By carrying out the measure of GPC erythritol polymer molecular weight, analysis condition is as described below：
Post：Asahipak GF-510HQ gel columns (are purchased from Shanghai ANPEL Scientific Instrument Co., Ltd.)
Temperature：30℃
Elutriant：Water/acetonitrile=90/10
Sample concentration：1.0g/L
Flow：1.0mL/min
Injection rate：5μL
Analysis time：15min
The structure of the erythritol polymer is by infrared spectrum characterization：A small amount of erythritol polymer is taken to be coated in KBr pressures
On piece, then infrared scan is carried out with Shimadzu IR Prestige-21 infrared spectrometers, product is removed in 3400cm-1There is hydroxyl suction in place
Receive outside peak, separately in 1050cm-1There is ehter bond absworption peak in place, it was demonstrated that erythritol polymer is generated.
Table 1 below -4 is shown in four embodiments of the above using different carriers and without using resulting under conditions of carrier
Weight average molecular weight, color and luster number and the product yield characterization result of product.
Table 1.K2CO3And its catalytic action after load
Table 2.Na2CO3And its catalytic action after load
Table 3.KOH and its load after catalytic action
Table 4.NaOH and its load after catalytic action
Characterization result from upper table can draw to draw a conclusion：
(1) under the same reaction conditions, activated carbon supported K2CO3/Na2CO3/ KOH/NaOH prepares dividing equally again for product
Son amount is maximum, i.e., the degree of polymerization is maximum, illustrates that activated carbon supported catalyst has more preferable catalytic effect.
(2) under the same conditions, activated carbon supported K2CO3/Na2CO3/ KOH/NaOH prepares the color and luster minimum of product,
I.e. color is most shallow, illustrates that activated carbon supported catalyst has good decolorizing effect.
(3) under the same conditions, the yield highest of activated carbon supported catalyst preparation product.
(4) in addition, using the present invention activated carbon supported type catalyst when, be filtered to remove solid catalyst it
Afterwards, the pH value of the product aqueous solution is about 7.06, it was demonstrated that base catalyst is all supported on carrier active carbon securely, therefore
Product can need not carry out ion-exchange treatment and directly use.By comparison, when using unsupported catalyst, take off
The product aqueous solution obtained after color step is in strong basicity, it was demonstrated that there are a large amount of base catalysts in the aqueous solution, it is therefore desirable to enter
The ion-exchange treatment that row is complicated and takes.
In addition to the degree of polymerization, decolorizing effect and yield, the reaction rate of catalytic reaction be also in industrial circle very by
One factor of people's concern.The reaction rate can be characterized with the reaction time needed for acquisition specific aggregation degree.With
In lower embodiment 5 and 6, applicant be prepared for different weight than loaded catalyst.In following embodiment 7-10, application
People was measured the reaction time needed for reaching the 5-8 degree of polymerization using four kinds of different types of catalyst.
Embodiment 5：Prepare the loaded catalyst of mass ratio 1: 6
A. the preparation of activated carbon supported catalyst
The activated carbon that the present embodiment is used is available from the Norit CA of Dutch Nuo Ruite (Norit) companyTMGranular active carbon.
Take 240 grams of activated carbons to be placed in the container comprising 1000 milliliters of water, be stirred overnight on magnetic stirring apparatus.Then vacuum is carried out to take out
Filter, is placed in vacuum drying oven and is dried at a temperature of 90 DEG C to constant weight.By 40 grams thus treated of activated carbon respectively in 300 millis
Rise concentration be respectively the potassium carbonate of 0.8 mol/L, the sodium carbonate of 0.9 mol/L, 1.0 mol/L potassium hydroxide, 1.1 moles/
Stir 24 hours, drained with Buchner funnel in the aqueous solution of the sodium hydroxide risen, it is small then to dry 5 in 80 DEG C in vacuum drying oven
When, take out after cooling, it is respectively 1: 5.95,1: 5.97,1: 6.04,1 to weigh and measure the mass ratio of catalyst and activated carbon:
6.05, it is then transferred into stand-by in drier.
B. the preparation of the catalyst of gama-alumina load
The gama-alumina that the present embodiment is used is available from the AR level gama-aluminas of Chemical Reagent Co., Ltd., Sinopharm Group.
Take 240 grams of gama-aluminas to be placed in the container comprising 1000 milliliters of water, be stirred overnight on magnetic stirring apparatus.Then carry out true
Empty suction filtration, is placed in vacuum drying oven and is dried at a temperature of 90 DEG C to constant weight.Thus 40 grams treated of aluminum oxide is existed respectively
300 milliliters of concentration be respectively the potassium carbonate of 1.8 mol/Ls, the sodium carbonate of 1.9 mol/Ls, the potassium hydroxide of 2.0 mol/Ls,
Stir 24 hours, drained with Buchner funnel, then in 80 in vacuum drying oven in the aqueous solution of the sodium hydroxide of 2.1 mol/Ls
DEG C dry 5 hours, take out after cooling, weighing measures the mass ratio of catalyst and aluminum oxide and be each about 1: 5.94,1: 6.01,1:
5.97,1: 5.99, it is then transferred into stand-by in drier.
C. the preparation of molecular sieve carried catalyst
The molecular sieve that the present embodiment is used is available from the 4A molecular sieves of Chemical Reagent Co., Ltd., Sinopharm Group.Take 240 grams
Molecular sieve is placed in the container comprising 1000 milliliters of water, is stirred overnight on magnetic stirring apparatus.Then it is filtered by vacuum, is placed in
Dried in vacuum drying oven at a temperature of 90 DEG C to constant weight.By 40 grams thus treated of molecular sieve respectively in 300 milliliters of concentration
The respectively potassium carbonate of 2.9 mol/Ls, the sodium carbonate of 3.0 mol/Ls, the potassium hydroxide of 3.1 mol/Ls, 3.2 mol/Ls
Stir 24 hours, drained with Buchner funnel in the aqueous solution of sodium hydroxide, then dried 5 hours in 80 DEG C in vacuum drying oven,
Take out after cooling, weighing measures the mass ratio of catalyst and molecular sieve and be each about 1: 6.02,1: 5.96,1: 6.03,1: 5.98, so
After be transferred to it is stand-by in drier.
Embodiment 6：Prepare the loaded catalyst of mass ratio 1: 10
A. the preparation of activated carbon supported catalyst
The activated carbon that the present embodiment is used is available from the Norit CA of Dutch Nuo Ruite (Norit) companyTMGranular active carbon.
Take 240 grams of activated carbons to be placed in the container comprising 1000 milliliters of water, be stirred overnight on magnetic stirring apparatus.Then vacuum is carried out to take out
Filter, is placed in vacuum drying oven and is dried at a temperature of 90 DEG C to constant weight.By 40 grams thus treated of activated carbon respectively in 300 millis
Rise concentration be respectively the potassium carbonate of 0.6 mol/L, the sodium carbonate of 0.7 mol/L, 0.8 mol/L potassium hydroxide, 0.9 mole/
Stir 24 hours, drained with Buchner funnel in the aqueous solution of the sodium hydroxide risen, it is small then to dry 5 in 80 DEG C in vacuum drying oven
When, take out after cooling, it is respectively 1: 9.96,1: 10.04,1: 9.01,1 to weigh and measure the mass ratio of catalyst and activated carbon:
10.02, it is then transferred into stand-by in drier.
B. the preparation of the catalyst of gama-alumina load
The gama-alumina that the present embodiment is used is available from the AR level gama-aluminas of Chemical Reagent Co., Ltd., Sinopharm Group.
Take 240 grams of gama-aluminas to be placed in the container comprising 1000 milliliters of water, be stirred overnight on magnetic stirring apparatus.Then carry out true
Empty suction filtration, is placed in vacuum drying oven and is dried at a temperature of 90 DEG C to constant weight.Thus 40 grams treated of aluminum oxide is existed respectively
300 milliliters of concentration be respectively the potassium carbonate of 1.3 mol/Ls, the sodium carbonate of 1.4 mol/Ls, the potassium hydroxide of 1.5 mol/Ls,
Stir 24 hours, drained with Buchner funnel, then in 80 in vacuum drying oven in the aqueous solution of the sodium hydroxide of 1.6 mol/Ls
DEG C dry 5 hours, take out after cooling, weighing measures the mass ratio of catalyst and aluminum oxide and be each about 1: 9.95,1: 9.98,1:
10.05,1: 10.97, it is then transferred into stand-by in drier.
C. the preparation of molecular sieve carried catalyst
The molecular sieve that the present embodiment is used is available from the 4A molecular sieves of Chemical Reagent Co., Ltd., Sinopharm Group.Take 240 grams
Molecular sieve is placed in the container comprising 1000 milliliters of water, is stirred overnight on magnetic stirring apparatus.Then it is filtered by vacuum, is placed in
Dried in vacuum drying oven at a temperature of 90 DEG C to constant weight.By 40 grams thus treated of molecular sieve respectively in 300 milliliters of concentration
The respectively potassium carbonate of 2.0 mol/Ls, the sodium carbonate of 2.1 mol/Ls, the potassium hydroxide of 2.2 mol/Ls, 2.3 mol/Ls
Stir 24 hours, drained with Buchner funnel in the aqueous solution of sodium hydroxide, then dried 5 hours in 80 DEG C in vacuum drying oven,
Take out after cooling, weighing measures the mass ratio of catalyst and molecular sieve and be each about 1: 9.97,1: 9.94,1: 10.02,1: 10.03,
It is then transferred into stand-by in drier.
Embodiment 7：The preparation of erythritol polymer is carried out using activated carbon supported catalyst
500 grams of antierythrites (being purchased from Cargill Inc.) are weighed in three-necked flask, 130 DEG C are heated to so that antierythrite
All after fusing, 6% (i.e. 30 grams) the activated carbon supported K that as described above prepared by embodiment 5 and 6 is separately added into2CO3/
Na2CO3/ KOH/NaOH (mass ratio 1: 6 and 1: 10), is evacuated to rapidly pressure and reaches 45 millimetress of mercury or so, and raise temperature
It is stirred, reacts 12 hours on this condition to 230 DEG C, and to reaction system, sampled, produced with gpc analysis every 0.5 hour
The degree of polymerization of product molecular weight and in prediction on such basis product, analysis condition is same as Example 1.
Also by the way of same as Example 1, the structure of the erythritol polymer is carried out by infrared spectrum
Characterize, as a result product is removed in 3400cm-1Place occurs outside hydroxyl absorption peak, separately in 1050cm-1There is ehter bond absworption peak in place, it was demonstrated that
Erythritol polymer is generated.
Embodiment 8 (comparative example of embodiment 7)：The preparation of erythritol polymer is carried out using unsupported catalyst
Catalyst K is weighed by the 1 mass % (i.e. 5 grams) of antierythrite (being purchased from Cargill Inc.) addition2CO3/Na2CO3/
KOH/NaOH, adding 30g distilled water makes it all dissolve, standby.
Weigh 500 grams of antierythrites to be placed in three-necked flask, be heated to 130 DEG C, after antierythrite is completely melt, rapidly
Aqueous catalyst solution is poured into antierythrite, because the temperature in reaction system is higher than the boiling point of water, it is observed that water is acute
Strong explosive evaporation, after the water evaporating completely of solvent, is evacuated to rapidly pressure and reaches 45 millimetress of mercury or so, rise
Temperature is stirred to 230 DEG C to reaction system, is reacted 12 hours on this condition, was sampled every 0.5 hour, is used gpc analysis
The degree of polymerization of molecular weight product and in prediction on such basis product, analysis condition is same as Example 2.
Also by the way of same as Example 2, the structure of the erythritol polymer is carried out by infrared spectrum
Characterize, as a result product is removed in 3400cm-1Place occurs outside hydroxyl absorption peak, separately in 1050cm-1There is ehter bond absworption peak in place, it was demonstrated that
Erythritol polymer is generated.
Embodiment 9 (comparative example of embodiment 7)：The catalyst loaded using gama-alumina carries out erythritol polymer
Prepare
500 grams of antierythrites (being purchased from Cargill Inc.) are weighed in three-necked flask, 130 DEG C are heated to so that antierythrite
All after fusing, the K of alumina load prepared by 6% (i.e. 30 grams) embodiment 5 and 6 as described above is separately added into2CO3/
Na2CO3/ KOH/NaOH (mass ratio 1: 6 and 1: 10), is evacuated to rapidly pressure and reaches 45 millimetress of mercury or so, and raise temperature
It is stirred, reacts 12 hours on this condition to 230 DEG C, and to reaction system, sampled, produced with gpc analysis every 0.5 hour
The degree of polymerization of product molecular weight and in prediction on such basis product, analysis condition is same as Example 3.
Also by the way of same as Example 3, the structure of the erythritol polymer is carried out by infrared spectrum
Characterize, as a result product is removed in 3400cm-1Place occurs outside hydroxyl absorption peak, separately in 1050cm-1There is ehter bond absworption peak in place, it was demonstrated that
Erythritol polymer is generated.
Embodiment 10 (comparative example of embodiment 7)：The system of erythritol polymer is carried out using molecular sieve carried catalyst
It is standby
500 grams of antierythrites (being purchased from Cargill Inc.) are weighed in three-necked flask, 130 DEG C are heated to so that antierythrite
All after fusing, 6% (i.e. 30 grams) the molecular sieve carried K that as described above prepared by embodiment 5 and 6 is separately added into2CO3/
Na2CO3/ KOH/NaOH (mass ratio 1: 6 and 1: 10), is evacuated to rapidly pressure and reaches 45 millimetress of mercury or so, and raise temperature
It is stirred, reacts 12 hours on this condition to 230 DEG C, and to reaction system, sampled, produced with gpc analysis every 0.5 hour
The degree of polymerization of product molecular weight and in prediction on such basis product, analysis condition is same as Example 4.
Also by the way of same as Example 4, the structure of the erythritol polymer is carried out by infrared spectrum
Characterize, as a result product is removed in 3400cm-1Place occurs outside hydroxyl absorption peak, separately in 1050cm-1There is ehter bond absworption peak in place, it was demonstrated that
Erythritol polymer is generated.
The structure of the erythritol polymer is by infrared spectrum characterization：A small amount of erythritol polymer is taken to be coated in KBr pressures
On piece, then infrared scan is carried out with Shimadzu IR Prestige-21 infrared spectrometers, product is removed in 3400cm-1There is hydroxyl suction in place
Receive outside peak, separately in 1050cm-1There is ehter bond absworption peak in place, it was demonstrated that erythritol polymer is generated.
As described above in Example, the weight of the polymer product during polymerisation is carried out obtained by continuous detection
Average molecular weight, records the molecular weight and falls into earliest in the range of 550-850, i.e., weight average degree of polymerization reaches the time needed for 5~8.Knot
Fruit is shown in Table 5.
Table 5. prepared for 5~8 poly- erythritol polymer (weight average molecular weight range is about 550~850) required time/hours
It can see from upper table 5, under identical reaction condition, prepare the product of same polymeric degree, it is activated carbon supported
It is most short the time required to catalyst, illustrate activated carbon supported K2CO3/Na2CO3/ KOH/NaOH shortens the reaction time, with more preferable
Catalytic effect.
Embodiment 11：The alkoxide loaded using different carriers carries out polymerisation.
According to the catalyst preparation step described in embodiment 1,3,4, catalyst is used as using sodium methoxide and potassium methoxide respectively
Component, it is 1: 4 loaded catalyst that catalyst and carrier quality ratio, which is made,.It is subsequently used for carrying out antierythrite polymerization experiment,
The result similar with shown in embodiment 1-4 has been obtained, i.e., has been urged using activated carbon supported sodium methoxide and potassium methoxide as catalyst
Change prepares weight average molecular weight, color and efficiency of pcr product of product etc. respectively better than the sodium methoxide and potassium methoxide not loaded,
Better than the sodium methoxide and the effect of potassium methoxide using molecular sieve or alumina load.
According to the catalyst preparation step described in embodiment 5,6, catalyst group is used as using sodium methoxide and potassium methoxide respectively
Point, catalyst is made respectively and the loaded catalyst that carrier quality ratio is 1: 6 and 1: 10, then using above-mentioned catalyst
Antierythrite polymerisation, its result is similar with embodiment 7-10, i.e., using activated carbon supported sodium methoxide and potassium methoxide as
Catalyst prepares weight average molecular weight, color, efficiency of pcr product and reaction rate of product etc. and is respectively better than what is do not loaded
Sodium methoxide and potassium methoxide, also superior to the sodium methoxide and the effect of potassium methoxide using molecular sieve or alumina load.
By above-described embodiment it can be seen that, the present invention base catalyst is loaded by using activated carbon, can obtain
Following benefit：
(1) catalyst need not be removed using the ion exchange technique wasted time and energy.Specifically, the present invention is only with normal
The filter operation of rule just in a short time can separate the catalyst of solid-state with the product aqueous solution.Due to that will be urged using activated carbon
Agent is maintained in solid phase, and few catalyst are dispensed into the product aqueous solution.PH value of water solution in embodiment 1 is 7.06,
Therefore the aqueous solution according to further ion-exchange treatment in embodiment 2 without just can directly carry out rotary evaporation water removal.
And in the embodiment 2 using unsupported catalyst, only the immersion of ion exchange resin, acid-alkali washing and dress post process will
Devote a tremendous amount of time.When column operation was carried out to the large batch of erythritol polymer aqueous solution, single batch operation can
It can continue more than three days, not only seriously drag slow speed of production, but also significant product can be caused to be lost, when industrialized
Wait, this shortcoming is infeasible for allowing for the production technology economically.
(2) it can see the present invention from embodiment 1 and embodiment 2-4 efficiency of pcr product, color, weight average molecular weight result
Higher yield, more shallow color and Geng Gao weight average molecular weight (the i.e. higher degree of polymerization) can be obtained.From embodiment 7 with
Embodiment 8-10 result is compared, and activated carbon supported catalyst of the invention can realize faster reaction rate.
(3) present invention plays a part of decolorising agent simultaneously as the activated carbon of carrier, therefore need not be again into reaction system
Add activated carbon and carclazyte.
(4) small molecule by-product that activated carbon can also be produced during adsorption reaction in time, promotes reaction to enter to positive direction
OK, the reaction time is shortened, yield is improved.
(5) compared with the embodiment 2 using unsupported catalyst, activated carbon supported catalyst can also be with less
Consumption realizes similar catalytic activity, can simultaneously be effectively saves the ion-exchange step wasted time and energy.
In summary, the present invention is loaded by using activated carbon to base catalyst, is reducing the same of catalyst amount
The catalytic activity of Shi Tigao catalyst, accelerates reaction rate, eliminates the ion-exchange process wasted time and energy the most, significantly carries
The high preparation efficiency of erythritol polymer.In addition, with other carriers commonly used in the art, such as gama-alumina and molecular sieve
Compare, the yield and product property significantly improved can be obtained using activated carbon as carrier.
Claims (10)
1. a kind of method for preparing erythritol polymer, this method comprises the following steps：In activated carbon supported base catalysis
Under the catalysis of agent so that polymerisation occurs for antierythrite monomer, so that erythritol polymer is made, wherein the alkalescence
Catalyst is selected from hydroxide, carbonate, alkoxide or its combination of alkali metal；
Methods described is further comprising the steps of：After polymerization, it is described obtained to dissolve that water is added into reaction system
Erythritol polymer, by filter operation by the obtained erythritol polymer aqueous solution with it is described activated carbon supported
Base catalyst is separated, and is then removed water and is directly obtained erythritol polymer.
2. the method for erythritol polymer is prepared as claimed in claim 1, it is characterised in that the base catalyst choosing
From：Potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium methoxide, sodium methoxide or its combination.
3. the method for erythritol polymer is prepared as claimed in claim 1, it is characterised in that methods described is additionally included in institute
Before stating polymerisation, in the antierythrite monomer that activated carbon supported base catalyst is added to molten condition.
4. the method for erythritol polymer is prepared as claimed in claim 1, it is characterised in that the polymerisation is in 20-
Carried out under the reduced pressure of 50 millimetress of mercury.
5. the method for erythritol polymer is prepared as claimed in claim 1, it is characterised in that the polymerisation is in 190-
Carried out under 250 DEG C of temperature conditionss.
6. the method for erythritol polymer is prepared as claimed in claim 1, it is characterised in that when the polymerisation continues
Between be 5-10 hours.
7. the method for erythritol polymer is prepared as claimed in claim 1, it is characterised in that to add the red of reaction system
Counted on the basis of moss sugar alcohol monomer gross mass, the consumption of the loaded catalyst is 1-10 mass %.
8. the method for erythritol polymer is prepared as claimed in claim 1, it is characterised in that described activated carbon supported
In base catalyst, the mass ratio of base catalyst and activated carbon is 1:10 to 1:4.
9. the method for erythritol polymer is prepared as claimed in claim 1, it is characterised in that the activated carbon supported alkali
Property catalyst is prepared in the following manner：Activated carbon is impregnated with the aqueous solution of the base catalyst, then to dipping
Activated carbon afterwards is filtered and dried.
10. the method for erythritol polymer is prepared as claimed in claim 1, it is characterised in that the antierythrite polymerization
The degree of polymerization of thing is 2-18.
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