CN106905522A - A kind of composite calcium-base catalyst and its application - Google Patents
A kind of composite calcium-base catalyst and its application Download PDFInfo
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- CN106905522A CN106905522A CN201510979176.0A CN201510979176A CN106905522A CN 106905522 A CN106905522 A CN 106905522A CN 201510979176 A CN201510979176 A CN 201510979176A CN 106905522 A CN106905522 A CN 106905522A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
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Abstract
The invention discloses a kind of composite calcium-base catalyst and its application.The raw material of the composite calcium-base catalyst includes the component of following weight fraction：The co-catalyst of the alkali metal hydrogen hydroxide, the calcium salt of 40%-80% and 10%-30% of 10%-40%.Composite calcium-base catalyst of the invention can be used in preparing polyethylene glycol of the molecular weight more than 8000, and process is simple is workable, it is easy to implement, and reaction speed is fast, is conducive to large-scale industrial production；Obtained molecular weight polyethylene glycol precise control simultaneously, narrow molecular weight distribution, non-residual toxicity metal ion, security is good；Additionally, the raw material in composite calcium-base catalyst of the invention is cheap and easy to get, activity is high, and induction period is short.
Description
Technical field
The present invention relates to a kind of composite calcium-base catalyst and its application.
Background technology
Polyethylene glycol (PEG) is the linear polymer generated with oxirane and water or glycol reaction,
Its structural formula is H (OCH2CH2)nOH, n represents the average adduct number of oxirane in formula.PEG dashes forward
The characteristic for going out is that, with extensive range of viscosities and hygroscopicity, and have extensive intermiscibility with solvent.
PEG also has good lubricity, heat endurance, difficult volatility and hypotoxicity.
Polyethylene glycol (or high molecular weight polyethylene glycol) is that oxirane passes through second under catalyst action
Progressively polymerization is obtained the segmentation of oxygen glycosylation reaction.The catalyst master for being used in ethoxylation in the prior art
Have following several：
(1) base metal catalysts, such as KOH, NaOH；But the tradition alkali gold such as KOH, NaOH
Metal catalyst can only produce polyethylene glycol of the relative molecular weight below 8000, and obtained polyethylene glycol is deposited
The shortcomings of molecular weight distribution is wider.
(2) alkaline earth metal compound catalyst：United States Patent (USP) US4239917 disclose BaO,
Ba(OH)2；US4223164 discloses SrO, Sr (OH)2；US4946984 discloses CaSO4；
EP85167 discloses the carboxylate of calcium：The calcium such as 2 ethyl hexanoic acid calcium, calcium oleate, calcium stearate base is complexed
Thing；United States Patent (USP) US5220077 discloses calcium oxide with calcium base complex catalysis obtained in glycol reaction
Agent.The polyethylene glycol of HMW, narrow ditribution can be obtained using above-mentioned alkaline-earth metal class catalyst, but
These catalyst have that catalysis activity is relatively low, and induction period is more long, it is impossible to be applied to the industry of polyethylene glycol
The shortcomings of metaplasia is produced.Patent WO9304030, US4453023, US5220077 are disclosed using polynary
Sour such as phosphoric acid, oxalic acid, citric acid, tartaric acid makees co-catalyst, and ethoxylation induction period substantially shortens,
Reaction speed is greatly improved.But the size of co-catalyst addition is to the relative molecular mass distribution shadow of product
Sound is larger.
After ethoxylation terminates, catalyst is difficult to be separated from product；Some alkaline-earth metal from
Son such as Ba2+With certain toxicity, the toxicity alkali salt of these residuals will influence the safety of product
Property, there is potential safety hazard.
Therefore, this area need badly it is a kind of new for the catalyst in ethoxylation, it is existing to overcome
Above-mentioned technical problem present in technology.
The content of the invention
The technical problems to be solved by the invention are in order in overcoming the preparation method of existing polyethylene glycol
What the catalyst used in ethoxylation was present cannot prepare poly- second two of the molecular weight more than 8000
Alcohol, or catalyst activity is low, induction period is long, it is impossible to be applied to the industrialized production of polyethylene glycol, right
The molecular weight distribution of polyethylene glycol has considerable influence, is difficult to that certain safety is separated and existed from product
The defect of hidden danger etc., and provide a kind of composite calcium-base catalyst and its application.Composite calcium-base of the invention
Catalyst can be used in preparing polyethylene glycol of the molecular weight more than 8000, process is simple, operability
By force, it is easy to embodiment, reaction speed is fast, is conducive to large-scale industrial production；Poly- second obtained in simultaneously
Glycol molecular weight precise control, narrow molecular weight distribution, non-residual toxicity metal ion, security is good；This
Outward, the raw material in composite calcium-base catalyst of the invention is cheap and easy to get, and activity is high, and induction period is short.
The present invention mainly solves above-mentioned technical problem by the following technical programs.
The invention provides a kind of composite calcium-base catalyst, its raw material includes the component of following weight fraction：
The co-catalyst of the alkali metal hydrogen hydroxide, the calcium salt of 40%-80% and 10%-30% of 10%-40%, institute
The percentage (%) stated refers to that the quality of above-mentioned each component accounts for the percentage of the raw material gross mass.
In described composite calcium-base catalyst, the content of described alkali metal hydrogen hydroxide is preferably
10%-30%, is more preferably 20%-30%.The content of described calcium salt is preferably 40%-70%, more
It is goodly 45%-60%.The content of described co-catalyst is preferably 15%-20%.Above content is equal
Refer to weight/mass percentage composition, described percentage (%) refers to that the quality of above-mentioned each component accounts for the raw material
The percentage of gross mass.
It is preferred that described composite calcium-base catalyst, its raw material is made up of the component of following weight fraction：
The co-catalyst of the alkali metal hydrogen hydroxide, the calcium salt of 40%-80% and 10%-30% of 10%-40%, institute
The percentage (%) stated refers to that the quality of above-mentioned each component accounts for the percentage of the raw material gross mass.
In described composite calcium-base catalyst, the alkali metal in described alkali metal hydroxide is generally referred to
IA races metallic element.Described alkali metal hydroxide is preferably NaOH, potassium hydroxide and hydrogen
One or more in cesium oxide.Described calcium salt can be the calcium salt of routine in ethoxylation technique, preferably
Ground is inorganic calcium salt and/or organic calcium salt.Described inorganic calcium salt be preferably calcium hydroxide, calcium oxide,
One or more in calcium sulfate and calcium phosphate.Described organic calcium salt be preferably calcium formate, calcium acetate,
Calcium propionate (such as n Propanoic acid calcium), calcium citrate, calcium laurate, calcium stearate, detergent alkylate sulphur
One or more in sour calcium, p-methyl benzenesulfonic acid calcium, calcium glycerophosphate, 2 ethyl hexanoic acid calcium and calcium oleate.
Described co-catalyst can be the co-catalyst of routine in ethoxylation technique, preferably Bronsted acid.Institute
The Bronsted acid stated preferably sulfuric acid, phosphoric acid, oxalic acid, citric acid, tartaric acid, p-methyl benzenesulfonic acid and ammonia
One or more in base sulfonic acid.
Present invention also offers a kind of foregoing composite calcium-base catalyst in the preparation side of polyethylene glycol
As the application of catalyst in method.
The preparation method of described polyethylene glycol is preferably comprised the following steps：In inert gas and/or nitrogen
Under protection and anhydrous condition, under the catalysis of foregoing composite calcium-base catalyst, by low-molecular-weight two
Alcohol and oxirane carry out polymerisation, you can；More preferably comprise the following steps：Inert gas and/
Or under nitrogen protection, low molecular weight diols and described composite calcium-base catalyst are mixed, then anhydrous
Under the conditions of, oxirane is added, carry out polymerisation, you can.
In the preparation method of described polyethylene glycol, described inert gas is generally helium, neon, argon
Gas, Krypton, xenon or radon gas.In the present invention, described inert gas is preferably argon gas.
Described low molecular weight diols can be the low molecular weight diols of routine in polyethylene glycol preparation field, compared with
Be goodly ethylene glycol, one or more in diethylene glycol (DEG), triethylene glycol and tetraethylene glycol.Described composite calcium-base
The consumption of catalyst can be the conventional amount used of catalyst in ethoxylation technique, and its better quality ground is low point
Son amount glycol and oxirane gross mass 0.05%-1%, be more preferably 0.1%-0.5%, most preferably for
0.2%-0.5%.The temperature of described polymerisation can be the temperature of routine in ethoxylation technique, preferably
Ground is 80-180 DEG C, is more preferably 100-160 DEG C, is most preferably 120-160 DEG C.Described polymerisation
Pressure can be conventional pressure in ethoxylation technique, preferably 0-0.5MPa, more preferably for
0.1-0.4MPa, is most preferably 0.2-0.4MPa.The time of described polymerisation can be ethyoxyl chemical industry
Conventional time, preferably 1-8 hours in skill.In the present invention, temperature and the reaction of the reaction
The holding of pressure can be realized by controlling and adjusting the addition speed of oxirane.It is described in the present invention
Time of reaction be addition time of oxirane.
It is anhydrous described in realization preferably by operating for dehydration in the preparation method of described polyethylene glycol
Condition.The operation of described dehydration can be the operation of routine in ethoxylation technique, and preferably negative pressure takes off
Water.Negative pressure in described negative pressure dehydration is preferably -0.08~-0.1MPa, is more preferably -0.09MPa.
The temperature of described negative pressure dehydration is preferably 90 DEG C -130 DEG C, is more preferably 100 DEG C -110 DEG C.It is described
Negative pressure dehydration time be preferably 20min~60min.It is former that described negative pressure dehydration generally refers to removing
Before water or oxirane in material are added, the alkali metal in low molecular weight diols and composite calcium-base catalyst
Calcium hydroxide reaction in hydroxide and/or calcium salt generates the water produced during alkoxide.
The preparation method of described polyethylene glycol also can further include curing, degassing and the operation for neutralizing.
Wherein, the operation of described curing can be the operation of routine in ethoxylation technique.The temperature of described curing
Preferably 110~160 DEG C of degree.The time of described curing is preferably 30min.Described degassing
Operation can be the operation of routine in ethoxylation technique, generally negative pressure degasification, in described negative pressure degasification
Negative pressure be preferably -0.08~-0.1MPa, be more preferably -0.09MPa.The time of described negative pressure degasification
Preferably 30min.The operation of described neutralization generally with it is sour by the pH value of reaction system adjust to
5.5~7.0.Described acid can be the conventional use of acid of neutralization operation in ethoxylation technique, as long as can adjust
The pH to 5.5-7.0 of reaction system, described acid is preferably in acetic acid, phosphoric acid and lactic acid
Plant or various.
Before described neutralization operation is carried out, preferably also include carrying out the reaction system cured after degassing
The operation of cooling.Described is cooled to this area routine operation, and described cooling is preferably reactant
System is cooled to 80 DEG C -100 DEG C, more preferably to be cooled to 90 DEG C.
In the preparation method of described polyethylene glycol, the number-average molecular weight of obtained polyethylene glycol is preferably
200-30000, is more preferably 2000-20000, is most preferably 8000-20000.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can be combined, and obtain final product this
Invent each preferred embodiments.
In the present invention, ethoxylation refers to that oxirane is opened with the organic compound containing active hydrogen
Cyclopolymerization is reacted；Ethoxylation technique includes that batch tank technique, Press atomizings technique, Buss are returned
Road technique and continuous pipe type technique.
Agents useful for same of the present invention and raw material are commercially available.
Positive effect of the invention is：
Composite calcium-base catalyst of the invention can be used in preparing polyethylene glycol of the molecular weight more than 8000,
Process is simple, workable, it is easy to embodiment, reaction speed is fast, is conducive to large-scale industry metaplasia
Produce；Obtained molecular weight polyethylene glycol precise control, narrow molecular weight distribution, non-residual toxicity metal simultaneously
Ion, security is good；Additionally, the raw material in composite calcium-base catalyst of the invention is cheap and easy to get, activity
Height, induction period is short.
Brief description of the drawings
Fig. 1 is the GPC chromatograms of polyethylene glycol obtained in embodiment 7.
Fig. 2 is the GPC chromatograms of polyethylene glycol obtained in comparative example 2.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but is not therefore limited the present invention to
Among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to normal
Rule method and condition, or selected according to catalogue.
Embodiment 1
To input 400g diethylene glycol (DEG)s, 1.6g composite calcium-base catalyst (its in dry 2L pressure reaction stills
Middle potassium hydroxide accounts for the 20% of catalyst weight, and calcium hydroxide accounts for 70%, and 10%) sulfuric acid account for, and sealing is anti-
Answer kettle；With air in nitrogen displacement reactor 3 times, stirring is opened；100 DEG C are warming up to, in -0.09MPa
Pressure under be dehydrated 60min；100 DEG C are warming up to, being slowly added to 1200g oxirane be polymerized instead
Should；Wherein, by controlling the addition speed of oxirane so that reaction pressure is maintained at 0.3MPa, instead
Answer temperature to be maintained at 130 DEG C, last 417min；After reaction terminates, in curing 30min at 130 DEG C,
Deaerate 15min under the pressure of -0.09MPa again, after being subsequently cooled to 90 DEG C, with vinegar acid for adjusting pH extremely
7.0, polyethylene glycol is obtained final product, the number-average molecular weight and molecular weight of product are characterized by GPC exclusion chromatographies
Distribution, is as a result listed in table 1.
Embodiment 2
It is multiple to the product, 3.75g that are put into dry 2L pressure reaction stills described in 250g embodiments 1
Conjunction calcium based catalysts (wherein NaOH accounts for the 30% of catalyst weight, and 2 ethyl hexanoic acid calcium accounts for 60%,
10%) oxalic acid account for, sealed reactor；With air in nitrogen displacement reactor 3 times, stirring is opened；Rise
Temperature is dehydrated 60min to 100 DEG C under the pressure of -0.09MPa；100 DEG C are warming up to, 1000 are slowly added to
G oxirane carries out polymerisation；Wherein, by controlling the addition speed of oxirane so that reaction pressure
Power is maintained at 0.25MPa, and reaction temperature is maintained at 140 DEG C, lasts 99min；After reaction terminates, in
30min is cured at 140 DEG C, then the 20min that deaerated under the pressure of -0.09MPa, it is subsequently cooled to 90 DEG C
Afterwards, polyethylene glycol is obtained final product to 7.0 with newborn acid for adjusting pH, product is characterized by GPC exclusion chromatographies
Number-average molecular weight and molecular weight distribution, be as a result listed in table 1.
Embodiment 3
It is multiple to the product, 3.75g that are put into dry 2L pressure reaction stills described in 150g embodiments 1
(wherein potassium hydroxide accounts for the 30% of catalyst weight, and calcium phosphate accounts for 55%, citric acid to close calcium based catalysts
Account for 15%), sealed reactor；With air in nitrogen displacement reactor 3 times, stirring is opened；It is warming up to
100 DEG C, 60min is dehydrated under the pressure of -0.09MPa；120 DEG C are warming up to, 1350g is slowly added to
Oxirane carries out polymerisation；Wherein, by controlling the addition speed of oxirane so that reaction pressure
0.3MPa is maintained at, reaction temperature is maintained at 150 DEG C, lasts 144min；After reaction terminates, in 150 DEG C
Lower curing 30min, then the 20min that deaerated under the pressure of -0.09MPa, after being subsequently cooled to 90 DEG C, use
Newborn acid for adjusting pH obtains final product polyethylene glycol to 7.0, and the number for characterizing product by GPC exclusion chromatographies is equal
Molecular weight and molecualr weight distribution, is as a result listed in table 1.
Embodiment 4
It is multiple to the product, 8.2g that are put into dry 2L pressure reaction stills described in 400g embodiments 2
(wherein potassium hydroxide accounts for the 40% of catalyst weight, and calcium propionate accounts for 40%, tartaric acid to close calcium based catalysts
Account for 20%), sealed reactor；With air in nitrogen displacement reactor 3 times, stirring is opened；It is warming up to
100 DEG C, 60min is dehydrated under the pressure of -0.09MPa；100 DEG C are warming up to, 1240g is slowly added to
Oxirane carries out polymerisation；Wherein, by controlling the addition speed of oxirane so that reaction pressure
0.15MPa is maintained at, reaction temperature is maintained at 120 DEG C, lasts 54min；After reaction terminates, in 120 DEG C
Lower curing 30min, then the 20min that deaerated under the pressure of -0.09MPa, after being subsequently cooled to 90 DEG C, use
Vinegar acid for adjusting pH obtains final product polyethylene glycol to 7.0, and the number for characterizing product by GPC exclusion chromatographies is equal
Molecular weight and molecualr weight distribution, is as a result listed in table 1.
Embodiment 5
It is multiple to the product, 4.63g that are put into dry 2L pressure reaction stills described in 300g embodiments 2
(wherein NaOH accounts for the 25% of catalyst weight, and calcium laurate accounts for 45%, to first to close calcium based catalysts
30%) benzene sulfonic acid accounts for, sealed reactor；With air in nitrogen displacement reactor 3 times, stirring is opened；
100 DEG C are warming up to, 60min is dehydrated under the pressure of -0.09MPa；100 DEG C are warming up to, are slowly added to
1245g oxirane carries out polymerisation；Wherein, by controlling the addition speed of oxirane so that anti-
Pressure is answered to be maintained at 0.25MPa, reaction temperature is maintained at 160 DEG C, lasts 95min；After reaction terminates,
In curing 30min at 160 DEG C, then the 25min that deaerated under the pressure of -0.09MPa, it is subsequently cooled to 90 DEG C
Afterwards, polyethylene glycol is obtained final product to 7.0 with vinegar acid for adjusting pH, product is characterized by GPC exclusion chromatographies
Number-average molecular weight and molecular weight distribution, be as a result listed in table 1.
Embodiment 6
It is multiple to the product, 6.2g that are put into dry 2L pressure reaction stills described in 200g embodiments 2
(wherein potassium hydroxide accounts for the 10% of catalyst weight, p-methyl benzenesulfonic acid calcium 70%, phosphorus to close calcium based catalysts
20%) acid account for, sealed reactor；With air in nitrogen displacement reactor 3 times, stirring is opened；Heat up
To 110 DEG C, 60min is dehydrated under the pressure of -0.09MPa；At 110 DEG C, 1360g is slowly added to
Oxirane carries out polymerisation；Wherein, by controlling the addition speed of oxirane so that reaction pressure
0.4MPa is maintained at, reaction temperature is maintained at 140 DEG C, lasts 109min；After reaction terminates, in 140 DEG C
Lower curing 30min, then the 30min that deaerated under the pressure of -0.09MPa, after being subsequently cooled to 90 DEG C, use
Vinegar acid for adjusting pH obtains final product polyethylene glycol to 7.0, and the number for characterizing product by GPC exclusion chromatographies is equal
Molecular weight and molecualr weight distribution, is as a result listed in table 1.
Embodiment 7
It is multiple to the product, 2.6g that are put into dry 2L pressure reaction stills described in 250g embodiments 3
(wherein potassium hydroxide accounts for the 30% of catalyst weight, and calcium sulfate accounts for 55%, amino sulphur to close calcium based catalysts
15%) acid account for, sealed reactor；With air in nitrogen displacement reactor 3 times, stirring is opened；Heat up
To 110 DEG C, 60min is dehydrated under the pressure of -0.09MPa；At 110 DEG C, 1063g is slowly added to
Oxirane carries out polymerisation；Wherein, by controlling the addition speed of oxirane so that reaction pressure
0.3MPa is maintained at, reaction temperature is maintained at 145 DEG C, lasts 225min；After reaction terminates, in 145 DEG C
Lower curing 30min, then the 30min that deaerated under the pressure of -0.09MPa, after being subsequently cooled to 90 DEG C, use
Vinegar acid for adjusting pH obtains final product polyethylene glycol to 7.0, and the number for characterizing product by GPC exclusion chromatographies is equal
Molecular weight and molecualr weight distribution, is as a result listed in table 1, and its GPC chromatogram is shown in Fig. 1.
Comparative example 1
To the product, the 2.6g hydrogen that are put into dry 2L pressure reaction stills described in 250g embodiments 3
Potassium oxide, sealed reactor；With air in nitrogen displacement reactor 3 times, stirring is opened；It is warming up to
110 DEG C, 60min is dehydrated under the pressure of -0.09MPa；At 110 DEG C, 1063g rings are slowly added to
Oxidative ethane carries out polymerisation；Wherein, by controlling the addition speed of oxirane so that reaction pressure is tried hard to keep
Hold in 0.3MPa, reaction temperature is maintained at 130 DEG C, lasts 116min；After reaction terminates, in 130 DEG C
Lower curing 30min, then the 30min that deaerated under the pressure of -0.09MPa, after being subsequently cooled to 90 DEG C, use
Vinegar acid for adjusting pH obtains final product polyethylene glycol to 7.0, and the number for characterizing product by GPC exclusion chromatographies is equal
Molecular weight and molecualr weight distribution, is as a result listed in table 1.
Comparative example 2
To the product, the 0.78g hydrogen that are put into dry 2L pressure reaction stills described in 250g embodiments 3
Potassium oxide and 1.82g calcium sulfate, sealed reactor；With air in nitrogen displacement reactor 3 times, open
Stirring；110 DEG C are warming up to, 60min is dehydrated under the pressure of -0.09MPa；At 110 DEG C, slowly
Adding 1063g oxirane carries out polymerisation；Wherein, by control the addition speed of oxirane with
Reaction pressure is set to be maintained at 0.3MPa, reaction temperature is maintained at 145 DEG C, lasts 270min；Reaction knot
Shu Hou, in curing 30min at 145 DEG C, then deaerated under the pressure of -0.09MPa 30min, Ran Houleng
But to after 90 DEG C, with vinegar acid for adjusting pH to 7.0, polyethylene glycol is obtained final product, by GPC exclusion chromatographies
The number-average molecular weight and molecular weight distribution of product are characterized, table 1 is as a result listed in, its GPC chromatogram is shown in Fig. 2.
Comparative example 3
To the product, the 2.08g sulphur that are put into dry 2L pressure reaction stills described in 250g embodiments 3
Sour calcium and 0.52g sulfamic acids, sealed reactor；With air in nitrogen displacement reactor 3 times, open
Stirring；110 DEG C are warming up to, 60min is dehydrated under the pressure of -0.09MPa；140 DEG C are warming up to, are delayed
Slow addition 1063g oxirane carries out polymerisation；Wherein, by controlling the addition speed of oxirane
So that reaction pressure is maintained at 0.3MPa, reaction temperature is maintained at 180 DEG C, lasts 810min；Reaction
After end, in curing 30min at 160 DEG C, then the 30min that deaerated under the pressure of -0.09MPa, then
After being cooled to 90 DEG C, with vinegar acid for adjusting pH to 7.0, polyethylene glycol is obtained final product, by GPC gel chromatographies
Method characterizes the number-average molecular weight and molecular weight distribution of product, is as a result listed in table 1.
Comparative example 4
To the product, the 0.13g hydrogen that are put into dry 2L pressure reaction stills described in 250g embodiments 3
Potassium oxide, 1.58g calcium propionates and 0.92g p-methyl benzenesulfonic acid, sealed reactor；Reacted with nitrogen displacement
Air 3 times in kettle, open stirring；110 DEG C are warming up to, 60min is dehydrated under the pressure of -0.09MPa；
140 DEG C are warming up to, being slowly added to 1063g oxirane carries out polymerisation；Wherein, by control ring
So that reaction pressure is maintained at 0.3MPa, reaction temperature is maintained at 165 DEG C, goes through for the addition speed of oxidative ethane
When 405min；After reaction terminates, in curing 30min at 165 DEG C, then under the pressure of -0.09MPa
Degassing 30min, after being subsequently cooled to 90 DEG C, with vinegar acid for adjusting pH to 7.0, obtains final product polyethylene glycol, leads to
Number-average molecular weight and molecular weight distribution that GPC exclusion chromatographies characterize product are crossed, table 1 is as a result listed in.
Comparative example 5
To the product, the 1.58g hydrogen that are put into dry 2L pressure reaction stills described in 250g embodiments 3
Potassium oxide, 0.79g calcium phosphate and 0.26g oxalic acid, sealed reactor；With sky in nitrogen displacement reactor
Gas 3 times, opens stirring；110 DEG C are warming up to, 60min is dehydrated under the pressure of -0.09MPa；Heat up
To 130 DEG C, being slowly added to 1063g oxirane carries out polymerisation；Wherein, by controlling epoxy second
So that reaction pressure is maintained at 0.3MPa, reaction temperature is maintained at 145 DEG C, lasts for the addition speed of alkane
135min；After reaction terminates, in curing 30min at 145 DEG C, then deaerated under the pressure of -0.09MPa
30min, after being subsequently cooled to 90 DEG C, with vinegar acid for adjusting pH to 7.0, obtains final product polyethylene glycol, passes through
GPC exclusion chromatographies characterize the number-average molecular weight and molecular weight distribution of product, are as a result listed in table 1.
Catalyst amount, reaction temperature, catalyst activity and system in the embodiment 1-7 of table 1 and comparative example 1-5
The number-average molecular weight and polydispersity index of the PEG for obtaining
Mn represents number-average molecular weight, and PDI is polyethylene glycol polydispersity index, represents molecular weight distribution.
The composition of the catalyst used in the embodiment 1-7 of table 2 and comparative example 1-5
As shown in Table 1, embodiment 1-7 uses composite calcium-base catalyst of the invention, obtained PEG to produce
Not only molecular weight control is precisely and molecular weight distribution is very narrow for product, the PDI of polyethylene glycol 1.02-1.05 it
Between；Particularly embodiment 5,6 and 7 can obtain high molecular weight PEGs product of the molecular weight more than 8000
Product.Using only alkali metal hydroxide KOH as catalyst in comparative example 1, chemical reaction meter is passed through
The oxirane (product molecule set amount is 20000) of amount, finds that its number is divided equally after GPC is detected
Son amount is only 8513, it is impossible to obtain the PEG products of HMW.Alkali metal is employed in comparative example 2
As a result hydroxide KOH and calcium sulfate compounding find that the catalyst can be more accurate as catalyst
The high molecular weight PEGs product for being set, but exist that catalyst activity is weaker and molecular weight product
The defects such as wider distribution.And calcium sulfate and the compounding conduct of co-catalyst sulfamic acid are employed in comparative example 3
Catalyst, equally exists the problems such as catalyst activity is weak and product molecular weight distribution is wide.
Claims (10)
1. a kind of composite calcium-base catalyst, it is characterised in that its raw material includes the group of following weight fraction
Point：The co-catalyst of the alkali metal hydrogen hydroxide, the calcium salt of 40%-80% and 10%-30% of 10%-40%,
Described percentage refers to that the quality of above-mentioned each component accounts for the percentage of the raw material gross mass.
2. composite calcium-base catalyst as claimed in claim 1, it is characterised in that described alkali metal
The content of hydrogen hydroxide is 10%-30%, preferably 20%-30%；And/or, described calcium salt
Content is 40%-70%, preferably 45%-60%；And/or, the content of described co-catalyst is
15%-20%；Above content each means weight/mass percentage composition, and described percentage refers to above-mentioned each component
Quality accounts for the percentage of the raw material gross mass.
3. composite calcium-base catalyst as claimed in claim 1 or 2, it is characterised in that described alkali
Alkali metal in metal hydroxides refers to IA races metallic element；And/or, described calcium salt is inorganic calcium
Salt and/or organic calcium salt；And/or, described co-catalyst is Bronsted acid.
4. composite calcium-base catalyst as claimed in claim 3, it is characterised in that described alkali metal
Hydroxide is one or more in NaOH, potassium hydroxide and cesium hydroxide；And/or, it is described
Inorganic calcium salt is one or more in calcium hydroxide, calcium oxide, calcium sulfate and calcium phosphate；And/or, institute
The organic calcium salt stated be calcium formate, calcium acetate, calcium propionate, calcium citrate, calcium laurate, calcium stearate,
In calcium dodecyl benzene sulfonate, p-methyl benzenesulfonic acid calcium, calcium glycerophosphate, 2 ethyl hexanoic acid calcium and calcium oleate
One or more；And/or, described Bronsted acid is sulfuric acid, phosphoric acid, oxalic acid, citric acid, tartaric acid,
One or more in p-methyl benzenesulfonic acid and sulfamic acid.
5. system of a kind of composite calcium-base catalyst as described in claim any one of 1-4 in polyethylene glycol
As the application of catalyst in Preparation Method.
6. application as claimed in claim 5, it is characterised in that the preparation side of described polyethylene glycol
Method comprises the following steps：Under inert gas and/or nitrogen protection and anhydrous condition, in such as claim
Under the catalysis of the composite calcium-base catalyst described in any one of 1-4, low molecular weight diols and oxirane are entered
Row polymerisation, you can.
7. application as claimed in claim 6, it is characterised in that the preparation side of described polyethylene glycol
In method, described inert gas is helium, neon, argon gas, Krypton, xenon or radon gas；And/or, institute
The low molecular weight diols stated are one or more in ethylene glycol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol；With
/ or, the quality of described composite calcium-base catalyst is low molecular weight diols and oxirane gross mass
0.05%-1%, preferably 0.1%-0.5%, are more preferably 0.2%-0.5%；And/or, described polymerization
Reaction temperature is 80-180 DEG C, and preferably 100-160 DEG C, be more preferably 120-160 DEG C；And/or,
The pressure of described polymerisation be 0-0.5MPa, preferably 0.1-0.4MPa, more preferably for
0.2-0.4MPa；And/or, the time of described polymerisation is 1-8 hours.
8. application as claimed in claim 6, it is characterised in that the preparation side of described polyethylene glycol
In method, by the anhydrous condition described in realizing that operates being dehydrated；The operation of described dehydration is preferably negative
Press-dehydrating；Negative pressure in described negative pressure dehydration is preferably -0.08~-0.1MPa, more preferably for
-0.09MPa；The temperature of described negative pressure dehydration is preferably 90 DEG C -130 DEG C, more preferably for
100℃-110℃；The time of described negative pressure dehydration is preferably 20min~60min.
9. application as claimed in claim 6, it is characterised in that the preparation side of described polyethylene glycol
Method further comprises curing, degassing and the operation for neutralizing；Wherein, the temperature of described curing is preferably
It is 110~160 DEG C；The time of described curing is preferably 30min；The operation of described degassing is preferable
Ground is negative pressure degasification, and the negative pressure in described negative pressure degasification is preferably -0.08~-0.1MPa, more preferably for
-0.09MPa；The time of described negative pressure degasification is preferably 30min；The operation of described neutralization is preferable
Ground is to be adjusted to 5.5~7.0 the pH value of reaction system with acid；Described acid is preferably acetic acid, phosphoric acid
With one or more in lactic acid.
10. application as claimed in claim 9, it is characterised in that the preparation side of described polyethylene glycol
In method, before described neutralization operation is carried out, also including the reaction system cured after degassing is cooled down
Operation；Described cooling is preferably and for reaction system to be cooled to 80 DEG C -100 DEG C, is more preferably cooling
To 90 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019034150A1 (en) * | 2017-08-18 | 2019-02-21 | 佳化化学（茂名）有限公司 | Catalyst for synthesizing polyethylene oxide polymer and synthesis method thereof |
| CN110628010A (en) * | 2019-10-18 | 2019-12-31 | 辽宁奥克医药辅料股份有限公司 | Catalyst composition and method for preparing medium molecular weight polyethylene glycol by using same |
| WO2024086464A1 (en) | 2022-10-19 | 2024-04-25 | Dow Global Technologies Llc | Liquid polyethylene glycols |
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| CN1062680A (en) * | 1991-11-04 | 1992-07-15 | 中国石油化工总公司 | The basic compound catalysis alkyl phenolic alkoxy of calcium |
| CN101070272A (en) * | 2007-06-12 | 2007-11-14 | 无锡百川化工股份有限公司 | Process for producing oxyalkylated trihydroxy methyl-propane |
| CN102477154A (en) * | 2012-02-28 | 2012-05-30 | 三江化工有限公司 | Preparation method of fatty alcohol polyoxyethylene ether |
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| CN1062680A (en) * | 1991-11-04 | 1992-07-15 | 中国石油化工总公司 | The basic compound catalysis alkyl phenolic alkoxy of calcium |
| CN101070272A (en) * | 2007-06-12 | 2007-11-14 | 无锡百川化工股份有限公司 | Process for producing oxyalkylated trihydroxy methyl-propane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019034150A1 (en) * | 2017-08-18 | 2019-02-21 | 佳化化学（茂名）有限公司 | Catalyst for synthesizing polyethylene oxide polymer and synthesis method thereof |
| US11634541B2 (en) | 2017-08-18 | 2023-04-25 | Jiahua Chemicals (Maoming) Co., Ltd. | Catalyst for synthesizing polyethylene oxide polymer and synthesis method thereof |
| CN110628010A (en) * | 2019-10-18 | 2019-12-31 | 辽宁奥克医药辅料股份有限公司 | Catalyst composition and method for preparing medium molecular weight polyethylene glycol by using same |
| CN110628010B (en) * | 2019-10-18 | 2022-09-27 | 辽宁奥克医药辅料股份有限公司 | Catalyst composition and method for preparing polyethylene glycol with medium molecular weight by using same |
| WO2024086464A1 (en) | 2022-10-19 | 2024-04-25 | Dow Global Technologies Llc | Liquid polyethylene glycols |
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