CN110016128A - A kind of reuse method of 6-caprolactone by-product - Google Patents
A kind of reuse method of 6-caprolactone by-product Download PDFInfo
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- CN110016128A CN110016128A CN201910369438.XA CN201910369438A CN110016128A CN 110016128 A CN110016128 A CN 110016128A CN 201910369438 A CN201910369438 A CN 201910369438A CN 110016128 A CN110016128 A CN 110016128A
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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/88—Post-polymerisation treatment
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Abstract
The invention discloses a kind of reuse methods of 6-caprolactone by-product, caprolactone by-product and small molecule polyol are fed intake by a certain percentage, antioxidant, catalyst is added, it is reacted under the conditions of 140-200 DEG C, then 1-3h is kept the temperature under the conditions of 205-240 DEG C, catalyst is added and gradually reduces pressure, finally makes system acid value≤2.0mg KOH/g.Then decolorization is carried out to product.The present invention can solve the problems, such as that Caprolactone oligomers recycling is a kind of environmentally friendly, efficient processing method.
Description
Technical field
The present invention relates to returning for a kind of reuse method for the by-product that chemical products generate, especially 6-caprolactone by-product
Use method.
Background technique
6-caprolactone (ε-CL) is a kind of important organic synthesis intermediate, be mainly used for synthesizing polycaprolactone polyol,
The copolymerization and modification of polycaprolactone and other esters polymers, because polycaprolactone has good nontoxicity, biological degradability, compatible
Property, seep pharmacological property, so its degradative plastics and biomedicine in obtain preferable application.
Generally by cyclohexanone, Peracetic acid or Perpropionic Acid Baeyer-occurs under certain condition for the synthesis of 6-caprolactone
Vertical reaction grid is tieed up to generate.6-caprolactone is a kind of temperature sensitivity substance, is easily polymerized to the oligomeric of the 2-10 degree of polymerization certainly at high temperature
Object, and in 6-caprolactone production process, rectification working process temperature is higher, and 6-caprolactone generates a degree of autohemagglutination, generates oneself
Interior ester oligomer, causes amount of waste to increase, and production cost rises.Domestic manufacturer produces 6-caprolactone yield and generally there was only 80%,
And there is 20% by-product to generate.By-product is analyzed wherein containing 6-caprolactone about 10-20%, 78-88% low molecular weight
Carboxyl end group polycaprolactone, 0.5% hydroxycaproic acid, in addition there are about 1.5% light component and heavy constituents.
Caprolactone by-product is mud shape fluid at normal temperature, but will become solid after placing a period of time, and processing is difficult
Degree is big, causes intractable environmental issue.Patent of invention CN104292206A describes a kind of method by depolymerization to handle ε-
The oligomer generated in caprolactone production process, the collection rate of 6-caprolactone are 65%, and still suffering from cannot largely recycle
Substance can not depolymerization and need to handle, in addition industrializing depolymerizer equipment investment has biggish economic press to small business greatly
Power.
Current all 6-caprolactone manufacturing enterprises face the common the difficult problem of environmental protection of caprolactone by-product processing.In order to solve
This problem, present inventor has performed careful scientific researches, have developed the pair generated in processing 6-caprolactone production process
The method of product makes caprolactone by-product turn waste into wealth, increases economic efficiency, and solves the difficult problem of environmental protection.
Summary of the invention
The present invention provides a kind of method for recycling caprolactone by-product, generates in solution 6-caprolactone production process
The problem of by-product.Caprolactone by-product is turned waste into wealth, improved by polymerization polycaprolactone polyol using this method
Economic benefit solves environment difficulties.
Particular content of the invention are as follows:
A kind of recoverying and utilizing method of 6-caprolactone by-product first detects the acid value and hydroxyl value of by-product, then passes through gas
Phase chromatography determines the content of 6-caprolactone, Caprolactone oligomers, other products.Then it is polynary that a certain proportion of small molecule is added
Alcohol is reacted.Decolorization finally is carried out to product.Specific step is as follows:
A certain amount of caprolactone by-product, antioxidant, catalyst are put into a kettle, are put by the index of detection opposite
The small molecule polyol that should be measured, then heats up, and is reacted that (heating rate is 5-15 DEG C/h, and in corresponding temperature at 140-200 DEG C
Degree is lower to react 1h), after the by-product water of the overwhelming majority of generation is evaporated off in normal pressure, in 200~240 DEG C of heat preservation 1-3h, continue
Reaction.Catalyst is added in second stage, then vacuumizes, and step up vacuum degree, and minor amount of water and extra small is removed under reduced pressure
Molecular polylol compound makes to react the direction progress to low acid value polyester polyol is generated, until acid value≤2mg KOH/g.
Then product is subjected to decolorization.
The small molecule polyol being added is selected from ethylene glycol, diglycol, neopentyl glycol, 1,4- butanediol, 1,3-
Butanediol, 1,2 propylene glycol, 1,3 propylene glycol, 2- methyl propanediol, 1,5- pentanediol, 3- methyl-1,5- pentanediol, 1,6- oneself two
The dihydric alcohols such as alcohol, 1,4- hydroxymethyl-cyclohexane, 1,4- cyclohexanediol；The trihydroxylic alcohols such as glycerol, trimethylolpropane；Pentaerythrite
Equal tetrahydroxylic alcohols；The pentabasis alcohols such as xylitol；The hexahydroxylic alcohols such as sorbierite, mannitol；Eight yuan of alcohol such as sucrose etc..Preferably ethylene glycol, new
Pentanediol, glycerol, trimethylolpropane, pentaerythrite, xylitol, sorbierite, mannitol, sucrose；More preferably ethylene glycol, sweet
Oil, xylitol, sucrose.
The catalyst that the reaction process first step is added is antimony glycol, antimony oxide, Mono-n-butyltin, octanoic acid Asia
Tin, dialkyl tin dimaleate, butyl titanate and tetraisopropyl titanate etc.；Preferably Mono-n-butyltin and dialkyl tin
Dimaleate.Additional amount is 0-1000ppm, preferably 30-100ppm.
The temperature of first step reaction is 140-200 DEG C, and each thermotonus 1h, process takes the mode of ladder-elevating temperature, rank
The rate of ladder heating is 5-20 DEG C/h；Preferably 5-15 DEG C/h.
After water is evaporated off in normal pressure, in 200~240 DEG C of heat preservations 1~3h, preferably 215-225 DEG C heat preservation 1.5-2.5h.
The catalyst that reaction process second step is added is antimony glycol, antimony oxide, Mono-n-butyltin, octanoic acid Asia
Tin, dialkyl tin dimaleate, butyl titanate and tetraisopropyl titanate etc.；Preferably four isopropyl of butyl titanate and metatitanic acid
Ester.Additional amount is 0-200ppm, preferably 10-50ppm.
The antioxidant of addition is one of phosphite ester antioxidant, hindered phenol antioxygen or two kinds.Preferably by
It hinders phenolic antioxidant 1010 and adds triphenyl phosphite.Additional amount is 0.05%-2%, preferably 0.1%-0.6%.
Second step reaction vacuum degree, which steps up, (can't see after drop drips in reaction kettle recycling can visor 10min and mentions again
Condition of high vacuum degree).Vacuum degree should not rise too fast, otherwise be easy that alcohol is taken out of to and occurred Concerning Flooding Phenomenon.Absolute vacuum presses 60K in kettle
Pa, 40KPa, 20KPa, 10KPa, 5KPa, 2KPa, 1KPa, 0.5KPa are gradually reduced.
The molal quantity that small molecule polyol molal quantity should be more than system middle-end carboxy-polycaprolactone polyalcohol is added.It is preferred that
For the more 5%-15% of small molecule polyol mole ratio carboxyl end group polycaprolactone polyol molal quantity.
Polyol product after synthesis need to carry out decolorization.Decoloration can remove color except color or bleaching agent by absorption.
Except color adsorbent includes: active carbon, organobentonite etc.；Bleaching agent includes sodium sulfite, sodium hydrogensulfite, Jiao Ya
Sodium sulphate, H2O2, hypochlorous acid etc..Preferably sodium pyrosulfite, sodium sulfite.
The present invention solves 6-caprolactone and produced using caprolactone by-product as the method for Material synthesis polycaprolactone polyol
The problem of by-product generated in journey.Caprolactone by-product is become by polymerization polycaprolactone polyol using this method
Waste be changed into values, increase economic efficiency, solves environment difficulties.
The invention has the characteristics that:
Caprolactone by-product is reacted with small molecule polyol and then carries out decolorization becomes polycaprolactone polyol,
Solid waste is turned waste into wealth, environmental benefit it is obvious.
It is high to react utilization rate, can reach 98% or more, solid waste will not be generated again.
Using the reaction process of common similar polyester polyol, equipment is easy to get the present invention, industrializes and is easier to realize.
Catalyst for esterification reaction used in the present invention is common catalyst for esterification reaction, is easy to get and efficiently.
Decolorising agent used in the present invention is the common decolorising agent of industry, is efficiently easy to get.
The present invention economic benefit that turns waste into wealth is obvious.
The discharge of whole preparation process Bu Wataru and waste residue, waste water, exhaust gas of the present invention.
Specific embodiment:
Below with reference to example, invention is further explained:
Example 1
By 2000.00g caprolactone by-product (acid value is 128.02mg KOH/g, hydroxyl value is 10.31mg KOH/g, ε-oneself
Lactone content is 17%, Caprolactone oligomers 81%) it is added in 5L stainless steel cauldron, 148.61g ethylene glycol, 2.15g is added
Antioxidant 1010,4.30g antioxidant triphenyl phosphite, 80ppm catalyst Mono-n-butyltin.It is warming up under agitation
140 DEG C are reacted and then are heated up with the heating rate of 5 DEG C/h, and each temperature spot after heating reacts 1h；Then
1h is kept the temperature at 215 DEG C, the acid value of measurement system is 28.33mg KOH/g.
40ppm catalyst butyl titanate is added, vacuumize and controls absolute vacuum as 60K Pa and vacuum is gradually increased
Degree, the absolute pressure of system is followed successively by 40KPa, 20KPa, 10KPa, 5KPa, 2KPa, 1KPa, 0.5KPa after adjustment.In the process not
The acid value of disconnected monitoring system, final acid value are 1.92mg KOH/g.
Logical cooling water is carried out cooling to 80 DEG C and be kept the temperature to system.Sodium pyrosulfite is laid on funnel (funnel
First spread a filter paper), reaction product is then added thereto carry out decolorization.The polycaprolactone polyol obtained after decoloration
Acid value is 1.92mg KOH/g and hydroxyl value is 134.25mg KOH/g, coloration 80APHA.
Example 2
By 2000.00g caprolactone by-product (acid value is 128.02mg KOH/g, hydroxyl value is 10.31mg KOH/g, ε-oneself
Lactone content is 17%, Caprolactone oligomers 81%) it is added in 5L stainless steel cauldron, 155.69g ethylene glycol, 2.16g is added
Antioxidant 1010,4.31g antioxidant triphenyl phosphite, 80ppm catalyst dialkyl tin dimaleate.Under agitation
It is warming up to 140 DEG C of reaction 1h, then with the heating rate raising temperature of 10 DEG C/h, and each temperature spot after heating reacts
1h；Then 1h is kept the temperature at 220 DEG C, the acid value of measurement system is 27.45mg KOH/g.
40ppm catalyst tetraisopropyl titanate is added, vacuumize and controls absolute vacuum as 60K Pa and is gradually increased true
Reciprocal of duty cycle, the absolute pressure of system is followed successively by 40KPa, 20KPa, 10KPa, 5KPa, 2KPa, 1KPa, 0.5KPa after adjustment.In the process
The acid value of continuous monitoring system, the final acid value of system are 1.82mg KOH/g.
Reaction is cooled to 80 DEG C and is kept the temperature, sodium pyrosulfite is laid on funnel to (funnel first spreads a filter
Paper), then reaction product is poured into and wherein carries out decolorization.It is by obtained polycaprolactone polyol acid value after decoloration
1.82mg KOH/g and hydroxyl value are 136.54mg KOH/g, coloration 85APHA.
Example 3
By 2000.00g caprolactone by-product (acid value is 128.02mg KOH/g, hydroxyl value is 10.31mg KOH/g, ε-oneself
Lactone content is 17%, Caprolactone oligomers 81%) it is added in 5L stainless steel cauldron, it is anti-that 147.11g glycerol, 2.15g is added
4.29g antioxidant triphenyl phosphite, 80ppm catalyst Mono-n-butyltin is added in oxygen agent 1010.It heats up under agitation
1h is reacted, then with the heating rate raising temperature of 5 DEG C/h to 140 DEG C, and each temperature spot after heating reacts 1h；Then
1h is kept the temperature at 215 DEG C, the acid value of measurement system is 29.36mg KOH/g.
40ppm catalyst butyl titanate is added, vacuumize and controls absolute vacuum as 60K Pa and vacuum is gradually increased
Degree, the absolute pressure of system is followed successively by 40KPa, 20KPa, 10KPa, 5KPa, 2KPa, 1KPa, 0.5KPa after adjustment.In the process not
The acid value of disconnected monitoring system, system acid value is finally 1.94mg KOH/g.
Reaction is cooled to 80 DEG C and is kept the temperature, sodium pyrosulfite is laid on funnel to (funnel first spreads a filter
Paper), then reaction product is poured into and wherein carries out decolorization.It is by obtained polycaprolactone polyol acid value after decoloration
1.94mg KOH/g and hydroxyl value are 135.62mg KOH/g, coloration 80APHA.
Example 4
By 2000.00g caprolactone by-product (acid value is 128.02mg KOH/g, hydroxyl value is 10.31mg KOH/g, ε-oneself
Lactone content is 17%, Caprolactone oligomers 81%) it is added in 5L stainless steel cauldron, it is anti-that 154.12g glycerol, 2.15g is added
4.31g antioxidant triphenyl phosphite, 80ppm catalyst dialkyl tin dimaleate is added in oxygen agent 1010.In stirring condition
Under be warming up to 140 DEG C of reaction 1h, temperature then increased with the heating rate of 10 DEG C/h, and each temperature spot reaction after heating
1h；Then 1h is kept the temperature at 220 DEG C, the acid value of measurement system is 27.23mg KOH/g.
40ppm catalyst butyl titanate is added, vacuumize and controls absolute vacuum as 60K Pa and vacuum is gradually increased
Degree, the absolute pressure of system is followed successively by 40KPa, 20KPa, 10KPa, 5KPa, 2KPa, 1KPa, 0.5KPa after adjustment.In the process not
The acid value of disconnected monitoring system, final system acid value are 1.83mg KOH/g or less.
Reaction is cooled to 80 DEG C, sodium pyrosulfite is laid on funnel (funnel first spreads a filter paper), it then will be anti-
It answers product to pour into and wherein carries out decolorization.After decoloration by obtained polycaprolactone polyol acid value be 1.83mg KOH/g and
Hydroxyl value is 138.07mg KOH/g, coloration 80APHA.
Example 5
By 2000.00g caprolactone by-product (acid value is 128.02mg KOH/g, hydroxyl value is 10.31mg KOH/g, ε-oneself
Lactone content is 17%, Caprolactone oligomers 81%) it is added in 5L stainless steel cauldron, 161.12g glycerol, 2.16g antioxidant
1010,4.32g antioxidant triphenyl phosphite, 80ppm catalyst Mono-n-butyltin.It is warming up to 140 DEG C under agitation
React 1h, then with the heating rate raising temperature of 15 DEG C/h, and each temperature spot after heating reacts 1h；Then 215
1h is kept the temperature at DEG C, the acid value of measurement system is 27.26mg KOH/g.
40ppm catalyst butyl titanate is added, vacuumize and controls absolute vacuum as 60K Pa and vacuum is gradually increased
Degree, the absolute pressure of system is followed successively by 40KPa, 20KPa, 10KPa, 5KPa, 2KPa, 1KPa, 0.5KPa after adjustment.In the process not
The acid value of disconnected monitoring system, the final acid value of system are 1.80mg KOH/g.
Reaction is cooled to 80 DEG C and is kept the temperature, sodium pyrosulfite is laid on funnel to (funnel first spreads a filter
Paper), then reaction product is poured into and wherein carries out decolorization.It is by obtained polycaprolactone polyol acid value after decoloration
1.80mg KOH/g and hydroxyl value are 142.36mg KOH/g, coloration 80APHA.
Example 6
By 2000.00g caprolactone by-product (acid value is 128.02mg KOH/g, hydroxyl value is 10.31mg KOH/g, ε-oneself
Lactone content is 17%, Caprolactone oligomers 81%) it is added in 5L stainless steel cauldron, it is anti-that 161.12g glycerol, 4.32g is added
8.64g antioxidant triphenyl phosphite, 80ppm catalyst dialkyl tin dimaleate is added in oxygen agent 1010.In stirring condition
Under be warming up to 140 DEG C of reaction 1h, temperature then increased with the heating rate of 15 DEG C/h, and each temperature spot reaction after heating
1h；Then 1h is kept the temperature at 220 DEG C, the acid value of measurement system is 26.72mg KOH/g.
40ppm catalyst butyl titanate is added, vacuumize and controls absolute vacuum as 60K Pa and vacuum is gradually increased
Degree, the absolute pressure of system is followed successively by 40KPa, 20KPa, 10KPa, 5KPa, 2KPa, 1KPa, 0.5KPa after adjustment.In the process not
The acid value of disconnected monitoring system, final system acid value are 1.75mg KOH/g or less.
Reaction is cooled to 80 DEG C and is kept the temperature, sodium pyrosulfite is laid on funnel to (funnel first spreads a filter
Paper), then reaction product is poured into and wherein carries out decolorization.It is by obtained polycaprolactone polyol acid value after decoloration
1.75mg KOH/g and hydroxyl value are 141.65mg KOH/g, coloration 80APHA.
Example 7
By 2000.00g caprolactone by-product (acid value is 128.02mg KOH/g, hydroxyl value is 10.31mg KOH/g, ε-oneself
Lactone content is 17%, Caprolactone oligomers 81%) it is added in 5L stainless steel cauldron, 145.83g xylitol, 2.15g is added
4.29g antioxidant triphenyl phosphite, 80ppm catalyst Mono-n-butyltin is added in antioxidant 1010.It rises under agitation
Temperature reacts 1h, then with the heating rate raising temperature of 10 DEG C/h to 140 DEG C, and each temperature spot after heating reacts 1h；
Then 1h is kept the temperature at 215 DEG C, the acid value of measurement system is 28.44mg KOH/g.
40ppm catalyst butyl titanate is added, vacuumize and controls absolute vacuum as 60K Pa and vacuum is gradually increased
Degree, the absolute pressure of system is followed successively by 40KPa, 20KPa, 10KPa, 5KPa, 2KPa, 1KPa, 0.5KPa after adjustment.In the process not
The acid value of disconnected monitoring system, final system acid value are 1.86mg KOH/g or less.
Reaction is cooled to 80 DEG C and is kept the temperature, sodium pyrosulfite is laid on funnel to (funnel first spreads a filter
Paper), then reaction product is poured into and wherein carries out decolorization.It is by obtained polycaprolactone polyol survey acid value after decoloration
1.86mgKOH/g and hydroxyl value are 137.46mg KOH/g and coloration 80APHA.
Example 8
By 2000.00g caprolactone by-product (acid value is 128.02mg KOH/g, hydroxyl value is 10.31mg KOH/g, ε-oneself
Lactone content is 17%, Caprolactone oligomers 81%) it is added in 5L stainless steel cauldron, 152.77g xylitol, 2.15g is added
Antioxidant 1010,4.31g antioxidant triphenyl phosphite, 80ppm catalyst dialkyl tin dimaleate.Under agitation
It is warming up to 140 DEG C of reaction 1h, then with the heating rate raising temperature of 10 DEG C/h；Then 1h, measurement system are kept the temperature at 220 DEG C
Acid value be 26.35mg KOH/g.
40ppm catalyst butyl titanate is added, vacuumize and controls absolute vacuum as 60K Pa and vacuum is gradually increased
Degree, the absolute pressure of system is followed successively by 40K Pa, 20K Pa, 10K Pa, 5K Pa, 2KPa, 1KPa, 0.5KPa after adjustment.Process
In constantly monitoring system acid value, measurement system acid value be 1.78mg KOH/g or less.
Reaction is cooled to 80 DEG C and is kept the temperature, sodium sulfite is laid on funnel (funnel first spreads a filter paper),
Then reaction product is poured into and wherein carries out decolorization.After decoloration by obtained polycaprolactone polyol acid value be 1.78mg
KOH/g and hydroxyl value be 139.54mg KOH/g, coloration 85APHA.
Example 9
By 2000.00g caprolactone by-product (acid value is 128.02mg KOH/g, hydroxyl value is 10.31mg KOH/g, ε-oneself
Lactone content is 17%, Caprolactone oligomers 81%) it is added in 5L reaction kettle, 215.84g sucrose, 2.22g antioxidant is added
1010,4.43g antioxidant triphenyl phosphite, 80ppm catalyst Mono-n-butyltin.It is warming up to 140 DEG C under agitation
React 1h, then with the heating rate raising temperature of 5 DEG C/h；Then 1h is kept the temperature at 215 DEG C, the acid value of measurement system is
28.67mg KOH/g。
40ppm catalyst butyl titanate is added, vacuumize and controls absolute vacuum as 60K Pa and vacuum is gradually increased
Degree, the absolute pressure of system is followed successively by 40KPa, 20KPa, 10KPa, 5KPa, 2KPa, 1KPa, 0.5KPa after adjustment.In the process not
The acid value of disconnected monitoring system, final system acid value are 1.87mg KOH/g.
Reaction is cooled to 80 DEG C and is kept the temperature, sodium pyrosulfite is laid on funnel to (funnel first spreads a filter
Paper), then reaction product is poured into and wherein carries out decolorization.It is by obtained polycaprolactone polyol survey acid value after decoloration
1.87mg KOH/g and hydroxyl value 133.41mg KOH/g and coloration are 85APHA.
Experiment embodiment 10
By 2000.00g caprolactone by-product (acid value is 128.02mg KOH/g, hydroxyl value is 10.31mg KOH/g, ε-oneself
Lactone content is 17%, Caprolactone oligomers 81%) it is added in 5L reaction kettle, 226.12g sucrose, 2.23g antioxidant is added
1010,4.45g antioxidant triphenyl phosphite, 80ppm catalyst dialkyl tin dimaleate.It is warming up under agitation
140 DEG C are reacted 1h, then with the heating rate raising temperature of 10 DEG C/h；Then 1h, the acid value of measurement system are kept the temperature at 220 DEG C
For 27.35mg KOH/g.
40ppm catalyst tetraisopropyl titanate is added, vacuumize and controls absolute vacuum as 60K Pa and is gradually increased true
Reciprocal of duty cycle, the absolute pressure of system is followed successively by 40KPa, 20KPa, 10KPa, 5KPa, 2KPa, 1KPa, 0.5KPa after adjustment.In the process
The acid value of continuous monitoring system, final system acid value are 1.79mg KOH/g.
Reaction is cooled to 80 DEG C and is kept the temperature, sodium pyrosulfite is laid on funnel to (funnel first spreads a filter
Paper), then reaction product is poured into and wherein carries out decolorization.It is by obtained polycaprolactone polyol survey acid value after decoloration
1.79mg and hydroxyl value are 135.46mg KOH/g and coloration is 90APHA.
It is described above that limiting the invention.The some nonessential modifications and tune that other people make according to the present invention
It is whole, still fall within protection scope of the present invention.Other unspecified parts are the prior art.
Claims (10)
1. a kind of method for recycling 6-caprolactone by-product, it is characterised in that small molecule polyol is first added, antioxidant, urges
Agent is reacted, and reaction condition is controlled, so that the acid value of polyol product≤2mg KOH/g, then decolourizes product
Processing obtains the much lower first alcohol product of acid value.
2. the small molecule polyol being added in claim 1 includes dihydric alcohol, trihydroxylic alcohol, tetrahydroxylic alcohol, pentabasis alcohol, hexahydroxylic alcohols, eight
First alcohol etc..
3. narrating dihydric alcohol in claim 2 includes ethylene glycol, diglycol, neopentyl glycol, 1,4- butanediol, 1,3- fourth
Glycol, 1,2 propylene glycol, 1,3 propylene glycol, 2- methyl propanediol, 1,5- pentanediol, 3- methyl-1,5- pentanediol, 1,6- oneself two
Alcohol, 1,4- hydroxymethyl-cyclohexane, 1,4- cyclohexanediol etc..Trihydroxylic alcohol includes glycerol, trimethylolpropane etc..Tetrahydroxylic alcohol includes
Pentaerythrite etc..Pentabasis alcohol includes xylitol etc..Hexahydroxylic alcohols includes sorbierite, mannitol etc..Eight yuan of alcohol include sucrose etc..
4. in claim 1, synthesizing polyalcohol.Antioxidant and catalyst is added, by caprolactone by-product and small point in first stage
Sub- polyalcohol is reacted at 140~200 DEG C, after the by-product water of the overwhelming majority of generation is evaporated off in normal pressure, at 205~240 DEG C
1~3h is kept the temperature, continues to react.Catalyst is added then in second stage, vacuumizes, and step up vacuum degree, decompression removes
Minor amount of water and extra small molecule polyol compound are gone, makes to react the direction progress to low acid value polyester polyol is generated, directly
To acid value≤2mg KOH/g.
5. narrating antioxidant packages in claim 1 containing one of phosphite ester antioxidant, hindered phenol antioxygen or two kinds.
6. the discoloration method in claim 1 can remove color except color or by bleaching agent by absorption.
7. described adsorbent includes in claim 6: active carbon, organobentonite etc.；Bleaching agent includes sodium sulfite, sulfurous acid
Hydrogen sodium, sodium pyrosulfite, H2O2, hypochlorous acid etc..
8. caprolactone polyol is first carried out heating and melted, is added and inhale in filter device by discoloration method in claim 1
Attached dose or decolorising agent decolourized, filtration treatment.
9. the first step in claim 4, catalyst described in second step be antimony glycol, antimony oxide, Mono-n-butyltin, pungent
Sour stannous, dialkyl tin dimaleate, butyl titanate and tetraisopropyl titanate etc..
10. synthesizing the second stage of polyalcohol in claim 4, vacuum degree is gradually lower, and final system absolute pressure reaches 0.5KPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910369438.XA CN110016128B (en) | 2019-05-06 | 2019-05-06 | Recycling method of epsilon-caprolactone by-product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910369438.XA CN110016128B (en) | 2019-05-06 | 2019-05-06 | Recycling method of epsilon-caprolactone by-product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110016128A true CN110016128A (en) | 2019-07-16 |
| CN110016128B CN110016128B (en) | 2021-09-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110305280A (en) * | 2019-07-25 | 2019-10-08 | 湖南东为化工新材料有限公司 | A kind of 6-caprolactone by-product prepares polyurethane heat insulation material method |
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