CN109651557A - The preparation method of ethylene-vinyl alcohol copolymer - Google Patents
The preparation method of ethylene-vinyl alcohol copolymer Download PDFInfo
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- CN109651557A CN109651557A CN201710940953.XA CN201710940953A CN109651557A CN 109651557 A CN109651557 A CN 109651557A CN 201710940953 A CN201710940953 A CN 201710940953A CN 109651557 A CN109651557 A CN 109651557A
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- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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Abstract
The invention belongs to the copolymer technical fields of only one carbon-carbon double bond of the monomer containing 4 carbon atoms, more particularly to a kind of preparation method of ethylene-vinyl alcohol copolymer, including copolymerization and Alcoholysis Step, base catalyst is added in two portions and carries out alcoholysis reaction, first time period base catalyst dosage and second time period base catalyst amount ratio are 0.8:1-2:1, and first time period and second time period ratio are 1:1-1.5:1.By control base catalyst adding technology, alcoholysis efficiency and alcoholysis degree are all improved the present invention；Ethylene-vinyl alcohol copolymer degree of staining produced by the present invention is low, and smooth in appearance, form and aspect are whiter, and no white suitcase is wrapped up in, Good Heat-resistance, and yellowness index YI is 8-11, alcoholysis degree 99.3-99.7%.
Description
Technical field
The invention belongs to the copolymer technical fields of only one carbon-carbon double bond of the monomer containing 4 carbon atoms, specifically
It is related to a kind of preparation method of ethylene-vinyl alcohol copolymer.
Background technique
Ethylene-vinyl alcohol copolymer (EVOH), especially ethylene contents are the ethylene-second of 20-50% (molar percentage)
Enol copolymer, has an excellent barrier properties for gases, about the 10 of common polythene, and 000 times, in addition it is transparent, processable
Property, solvent resistance and antistatic property, so that it is widely used in packaging material, automotive oil tank, resistance oxygen floor heating pipe, textile material and doctor
With fields such as materials.Ethylene-vinyl alcohol copolymer is that ethylene-vinyl acetate copolymer alcoholysis obtains, and ethylene-vinyl alcohol is total
The high gas-obstructing character of polymers and its alcoholysis degree have a direct relation, and under the conditions of identical ethylene contents, alcoholysis degree is higher, gas barrier
Property is better, in order to guarantee that sufficient barrier properties for gases, the alcoholysis degree of usual EVOH reach 99% or more.
The alcoholysis process of high temperature and pressure is generallyd use in industrial production, alcoholysis reaction temperature is higher, and alcoholysis reaction efficiency is got over
Height, but influenced by the easy xanthochromia of resin high temperature, glycolysis temperature can only be kept within limits, therefore in tower alcoholysis, alcohol
The raising of solution efficiency can only seek other methods.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation method of ethylene-vinyl alcohol copolymer, this method
Alcoholysis is high-efficient.
To achieve the above object, the technical solution of the present invention is as follows:
Base catalyst progress is added in two portions in the preparation method of ethylene-vinyl alcohol copolymer, including copolymerization and Alcoholysis Step
Alcoholysis reaction, first time period base catalyst dosage and second time period base catalyst amount ratio are 0.8:1-2:1, at the first time
Section is 0.5:1-1.5:1, mole for the ethylene-vinyl acetate copolymer that base catalyst and copolymerization obtain with second time period ratio
Than for 0.01:1-0.3:1.
The copolymerization is emulsion polymerization, polymerisation in solution, suspension polymerisation or free radical polymerization, is preferably that free-atom aqueous solution is poly-
It closes.
Inventors be surprised to learn that the molar ratio for the ethylene-vinyl acetate copolymer that base catalyst is obtained with copolymerization is
0.01:1-0.3:1 is added in two portions base catalyst and carries out alcoholysis reaction, first time period base catalyst dosage and the second time
Section base catalyst amount ratio is 0.8:1-2:1, and first time period and second time period ratio are 0.5:1-1.5:1, for the present invention
In the preparation of ethylene-vinyl alcohol copolymer, alcoholysis efficiency and alcoholysis degree of the invention can be significantly improved.
Further, the copolymerization refers to 20-100 parts of solvent, 60-150 parts of vinylacetate, 0.005-1 parts of initiator
It is that raw material carries out copolyreaction with ethylene, it is 2.5-6MPa that control, which is passed through pressure in the kettle of ethylene, and the reaction time is that 2.0-8.0 is small
When.
Further, the temperature of the copolyreaction is 40-80 DEG C, pressure 2.0-6.5MPa.
Further, the solvent is the alcohols that carbon atom number is 1-4, and methanol, ethyl alcohol, propyl alcohol, butanol or the above alcohols are pressed
The mixture of one or more of mixture or the above alcohols according to arbitrary proportion with other alcohols, the wherein matter of other alcohols
Measure content < 50%.
Further, the initiator is azo-initiator, inorganic peroxygen species initiator or organic peroxide class
Initiator.
Further, the azo-initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl
Or 2,2'- azodiisobutyronitrile.
Further, the inorganic peroxygen species initiator is hydrogen peroxide, ammonium persulfate or potassium peroxydisulfate.
Further, the organic peroxide initiator is benzoyl peroxide, benzoyl peroxide, peroxide
Change methyl ethyl ketone, diisobutyryl peroxide, peroxidating neodecanoic acid spy pentyl ester, dicetyl peroxydicarbonate bis- (4- tertiary butyl cyclohexyls), mistake
Aoxidize the double butyl esters of pivalic acid spy pentyl ester, peroxidating tert-butyl acetate or dicetyl peroxydicarbonate.
Further, the base catalyst is sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide or potassium methoxide.
Further, alcoholysis initial stage base catalyst dosage and alcoholysis later period base catalyst amount ratio are 1:1-1.5:1, at the beginning of alcoholysis
Time phase and alcoholysis later time ratio are 0.8:1-1.2:1.
Further, further comprising the steps of: carboxylic acid compound aqueous solution, boride being added into the mixture that alcoholysis obtains
One or more of aqueous solution, phosphate cpd aqueous solution are post-processed.
Further, carboxylic acid compound aqueous solution, boride aqueous solution, phosphoric acid chemical combination are added into the mixture that alcoholysis obtains
One or more of object aqueous solution is post-processed, and the dosage of carboxylic acid compound aqueous solution is Carboxylation in solution after making to be added
The final concentration of 10-500ppm of object is closed, the dosage of boride aqueous solution is the final concentration of 10- of boride in solution after making to be added
1000ppm, the dosage of phosphate cpd aqueous solution are the final concentration of 10-300ppm of phosphate cpd in solution after making to be added,
Based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains.
The carboxylic acid compound aqueous solution, boride aqueous solution, phosphate cpd aqueous solution concentration be any concentration model
It encloses.
Further, the carboxylic acid compound is oxalic acid, succinic acid, benzoic acid, citric acid, acetic acid, propionic acid or lactic acid.
Preferably, the carboxylic acid compound is acetic acid or propionic acid.
Further, the boride is boric acid, metaboric acid, tetraboric acid, borate, borate or borine.
Further, the phosphate cpd is phosphoric acid, phosphorous acid, phosphate or phosphite.
The beneficial effects of the present invention are:
The present invention can significantly improve alcoholysis efficiency and alcoholysis degree, Neng Gou by control base catalyst adding technology
1h25min-1h55min internal alcoholysis ethylene-vinyl acetate copolymer obtains the ethylene-vinyl alcohol that alcoholysis degree is 99.3-99.7%
Copolymer.
Carboxylic acid compound aqueous solution in post-processing step of the invention, boride aqueous solution, in phosphate cpd aqueous solution
One or more be added in ethylene-vinyl alcohol copolymer solution with solution state so that carboxylic acid compound aqueous solution, boronation
One or more of object aqueous solution, phosphate cpd aqueous solution are evenly distributed in granules of copolymer of ethylene-vinyl alcohol, rather than
It is adhered merely in surface and gap, to further improve the heat resistance of ethylene-vinyl alcohol copolymer.
Ethylene-vinyl alcohol copolymer degree of staining produced by the present invention is low, and smooth in appearance, form and aspect are whiter, and no white suitcase is wrapped up in, resistance to
Hot property is excellent, and yellowness index YI is 8-11, alcoholysis degree 99.3-99.7%.
Specific embodiment
Illustrated embodiment is to preferably be illustrated to the contents of the present invention, but is not that the contents of the present invention only limit
In illustrated embodiment.So those skilled in the art carry out nonessential change to embodiment according to foregoing invention content
Into and adjustment, still fall within protection scope of the present invention.
Embodiment 1
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
Be copolymerized using 20 parts of methanol, 150 parts of vinylacetate, 0.005 part of azodiisobutyronitrile and ethylene as raw material anti-
It answers, it is 6MPa that control, which is passed through pressure in the kettle of ethylene, and copolyreaction temperature is 40 DEG C, pressure 6.5MPa, the reaction time 2.0
Hour；
B. alcoholysis
Sodium hydroxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period sodium hydroxide
Dosage and second time period sodium hydroxide concentration ratio are 2:1, and the ratio of first time period and second time period is 0.5:1, hydroxide
The molar ratio for the ethylene-vinyl acetate copolymer that sodium and copolymerization obtain is 0.3:1；
C. it post-processes:
Oxalic acid aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of oxalic acid aqueous solution is to make to be added
The final concentration of 10ppm of solution mesoxalic acid afterwards, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 17:1) on extrusion board
Bar is frozen into water out, cuts granulating, washing is dried after centrifugal dehydration.
Alcoholysis reaction total time is 1h25min.
Embodiment 2
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
Copolyreaction, control are carried out by raw material of 100 parts of ethyl alcohol, 60 parts of vinylacetate, 1 part of azobisisoheptonitrile and ethylene
It is 2.5MPa that system, which is passed through pressure in the kettle of ethylene, and copolyreaction temperature is 40 DEG C, pressure 2.0MPa, and the reaction time is 8.0 small
When；
B. alcoholysis
Potassium hydroxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period potassium hydroxide
Dosage and second time period potassium hydroxide amount ratio are 0.8:1, and the ratio of first time period and second time period is 1.5:1, hydrogen-oxygen
Changing potassium and being copolymerized the molar ratio of obtained ethylene-vinyl acetate copolymer is 0.01:1；
C. it post-processes:
Butanedioic acid aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of butanedioic acid aqueous solution is to make
After addition in solution succinic acid final concentration of 500ppm, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 15:1) on extrusion board
Bar is frozen into water out, cuts granulating, washing is dried after centrifugal dehydration.
Alcoholysis reaction total time is 1h50min.
Embodiment 3
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
It is carried out by raw material of 40 parts of normal propyl alcohol, 90 parts of vinylacetate, 0.05 part of azo-bis-iso-dimethyl and ethylene
Copolyreaction, it is 4.2MPa that control, which is passed through pressure in the kettle of ethylene, and copolyreaction temperature is 50 DEG C, pressure 4.5MPa, reaction
Time is 6.0 hours；
B. alcoholysis
Sodium methoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period sodium methoxide dosage
It is 1.2:1 with second time period sodium methoxide amount ratio, alcoholysis time at initial stage and alcoholysis later time ratio are 1:1, and sodium methoxide is together
The molar ratio of poly- obtained ethylene-vinyl acetate copolymer is 0.05:1；
C. it post-processes:
Benzoic acid aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of benzoic acid aqueous solution is to make
After addition in solution benzoic acid final concentration of 80ppm, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 3:1) on extrusion board
It is frozen into bar into the solution that the mass ratio of methanol and water is 1:6 out, cuts granulating, washing is done after centrifugal dehydration
It is dry.
Alcoholysis reaction total time is 1h40min.
Embodiment 4
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
It is total to using 50 parts of n-butanol, 120 parts of vinylacetate, 0.1 part of 2,2'- azodiisobutyronitrile and ethylene as raw material
Poly- reaction, it is 3.0MPa that control, which is passed through pressure in the kettle of ethylene, and copolyreaction temperature is 70 DEG C, pressure 3.8MPa, when reaction
Between be 6.0 hours；
B. alcoholysis
Sodium ethoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period sodium ethoxide dosage
It is 1:1 with second time period sodium ethoxide amount ratio, the ratio of first time period and second time period is 1.2:1, sodium ethoxide and copolymerization
The molar ratio of obtained ethylene-vinyl acetate copolymer is 0.2:1；
C. it post-processes:
Aqueous citric acid solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of aqueous citric acid solution is to make
After addition in solution citric acid final concentration of 200ppm, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 12:1) on extrusion board
Bar is frozen into water out, cuts granulating, washing is dried after centrifugal dehydration.
Alcoholysis reaction total time is 1h35min.
Embodiment 5
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
With 30 parts of solvent (methanol and ethyl alcohol are formed according to the mass ratio of 1:2), 70 parts of vinylacetate, hydrogen peroxide
0.008 part is that raw material carries out copolyreaction with ethylene, and it is 4.5MPa that control, which is passed through pressure in the kettle of ethylene, and copolyreaction temperature is
55 DEG C, pressure 5.1MPa, the reaction time is 7.0 hours；
B. alcoholysis
Potassium methoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period methanol potassium application rate
It is 1.5:1 with second time period potassium methoxide amount ratio, the ratio of first time period and second time period is 1:1, potassium methoxide and copolymerization
The molar ratio of obtained ethylene-vinyl acetate copolymer is 0.2:1；
C. it post-processes:
Acetic acid aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of acetic acid aqueous solution is to make to be added
Afterwards in solution acetic acid final concentration of 300ppm, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 10:1) on extrusion board
It is frozen into bar into the solution that the mass ratio of methanol and water is 9:4 out, cuts granulating, washing is done after centrifugal dehydration
It is dry.
Alcoholysis reaction total time is 1h30min.
Embodiment 6
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
With 90 parts of solvent (methanol, ethyl alcohol and isobutanol are formed according to the mass ratio of 3:2:4), 75 parts of vinylacetate, mistake
0.03 part of ammonium sulfate and ethylene are that raw material carries out copolyreaction, and it is 4.8MPa, copolyreaction that control, which is passed through pressure in the kettle of ethylene,
Temperature is 75 DEG C, pressure 3.6MPa, and the reaction time is 5.0 hours；
B. alcoholysis
Sodium methoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period sodium methoxide dosage
It is 1:1 with second time period sodium methoxide amount ratio, the ratio of first time period and second time period is 0.8:1, sodium methoxide and copolymerization
The molar ratio of obtained ethylene-vinyl acetate copolymer is 0.06:1；
C. it post-processes:
Propionic acid aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of propionic acid aqueous solution is to make to be added
Afterwards in solution propionic acid final concentration of 360ppm, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 17:1) on extrusion board
Bar is frozen into water out, cuts granulating, washing is dried after centrifugal dehydration.
Alcoholysis reaction total time is 1h45min.
Embodiment 7
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
With 90 parts of solvent (methanol, ethyl alcohol, isopropanol and n-butanol are formed according to the mass ratio of 5:1:2:2), vinyl acetate
81 parts of ester, 0.04 part of potassium peroxydisulfate and ethylene are that raw material carries out copolyreaction, and it is 3.5MPa that control, which is passed through pressure in the kettle of ethylene,
Copolyreaction temperature is 54 DEG C, pressure 4.2MPa, and the reaction time is 5.5 hours；
B. alcoholysis
Potassium hydroxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period potassium hydroxide
Dosage and second time period potassium hydroxide amount ratio are 0.9:1, and the ratio of first time period and second time period is 0.9:1, hydrogen-oxygen
Changing potassium and being copolymerized the molar ratio of obtained ethylene-vinyl acetate copolymer is 0.08:1；
C. it post-processes:
Lactic acid aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of lactic acid aqueous solution is to make to be added
Afterwards in solution lactic acid final concentration of 60ppm, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 15:1) on extrusion board
Bar is frozen into water out, cuts granulating, washing is dried after centrifugal dehydration.
Alcoholysis reaction total time is 1h55min.
Embodiment 8
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
With 60 parts of solvent (methanol and n-amyl alcohol are formed according to the mass ratio of 51:49), 150 parts of vinylacetate, peroxidating
0.06 part of benzoyl and ethylene are that raw material carries out copolyreaction, and it is 4.8MPa, copolyreaction that control, which is passed through pressure in the kettle of ethylene,
Temperature is 43 DEG C, pressure 2.4MPa, and the reaction time is 3.5 hours；
B. alcoholysis
Sodium ethoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period sodium ethoxide dosage
It is 1.8:1 with second time period sodium ethoxide amount ratio, the ratio of first time period and second time period is 1.4:1, and sodium ethoxide is together
The molar ratio of poly- obtained ethylene-vinyl acetate copolymer is 0.05:1；
C. it post-processes:
Boric acid aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of boric acid aqueous solution is to make to be added
Afterwards in solution boric acid final concentration of 1000ppm, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 3:1) on extrusion board
It is frozen into bar into the solution that the mass ratio of methanol and water is 2:5 out, cuts granulating, washing is done after centrifugal dehydration
It is dry.
Alcoholysis reaction total time is 1h35min.
Embodiment 9
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
With 36 parts of solvent (ethyl alcohol and isooctanol are formed according to the mass ratio of 6:4), 810 parts of vinylacetate, benzoyl peroxide
0.5 part of the formyl tert-butyl ester and ethylene are that raw material carries out copolyreaction, and it is 2.8MPa that control, which is passed through pressure in the kettle of ethylene, and copolymerization is anti-
Answering temperature is 51 DEG C, pressure 2.5MPa, and the reaction time is 2.0 hours；
B. alcoholysis
Sodium hydroxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period sodium hydroxide
Dosage and second time period sodium hydroxide concentration ratio are 1.4:1, and the ratio of first time period and second time period is 0.6:1, hydrogen-oxygen
Changing sodium and being copolymerized the molar ratio of obtained ethylene-vinyl acetate copolymer is 0.03:1；
C. it post-processes:
Metaboric acid aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of metaboric acid aqueous solution is to make
After addition in solution metaboric acid final concentration of 10ppm, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 17:1) on extrusion board
It is frozen into bar into the solution that the mass ratio of methanol and water is 3:4 out, cuts granulating, washing is done after centrifugal dehydration
It is dry.
Alcoholysis reaction total time is 1h48min.
Embodiment 10
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
With 64 parts of solvent (methanol, ethyl alcohol and n-nonyl alcohol are formed according to the mass ratio of 4:3:1), 65 parts of vinylacetate, mistake
0.7 part of Methyl Ethyl Ketone Oxidation and ethylene are that raw material carries out copolyreaction, and it is 2.8MPa that control, which is passed through pressure in the kettle of ethylene, and copolymerization is anti-
Answering temperature is 45 DEG C, pressure 6.3MPa, and the reaction time is 7.5 hours；
B. alcoholysis
Potassium methoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period methanol potassium application rate
It is 1.6:1 with second time period potassium methoxide amount ratio, the ratio of first time period and second time period is 0.8:1, and potassium methoxide is together
The molar ratio of poly- obtained ethylene-vinyl acetate copolymer is 0.1:1；
C. it post-processes:
Tetraboric acid aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of tetraboric acid aqueous solution is to make
After addition in solution tetraboric acid final concentration of 800ppm, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 17:1) on extrusion board
It is frozen into bar into the solution that the mass ratio of methanol and water is 6:5 out, cuts granulating, washing is done after centrifugal dehydration
It is dry.
Alcoholysis reaction total time is 1h45min.
Embodiment 11
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
With 100 parts of solvent (normal propyl alcohol and isooctanol are formed according to the mass ratio of 7:1), 64 parts of vinylacetate, peroxidating
Two 0.09 part of isobutyryls and ethylene are that raw material carries out copolyreaction, and it is 6MPa, copolyreaction that control, which is passed through pressure in the kettle of ethylene,
Temperature is 50 DEG C, pressure 6.5MPa, and the reaction time is 2.5 hours；
B. alcoholysis
Sodium hydroxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period sodium hydroxide
Dosage and second time period sodium hydroxide concentration ratio are 1.5:1, and the ratio of first time period and second time period is 0.7:1, hydrogen-oxygen
Changing sodium and being copolymerized the molar ratio of obtained ethylene-vinyl acetate copolymer is 0.2:1；
C. it post-processes:
Borogen aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of borogen aqueous solution
For the final concentration of 70ppm for making borogen in solution after being added, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 15:1) on extrusion board
Bar is frozen into water out, cuts granulating, washing is dried after centrifugal dehydration.
Alcoholysis reaction total time is 1h40min.
Embodiment 12
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
It is new with 84 parts of solvent (isobutanol and n-heptanol are formed according to the mass ratio of 6:1), 72 parts of vinylacetate, peroxidating
0.7 part of capric acid spy pentyl ester and ethylene are that raw material carries out copolyreaction, and it is 2.5MPa that control, which is passed through pressure in the kettle of ethylene, and copolymerization is anti-
Answering temperature is 44 DEG C, pressure 4.7MPa, and the reaction time is 4 hours；
B. alcoholysis
Sodium ethoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period dosage and second
Period sodium ethoxide amount ratio is 1.8:1, and the ratio of first time period and second time period is 0.9:1, and sodium ethoxide is obtained with copolymerization
Ethylene-vinyl acetate copolymer molar ratio be 0.09:1；
C. it post-processes:
Borax solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of borax solution is to make to be added
Afterwards in solution borax final concentration of 300ppm, the ethylene-vinyl alcohol copolymer meter obtained for alcoholysis；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 17:1) on extrusion board
Bar is frozen into water out, cuts granulating, washing is dried after centrifugal dehydration.
Alcoholysis reaction total time is 1h42min.
Embodiment 13
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
It is with 0.3 part of 37 parts of methanol, 66 parts of vinylacetate, dicetyl peroxydicarbonate bis- (4- tertiary butyl cyclohexyls) and ethylene
Raw material carries out copolyreaction, and it is 2.5MPa that control, which is passed through pressure in the kettle of ethylene, and copolyreaction temperature is 60 DEG C, and pressure is
4.8MPa, reaction time are 6.0 hours；
B. alcoholysis
Sodium methoxide is added in the solution obtained to step A and carries out alcoholysis reaction, first time period sodium methoxide dosage and second
Period sodium methoxide amount ratio is 1.5:1, and the ratio of first time period and second time period is 1.2:1, and sodium methoxide is obtained with copolymerization
Ethylene-vinyl acetate copolymer molar ratio be 0.1:1；
C. it post-processes:
Pentaborane aqueous solution is added into the mixture that alcoholysis obtains in two times to be post-processed, the use of pentaborane aqueous solution
Amount is the final concentration of 500ppm of pentaborane in solution after making to be added, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 15:1) on extrusion board
It is frozen into bar into the solution that the mass ratio of methanol and water is 7:5 out, cuts granulating, washing is done after centrifugal dehydration
It is dry.
Alcoholysis reaction total time is 1h30min.
Embodiment 14
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
It is copolymerized using 35 parts of isobutanol, 75 parts of vinylacetate, 0.4 part of peroxidating tert-butyl acetate and ethylene as raw material
Reaction, it is 3.5MPa that control, which is passed through pressure in the kettle of ethylene, and copolyreaction temperature is 50 DEG C, pressure 3.5MPa, the reaction time
It is 5.0 hours；
B. alcoholysis
Potassium hydroxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period potassium hydroxide
Dosage and second time period potassium hydroxide amount ratio are 1.6:1, and the ratio of first time period and second time period is 0.8:1, hydrogen-oxygen
Changing potassium and being copolymerized the molar ratio of obtained ethylene-vinyl acetate copolymer is 0.1:1；
C. it post-processes:
It is added in phosphate aqueous solution and is post-processed into the mixture that alcoholysis obtains, the dosage of phosphate aqueous solution is to make to add
The final concentration of 100ppm for entering phosphoric acid in rear solution, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 17:1) on extrusion board
It is frozen into bar into the solution that the mass ratio of methanol and water is 1:4 out, cuts granulating, washing is done after centrifugal dehydration
It is dry.
Alcoholysis reaction total time is 1h45min.
Embodiment 15
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
With 60 parts of solvent (methanol, ethyl alcohol and normal propyl alcohol are formed according to the mass ratio of 12:7:1), 88 parts of vinylacetate, mistake
It aoxidizing 0.7 part of pivalic acid spy pentyl ester and ethylene is that raw material carries out copolyreaction, it is 3.6MPa that control, which is passed through pressure in the kettle of ethylene,
Copolyreaction temperature is 70 DEG C, pressure 2.5MPa, and the reaction time is 4.5 hours；
B. alcoholysis
Sodium methoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period sodium methoxide dosage
It is 1.6:1 with second time period sodium methoxide amount ratio, the ratio of first time period and second time period is 1.3:1, and sodium methoxide is together
The molar ratio of poly- obtained ethylene-vinyl acetate copolymer is 0.1:1；
C. it post-processes:
Biphosphate sodium water solution is added into the mixture that alcoholysis obtains to be post-processed, biphosphate sodium water solution
Dosage is the final concentration of 80ppm of sodium dihydrogen phosphate in solution after making to be added, the ethylene vinyl alcohol copolymer obtained relative to alcoholysis
Object meter；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 15:1) on extrusion board
Bar is frozen into water out, cuts granulating, washing is dried after centrifugal dehydration.
Alcoholysis reaction total time is 1h32min.
Embodiment 16
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
With 60 parts of solvent (methanol and n-heptanol are formed according to the mass ratio of 4:1), 96 parts of vinylacetate, two carbon of peroxidating
0.2 part of sour double butyl esters and ethylene are that raw material carries out copolyreaction, and it is 4.5MPa, copolyreaction that control, which is passed through pressure in the kettle of ethylene,
Temperature is 52 DEG C, pressure 5.5MPa, and the reaction time is 7.0 hours；
B. alcoholysis
Potassium methoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period methanol potassium application rate
It is 2:1 with second time period potassium methoxide amount ratio, the ratio of first time period and second time period is 0.5:1, potassium methoxide and copolymerization
The molar ratio of obtained ethylene-vinyl acetate copolymer is 0.01:1；
C. it post-processes:
Phosphorous acid aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of phosphorous acid aqueous solution is to make
The final concentration of 150ppm of solution phosphorous acid after addition, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 17:1) on extrusion board
It is frozen into bar into the solution that the mass ratio of methanol and water is 2:5 out, cuts granulating, washing is done after centrifugal dehydration
It is dry.
Alcoholysis reaction total time is 1h47min.
Embodiment 17
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
It is total to using 63 parts of ethyl alcohol, 100 parts of vinylacetate, 0.5 part of initiator azobisisoheptonitrile and ethylene as raw material
Poly- reaction, it is 6MPa that control, which is passed through pressure in the kettle of ethylene, and copolyreaction temperature is 48 DEG C, pressure 2.5MPa, the reaction time
It is 2.5 hours；
B. alcoholysis
Sodium ethoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period sodium ethoxide dosage
It is 2:1 with second time period sodium ethoxide amount ratio, the ratio of first time period and second time period is 1:1, sodium ethoxide and is copolymerized
The molar ratio of the ethylene-vinyl acetate copolymer arrived is 0.1:1；
C. it post-processes:
Potassium dihydrogen phosphate aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, potassium dihydrogen phosphate aqueous solution
Dosage is the final concentration of 250ppm of potassium dihydrogen phosphate in solution after making to be added, and the ethylene-vinyl alcohol obtained relative to alcoholysis is total
Polymers meter；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 17:1) on extrusion board
It is frozen into bar into the solution that the mass ratio of methanol and water is 3:4 out, cuts granulating, washing is done after centrifugal dehydration
It is dry.
Alcoholysis reaction total time is 1h38min.
Embodiment 18
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
Copolyreaction is carried out by raw material of 84 parts of methanol, 135 parts of vinylacetate, 1 part of hydrogen peroxide and ethylene, control is logical
Entering pressure in the kettle of ethylene is 6MPa, and copolyreaction temperature is 65 DEG C, pressure 6.5MPa, and the reaction time is 6.5 hours；
B. alcoholysis
Sodium hydroxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period sodium hydroxide
Dosage and second time period sodium hydroxide concentration ratio are 1:1, and the ratio of first time period and second time period is 0.8:1, hydroxide
The molar ratio for the ethylene-vinyl acetate copolymer that sodium and copolymerization obtain is 0.2:1；
C. it post-processes:
Sodium phosphite aqueous solution is added into the mixture that alcoholysis obtains to be post-processed, the dosage of sodium phosphite aqueous solution
For make be added after solution phosphorous acid sodium final concentration of 100ppm, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 15:1) on extrusion board
Bar is frozen into water out, cuts granulating, washing is dried after centrifugal dehydration.
Alcoholysis reaction total time is 1h40min.
Embodiment 19
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
Be copolymerized using 70 parts of ethyl alcohol, 60 parts of vinylacetate, 1 part of the double butyl esters of dicetyl peroxydicarbonate and ethylene as raw material anti-
It answers, it is 2.5MPa that control, which is passed through in the kettle of ethylene pressure, and copolyreaction temperature is 80 DEG C, pressure 5.5MPa, and the reaction time is
6.0 hour；
B. alcoholysis
Potassium methoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period methanol potassium application rate
It is 2:1 with second time period potassium methoxide amount ratio, the ratio of first time period and second time period is 1:1, potassium methoxide and is copolymerized
The molar ratio of the ethylene-vinyl acetate copolymer arrived is 0.1:1；
C. it post-processes:
Dihydrogen phosphite aqueous solutions of potassium is added into the mixture that alcoholysis obtains to be post-processed, potassium dihydrogen phosphite is water-soluble
The dosage of liquid is the final concentration of 50ppm of solution phosphorous acid potassium dihydrogen after making to be added, the ethylene-vinyl obtained relative to alcoholysis
Alcohol copolymer meter；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 17:1) on extrusion board
Bar is frozen into water out, cuts granulating, washing is dried after centrifugal dehydration.
Alcoholysis reaction total time is 1h25min.
Embodiment 20
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
Copolyreaction, control are carried out by raw material of 60 parts of methanol, 65 parts of vinylacetate, 0.8 part of potassium peroxydisulfate and ethylene
Being passed through pressure in the kettle of ethylene is 6.0MPa, and copolyreaction temperature is 49 DEG C, pressure 5.7MPa, and the reaction time is 4.5 hours；
B. alcoholysis
Sodium methoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, first time period sodium methoxide dosage
It is 1:1 with second time period sodium methoxide amount ratio, the ratio of first time period and second time period is 1:1, sodium methoxide and is copolymerized
The molar ratio of the ethylene-vinyl acetate copolymer arrived is 0.1:1；
C. it post-processes:
Oxalic acid aqueous solution is added into the mixture that alcoholysis obtains and phosphate aqueous solution is post-processed, oxalic acid aqueous solution
Dosage is the final concentration of 100ppm of solution mesoxalic acid after making to be added, and the dosage of phosphate aqueous solution is phosphoric acid in solution after making to be added
Final concentration of 100ppm, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 17:1) on extrusion board
Bar is frozen into water out, cuts granulating, washing is dried after centrifugal dehydration.
Alcoholysis reaction total time is 1h39min.
Embodiment 21
The preparation method of ethylene-vinyl alcohol copolymer, specifically follows the steps below:
A. it is copolymerized
Copolyreaction is carried out by raw material of 50 parts of ethyl alcohol, 100 parts of vinylacetate, 1 part of potassium peroxydisulfate and ethylene, control is logical
Entering pressure in the kettle of ethylene is 2.5MPa, and copolyreaction temperature is 65 DEG C, pressure 5.7MPa, and the reaction time is 6.5 hours；
B. alcoholysis
Sodium ethoxide is added in the solution obtained in two times to step A and carries out alcoholysis reaction, second time period sodium ethoxide dosage
It is 2:1 with second time period sodium ethoxide amount ratio, the ratio of first time period and second time period is 1:1, sodium ethoxide and is copolymerized
The molar ratio of the ethylene-vinyl acetate copolymer arrived is 0.2:1；
C. it post-processes:
Acetic acid aqueous solution, tetraboric acid aqueous solution and potassium dihydrogen phosphate aqueous solution are added into the mixture that alcoholysis obtains to carry out
Post-processing, the dosage of acetic acid aqueous solution are the final concentration of 200ppm of acetic acid in solution after making to be added, the use of tetraboric acid aqueous solution
Amount is the final concentration of 200ppm for making tetraboric acid in solution after being added, and the dosage of potassium dihydrogen phosphate aqueous solution is solution after making to be added
The final concentration of 200ppm of middle potassium dihydrogen phosphate, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains；
D. it is precipitated and is granulated, is dry
The obtained solution of step C is pumped into extruder to squeeze by the extrusion cavities (draw ratio 15:1) on extrusion board
It is frozen into bar into the solution that the mass ratio of methanol and water is 3:4 out, cuts granulating, washing is done after centrifugal dehydration
It is dry.
Alcoholysis reaction total time are as follows: 1h25min.
Appearance, alcoholysis degree and the yellowness index of ethylene-vinyl alcohol copolymer made from embodiment 1-21 are detected, as a result such as table
Shown in 1；
Wherein, appearance detects by an unaided eye；
Alcoholysis degree is detected using nucleus magnetic hydrogen spectrum method, by calculating the peak area of hydroxyl and the ratio of methine peak area
Obtain the alcoholysis degree of ethylene-vinyl alcohol copolymer；
The detection method of yellowness index are as follows: 30 grams of granules of copolymer of ethylene-vinyl alcohol is taken to be laid in 10cm × 10cm size
White polytetrafluoroethylpipe pallet in, pallet is moved into baking oven, setting temperature in baking oven is 230 DEG C, the thermostatic 5,10,
Take out after twenty minutes, it is lower using the smaller finished product degree of staining that represents of yellowness index YI, YI value of colour difference meter test sample, appearance compared with
It is white to show that heat resistance is better.
1 the performance test results of table
As seen from the above table, ethylene-vinyl alcohol copolymer smooth in appearance produced by the present invention, form and aspect are whiter；Alcoholysis degree is
99.3-99.7%, yellowness index YI are 8-11.Thus it proves, the alcoholysis degree of ethylene-vinyl alcohol copolymer produced by the present invention
Height, Good Heat-resistance, degree of staining are low.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (10)
1. the preparation method of ethylene-vinyl alcohol copolymer, including copolymerization and Alcoholysis Step, which is characterized in that alkali is added in two portions
Catalyst carries out alcoholysis reaction, and first time period base catalyst dosage and second time period base catalyst amount ratio are 0.8:1-2:
1, first time period and second time period ratio are 0.5:1-1.5:1, and the ethylene-vinyl acetate that base catalyst and copolymerization obtain is total
The molar ratio of polymers is 0.01:1-0.3:1.
2. method according to claim 1, which is characterized in that the copolymerization refers to 20-100 parts of solvent, vinylacetate
60-150 parts, 0.005-1 parts of initiator and ethylene are that raw material carries out copolyreaction, and it is 2.5- that control, which is passed through pressure in the kettle of ethylene,
6MPa, reaction time are 2.0-8.0 hours.
3. method according to claim 2, which is characterized in that the temperature of the copolyreaction is 40-80 DEG C, pressure 2.0-
6.5MPa。
4. according to claim 1,2 or 3 the method, which is characterized in that the base catalyst be sodium hydroxide, potassium hydroxide,
Sodium methoxide, sodium ethoxide or potassium methoxide.
5. according to claim 1,2,3 or 4 the method, which is characterized in that when first time period base catalyst dosage is with second
Between section base catalyst amount ratio be 1:1-1.5:1, first time period and second time period ratio are 0.8:1-1.2:1.
6. according to claim 1,2,3,4 or 5 the method, which is characterized in that further comprising the steps of: what is obtained to alcoholysis is mixed
It closes after the progress of one or more of carboxylic acid compound aqueous solution, boride aqueous solution, phosphate cpd aqueous solution is added in object
Processing.
7. method according to claim 6, which is characterized in that it is water-soluble that carboxylic acid compound is added into the mixture that alcoholysis obtains
One or more of liquid, boride aqueous solution, phosphate cpd aqueous solution are post-processed, the use of carboxylic acid compound aqueous solution
Amount is the final concentration of 10-500ppm for making carboxylic acid compound in solution after being added, and the dosage of boride aqueous solution is after making addition
The final concentration of 10-1000ppm of boride in solution, the dosage of phosphate cpd aqueous solution are phosphorylation in solution after making to be added
The final concentration of 10-300ppm for closing object, based on the ethylene-vinyl alcohol copolymer that alcoholysis obtains.
8. according to claim 6 or 7 the method, which is characterized in that the carboxylic acid compound be oxalic acid, succinic acid, benzoic acid,
Citric acid, acetic acid, propionic acid or lactic acid.
9. according to claim 6 or 7 the method, which is characterized in that the boride is boric acid, metaboric acid, tetraboric acid, boric acid
Ester, borate or borine.
10. according to claim 6 or 7 the method, which is characterized in that the phosphate cpd is phosphoric acid, phosphorous acid, phosphate
Or phosphite.
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| CN112707987A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Ethylene-vinyl alcohol copolymer and method for producing the same |
| CN112707998A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Ethylene-vinyl alcohol copolymer having excellent hue |
| CN113736004A (en) * | 2021-09-30 | 2021-12-03 | 盛虹石化集团上海新材料有限公司 | Ethylene-vinyl alcohol copolymer and preparation method and application thereof |
| WO2022078458A1 (en) | 2020-10-15 | 2022-04-21 | 中国石油化工股份有限公司 | Ethylene-vinyl alcohol copolymer composition and preparation method therefor |
| CN115991841A (en) * | 2021-10-19 | 2023-04-21 | 中国石油化工股份有限公司 | EVOH resin composition with excellent thermal stability and preparation method thereof |
| WO2023080384A1 (en) | 2021-11-02 | 2023-05-11 | 주식회사 엘지화학 | Preparation method for ethylene-vinyl alcohol copolymer |
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| CN112707987A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Ethylene-vinyl alcohol copolymer and method for producing the same |
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