CN109563279A - The manufacturing method of macromolecule membrane - Google Patents
The manufacturing method of macromolecule membrane Download PDFInfo
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- CN109563279A CN109563279A CN201780031776.1A CN201780031776A CN109563279A CN 109563279 A CN109563279 A CN 109563279A CN 201780031776 A CN201780031776 A CN 201780031776A CN 109563279 A CN109563279 A CN 109563279A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The purpose of the present invention is to provide a kind of methods of macromolecule membrane for efficiently manufacturing low water absorbable.The production method of macromolecule membrane of the invention includes: the process that makes the monomer polymerization to obtain granular polymer in the reaction solution containing surfactant peptides salt, the monomer with vinyl, polymerization initiator and aqueous solvent；And the process by granular polymer acquisition macromolecule membrane, wherein the concentration of monomer described in the reaction solution is set as 10 mass % or more and 60 mass % or less.
Description
Technical field
The present invention relates to a kind of methods of the macromolecule membrane of high efficiency manufacture low water absorbable.
Background technique
There are various methods by the monomer polymerization with vinyl, and as important method, there are emulsion polymerizations
Method and suspension polymerization.Since these methods use aqueous solvent, it is easy to remove the heat that polymerization reaction generates, has easy
In control reaction temperature the advantages of.In addition, have the further advantage that the polymer as product with it is small it is granular obtain, be easy to from
Separation, washing and drying in liquid phase.
More specifically, in emulsion polymerization method, made in an aqueous solvent using surfactant and polymerization initiator
Monomer polymerization.Monomer with vinyl is usually expressed as insoluble or slightly solubility for water, but it is by being typically entrapped within by surface
Activating agent formed micella and disperse in an aqueous solvent.In the micella, gathered by the free radical of polymerization initiator generation
Close monomer.Magnitude of the size of this micella at several nanometers, and be tens nanometers by the polymer that emulsion polymerization method obtains
~several hundred nanometers of very small substance has degree of polymerization excellent characteristics such greatly.It is obtained by emulsion polymerization method poly-
The dispersion liquid for closing object, can be directly used as coating or adhesive.
In suspension polymerisation, be often used without surfactant, by be mechanically vigorously stirred in an aqueous solvent monomer and
Polymerization initiator makes monomer polymerization to form the drop being made of monomer.This drop is bigger than the micella of emulsion polymerization method, leads to
Often with the size for having 0.01~1mm or so.In addition, this drop is bonded to each other and huge particlized, it is poly- that this may damage suspension
The advantages of closing itself.Therefore, in order to make droplets stable, addition gelatin, starch, polyvinyl alcohol, carboxymethyl cellulose etc. are water-soluble
The insoluble powder such as property polymer, calcium carbonate and magnesium carbonate.
But in the polymer obtained by emulsion polymerization method or suspension polymerization, exists and be mixed into the surfactant
The problem of deterioration in characteristics for making polymer with droplets stable agent itself.For example, since these surfactants etc. are hydrophilies
, even if polymer itself is non-hydrophilic, it is also possible to absorb moisture.Known acrylic resin has the high grade of transparency, but this
The kind transparency is reduced because of water suction.
In addition, these surfactants etc. can be also mixed into the waste liquid after isolating polymer, due to wherein existing to ring
Bring the substance of adverse effect in border, it is therefore desirable to reduce.On the other hand, when by it is not soluble in water or be insoluble in water monomer carry out cream
Whens changing polymerization etc., the surfactant etc. of specified rate is needed to come the micella of dispersed monomer, drop.When reduction surfactant etc.
When usage amount, the ratio for reducing monomer in polymerization liquid, and the emulsion intercalation method containing granular polymer are also had to
It may be decreased.
Furthermore it is known that surfactant peptides are as biosurfactant (surfactant from biology).Surface-active
Peptide has cyclic peptide structure, and bigger than conventional surfactants because of the hydrophily that the structure of the annulus is shown
It is more, therefore it is with excellent Action of Surfactant.Thus, for example its sodium salt is used as the surfactant of cosmetics etc. (specially
Sharp document 1).
In addition, it is living as surface used in emulsion polymerization method to have enumerated surfactant peptides salt in patent document 2~9
Property agent.In addition, applicant has developed the method (patents for using the surfactant peptides salt of low concentration to carry out polymerising ethylene base class monomer
Document 10).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2003-128512 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2005-15353 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2005-15537 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2007-296120 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2008-162975 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2009-155306 bulletin
Patent document 7: Japanese Unexamined Patent Publication 2010-284519 bulletin
Patent document 8: No. 2007/126067 volume of International Publication No.
Patent document 9: No. 2010/125691 volume of International Publication No.
Patent document 10: No. 2014/142177 volume of International Publication No.
Summary of the invention
Invent the technical issues of solved
As described above, the method as manufacture granular polymer, it is known that emulsion polymerization method and suspension polymerization.However,
The concentration that starting monomer in polymerization liquid cannot be improved in these methods, not can be carried out efficient production sometimes.
Specifically, since surfactant is the impurity of product and makes its quality deterioration, and it usually has environment
Evil, therefore its usage amount should be reduced as far as.But if the usage amount of surfactant is insufficient, in emulsion polymerization or
In suspension polymerisation, drop, the micella of monomer may merge and can not manufacture fine particle, and partial size becomes unevenly, and particle
Has the tendency that combination each other.Therefore, it is emulsified without using surfactant or using only the emulsifier-free of a small amount of surfactant
In the case where polymerization, the concentration of monomer is generally up to about 5~10 mass % in polymerization liquid.It is obtained by this polymerization liquid
Lotion in granular polymer concentration it is low, it is difficult to use.In addition, after polymerisation, preferably being purified from polymer
Surfactant etc. is removed, but this purifying may be decreased whole manufacture efficiency.
Therefore, the purpose of the present invention is to provide a kind of methods of the macromolecule membrane of high efficiency manufacture low water absorbable.
Technical means to solve problem
The present inventor has made intensive studies to solve the above problems.As a result, being found and being completed as follows
The present invention: when using surfactant peptides salt as surfactant, even if monomer concentration in polymerization liquid and previous
Compared to greatly improving, it also can sufficiently inhibit the merging of the drop, micella of monomer, combine, can be manufactured with fabulous efficiency uniform
And independent granular polymer, and the macromolecule membrane as obtained from this granular polymer has extremely low water imbibition.
The present invention is as follows.
[1] a kind of manufacturing method of macromolecule membrane, includes at least:
In the surfactant peptides salt, the monomer with vinyl, polymerization initiator and aqueous molten indicated containing following formula (I)s
In the reaction solution of agent, the process that makes the monomer polymerization to obtain granular polymer；And
The process that macromolecule membrane is obtained by the granular polymer,
Wherein, the concentration of monomer described in the reaction solution is set as 10 mass % or more and 60 mass % hereinafter,
[chemical formula 1]
In formula,
X indicates the amino acid residue selected from leucine, isoleucine and valine；
R indicates C9-18Alkyl；
M+Indicate alkali metal ion or quaternary ammonium ion.
[2] method according to above-mentioned [1], wherein
The concentration of the surfactant peptides salt (I) in the reaction solution is 10mM or less.
[3] method according to above-mentioned [1], wherein
The surfactant peptides salt (I) is 1.5 below the mass relative to the ratio of 100 mass parts of monomer.
[4] production method according to any one of above-mentioned [1]~[3], further include:
The process that obtained granular polymer is separated from the liquid phase of the reaction solution；
Polyvalent metal ion is added into liquid phase so that the cured process of surfactant peptides salt；And
The process that the surfactant peptides salt having cured is separated.
[5] production method according to above-mentioned [4], wherein
After polymerization process and before the separation process of granular polymer, by adding alkali gold into polymerization liquid
Belong to ion to make the cured process of granular polymer.
The effect of invention
Method according to the invention it is possible to make vinyl monomer carry out emulsion polymerization with the surfactant of relatively small amount
Or suspension polymerisation.Therefore, the significant reduced macromolecule membrane of residual quantity of surfactant can be manufactured.This macromolecule membrane
With extremely low water imbibition and high-quality.Further, since the residual quantity of the surfactant in waste liquid can be significantly inhibited, because
This does not need to dispose waste liquid, and can reduce labour and time.In addition, according to the method for the present invention, even if polymerization liquid
In monomer concentration be significantly increased compared with conventional method, also can inhibit monomer the merging of drop, micella, combination it is same
When, manufacture granular monomer.In addition, it is surprising that reaction solution as obtained by emulsion polymerization of the invention itself or will reaction
Granular polymer obtained by liquid is dry, manufactures macromolecule membrane even if not being further purified, water absorption rate is also very low.Cause
This, method of the present invention as the macromolecule membrane for capableing of high efficiency manufacture high-quality is industrially very excellent.
Detailed description of the invention
Fig. 1 is taken into consideration using the outer of reaction solution of the SDS of the SFNa or 80mM of the 8mM emulsion polymerization for having carried out styrene
The cohesion amount of piece and polymer particle.
Fig. 2 is the water imbibition for indicating film made from the polystyrene particle as obtained by the SDS for using the SFNa or 80mM of 8mM
The photo of test result.In every photo, left side is film made from SFNa using 8mM, and right side is the SDS system using 80mM
The film obtained.
Fig. 3 is the water imbibition for indicating film made from the polystyrene particle as obtained by the SDS for using the SFNa or 80mM of 8mM
The chart of test result.
Fig. 4 be indicate to carry out the emulsion polymerization of n-BMA using the SDS of the SFNa of 1.2mM or 12mM and
The appearance photo of the reaction solution obtained and the cohesion amount of polymer particle.
Fig. 5 be indicate SDS as using the SFNa or 12mM of 1.2mM or without using obtained by emulsifier by poly- methyl-prop
The chart of the water absorption test result of film made from olefin(e) acid N-butyl particle.
Specific embodiment
The manufacturing method of macromolecule membrane of the invention includes at least: containing surfactant peptides salt (I), is having vinyl
Monomer, polymerization initiator and aqueous solvent reaction solution in, the process that makes the monomer polymerization to obtain granular polymer；With
And the process by granular polymer acquisition macromolecule membrane, and the concentration of monomer described in the reaction solution is set as 10
Quality % or more and 60 mass % or less.Hereinafter, the method for the present invention will be described according to implementation sequence.
(1) polymerization process
In the present invention, the surfactant peptides salt for using following formula (I)s to indicate is as surfactant:
[chemical formula 2]
In formula,
X indicates the amino acid residue selected from leucine, isoleucine and valine；
R indicates C9-18Alkyl；
M+Indicate alkali metal ion or quaternary ammonium ion.Even if less than the amount used under the conditions of typical polymerization, this surface
Active peptide salt can also form micella in emulsion polymerization, and the drop in being polymerize with stable suspersion.It should be noted that
In the disclosure, " surfactant peptides salt (I) " is sometimes referred to as by the surfactant peptides salt that formula (I) is indicated.
As the amino acid residue of X, L-type or D type, but preferred L-type can be.
“C9-18Alkyl " refers to that carbon atom number is the univalent saturated hydrocarbon radical of 9 or more and 18 linear chain or branched chains below.For example,
N-nonyl, 6- Methyl Octyl, 7- Methyl Octyl, positive decyl, 8- Nonyl, n-undecane base, 9- methyldecyl, n-dodecane
Base, 10- methylundecyl, n-tridecane base, 11- methyl dodecyl, n-tetradecane base, n-pentadecane base, hexadecane
Base, n-heptadecane base, n-octadecane base etc..
Alkali metal ion is not particularly limited, and indicates lithium ion, sodium ion, potassium ion etc..
As the substituent group of quaternary ammonium ion, such as following organic group can be enumerated: methyl, ethyl, n-propyl, isopropyl,
The alkyl such as normal-butyl, tert-butyl；The aralkyl such as benzyl, methylbenzyl, phenethyl；The aryl such as phenyl, tolyl, xylyl.
As quaternary ammonium ion, such as tetramethyl ammonium, tetraethyl ammonium ion, pyridinium ion can be enumerated etc..
One or more kinds of surfactant peptides salt (I) can be used.It is, for example, possible to use containing there are many have not
With the mixture of the surfactant peptides salt (I) of R group.
Surfactant peptides salt (I) can for example belong to the micro- of bacterial strain of bacillus subtilis etc by known method culture
Biology, and be isolated from the culture solution, and its purifying product can be used, it can also directly use such as culture solution.This
Outside, it can be used in the same manner through surfactant peptides salt obtained by chemical synthesis.
In the present invention, the concentration of the surfactant peptides salt (I) in the reaction solution can in polymerization liquid monomer
Drop, micella nonjoinder, suitably determine in conjunction in the range of.For example, even if the concentration is 20mM hereinafter, by containing highly concentrated
The polymerization liquid for spending monomer can also be with high efficiency manufacture granular polymer.On the other hand, with the increase of monomer concentration, monomer
Drop, micella are easier to uniformly and have an independent existence, therefore the concentration is preferably 0.1mM or more.The concentration is more preferably 0.5mM
More than, further preferably 1mM or more, and preferably 10mM is hereinafter, further preferably 5mM or less.
In addition, for the reason identical as surfactant peptides salt (I) concentration in polymerization liquid, surfactant peptides salt
(I) ratio relative to 100 mass parts of monomer be preferably 0.02 mass parts or more and 10 below the mass.The ratio is more preferably
More than 0.1 mass parts, more than further preferably 0.2 mass parts, and more preferably 5 below the mass, further preferably
1.5 below the mass.
It can appropriate selective polymerization initiator.Such as it can enumerate: the peroxide of the ketone such as cyclohexanone peroxide or aldehyde；Peroxide
Change the diacyl peroxides classes such as acetyl；The hydroperoxide types such as tert-butyl hydroperoxide and cumene hydroperoxide；Two tertiary fourths
The dialkyl peroxides class such as base peroxide；Tert-butyl crosses the alkyl super-acid esters class such as isobutyrate；Tert-butyl hydroperoxide isopropyl
The organic peroxide of the percarbonic acids esters such as base carbonic ester etc.；The inorganic peroxides such as hydrogen peroxide and potassium peroxydisulfate；2,2 '-is even
Azo-compounds such as nitrogen bis-isobutyronitrile etc., but not limited to this.Wherein, organic peroxide and/or inorganic peroxide are being used
In the case where, it can be used as heat decomposition type polymerization initiator, it additionally can be with sodium ascorbate, sodium sulfoxylate formaldehyde etc.
The chelating agents such as co-catalysts and edetate such as reducing agent, optional ferrous sulfate are applied in combination, for use as oxidation
Reduced form polymerization initiator.It should be noted that using water-soluble polymerization initiator when carrying out emulsion polymerization, and works as and hanged
Oil-soluble polymerization initiator is used when floating polymerization.
The usage amount of polymerization initiator can be with appropriate adjustment, such as relative to 100 mass parts of monomer can be 0.1 mass parts
Above and 5 below the mass.
In addition it is possible to use the reducing agent that can be applied in combination with polymerization initiator.As this reducing agent, such as can enumerate
Sodium hydrogensulfite, sodium sulfoxylate formaldehyde, sodium pyrosulfite etc..
The usage amount of reducing agent can be with appropriate adjustment, such as can be to be more than 0.1 mass parts relative to 100 mass parts of monomer
And 5 below the mass.
Aqueous solvent used in the method for the present invention refers to containing water and makees solvent as main component with water, can be list
The mixed solvent of only water or water and miscible organic solvents.Here the type of water is not particularly limited, and steaming can be used
Any one of distilled water, pure water, ultrapure water, tap water etc..It, will when using the mixed solvent of water and miscible organic solvents
The ratio of the in the mixed solvent water is set as 50 volume % or more.The ratio is more preferably 60 volume % or more, further preferably
For 70 volume % or more, particularly preferably 80 volume % or more.Water more preferably is used only as solvent.
It as the miscible organic solvents being used in mixed way with water, such as can enumerate: the alcoholic solvents such as methanol and ethyl alcohol；Tetrahydro
The ether solvents such as furans；The ketone solvents such as acetone；The amide solvents such as dimethylformamide and dimethyl acetamide, as long as it is at normal temperature
It miscible with water can just be not particularly limited.
The monomer polymerizeing by the method for the invention, it should be the vinyl-based list with the vinyl of free redical polymerization
Body.Such as it can enumerate: the vinyl esters monomer such as vinyl acetate, vinyl propionate；The aromatic series such as styrene, vinyltoluene
Vinyl compound class monomer；The alpha-olefines monomer such as ethylene, propylene；(methyl) acrylic acid, (methyl) methyl acrylate, (first
Base) n-butyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, two (methyl) acrylic acid glycol esters, (methyl) acrylic acid acyl
Amine, Diacetone Acrylamide etc. (methyl) acrylic monomer；The vinyl halides such as vinyl chloride, vinylidene chloride, vinylidene fluoride
Base class monomer etc..They can be used alone, and two or more be copolymerized can also be applied in combination.
The amount of used monomer is not particularly limited, and can suitably adjust, such as can be by monomer in reaction solution
Concentration is set as 10 mass parts or more, also can be set to 60 below the mass.
Other than surfactant peptides salt (I), the monomer containing vinyl, polymerization initiator and aqueous solvent, it can also incite somebody to action
Common adding ingredient for emulsion polymerization be mixed into reaction it is molten in.As other adding ingredients, such as pH adjusting can be enumerated
Agent.As pH adjusting agent, such as bicarbonate, carbonate, hydroxide and the ammonia and dimethylamino of alkali metal can be enumerated
The amines such as ethyl alcohol.The pH appropriate adjustment of reaction solution, is not particularly limited, such as can be adjusted to 4 or more and 12 hereinafter, from table
From the perspective of the stability of face active peptide salt (I), it is preferably regulated as 7 or more and 10 or less.
The actual conditions of polymerization reaction are referring to conventional method.For example, all components can be mixed, then plus
One or more of described component can also be added portionwise to start to react in heat.In addition, by a part of aqueous solvent, a part
Water-soluble polymerization initiator, a part of surfactant peptides salt (I) and monomer mixing, will be remaining aqueous molten to manufacture pre-emulsion
Agent, polymerization initiator are mixed with surfactant peptides salt (I) using as solution, and pre- cream can be added dropwise while stirring the solution
Liquid.
It is preferable to use the non-active gas such as nitrogen or argon gas to be replaced for reaction atmosphere, to stablize necessary to polymerization reaction
Free radical.In addition, for the same reason, preferably being dissolved by being blown into the processing such as non-active gas to be removed from aqueous solvent
Oxygen.
Reaction temperature and reaction time are not particularly limited, appropriate adjustment.For example, reaction temperature can substantially be set as 40
DEG C or more and 120 DEG C hereinafter, the reaction time can substantially be set as 1 hour or more and 20 hours or less.
Since there is high stability in the reaction solution that obtains in the polymerization process and be formed by granular polymer hardly possible
With precipitating, therefore it can be directly used as adhesive, coating, coating material etc..In the present invention, made using surfactant peptides salt
For surfactant, and its amount be less than amount in the prior art also can, it can be said that, in obtained reaction solution (latex)
The mixed volume of surfactant is less, and inhibits its adverse effect.
When directly using the reaction solution, common adding ingredient can be mixed into each product.These adding ingredients do not have
There is special limitation, such as water-soluble resin, solvent, plasticizer, defoaming agent, thickener, levelling agent, dispersing agent, coloring can be enumerated
Agent, waterproofing agent, lubricant, pH regulator/preservative, inorganic pigment, organic pigment, surfactant, crosslinking agent etc..
(2) curing process of granular polymer
As described above, the reaction solution can be used directly.But it is also possible to by the granular polymer of generation from liquid phase
Separation, realizes being further reduced for surfactant.Therefore, in this process, solidify granular polymer.But this process
Be it is optional, can not implement.
In the present invention, it is preferred to consolidate granular polymer by adding alkali metal ion into the reaction solution after reaction
Change.
The curing agent of granular polymer is following substance: preventing the ionization of the hydrophilic radical of surfactant, weakens
The surface activation ability of surfactant, and granular polymer is agglomerated by hydrophobic interaction.As this
Curing agent, it is previous to use: aluminum aluminum sulfate, trien, sodium hydroxide, potassium hydroxide, sodium chloride, magnesium chloride, calcium chloride,
Hydrochloric acid, sulfuric acid, sodium sulphate etc., but sufficient cohesiveness cannot be obtained since alkali metal ion is used alone, it can combine
Use polyvalent metal ion and sodium hydroxide etc..Especially in the present invention, due to using the alkali metal salts etc. of surfactant peptides
As surfactant, then think that individual alkali metal ion cannot reduce the surface activation ability of surface active peptide, no
Granular polymer can be made to solidify.However it is contrary to expectations, even if discovery only adds alkali metal ion into the reaction solution after reaction,
Granular polymer can also solidify.
As alkali metal ion, sodium ion, potassium ion, lithium ion, preferably sodium ion and potassium ion, more preferable sodium can be enumerated
Ion.In addition, convenience is higher when using alkali metal ion in a salt form.As this salt, such as chloride can be enumerated
With halide salts, sulfate, carbonate, the bicarbonate such as bromide etc..In addition, about alkali metal ion, the aqueous solution of salt
It is easily added in reaction solution.
About the usage amount of alkali metal ion, as long as appropriate adjustment is i.e. in the range of granular polymer can sufficiently solidify
It can., can be with appropriate adjustment in addition, temperature when granular polymer solidifies is not particularly limited, such as preferably 5 DEG C or more and 50
DEG C or less.
(3) separation process of granular polymer
Regardless of whether carrying out the curing process, granular polymer can be separated from liquid phase.It, can by this process
To separate granular polymer from the liquid phase containing surfactant, the table being mixed into granular polymer can be further reduced
The amount of face activating agent.But this process optionally carries out, and as set forth above, it is possible to directly utilizes granular polymer and liquid
The mixture of phase.
As the method for separation granular polymer and liquid phase, conventional method can be used.It is, for example, possible to use filtering or from
Heart separation, and will be stood by the mixture of the curing process and solidify obtained granular polymer and precipitate, pass through later
The liquid phases of the removings as supernatant such as decantation.
Alternatively, the volatile components such as solvent can only be distilled off by heating the reaction solution.It is molten when being only distilled off
Whens agent etc., the solid components such as surfactant peptides salt (I) remain in resulting granular polymer, but, it is surprising that even if
From the particulate polymer for remaining surfactant peptides salt (I), macromolecule membrane, the water imbibition of this macromolecule membrane are manufactured
It is relatively low.Although its reason is not yet clear, other than the usage amount of surfactant peptides salt (I) script is less, surface-active
Peptide salt (I) is not it is also possible to damage high molecular low water absorbable.
(4) curing process of surfactant peptides salt
In the separation process of the granular polymer, table is contained by the liquid phase of the acquisitions such as filtering, centrifuge separation, decantation
Face active peptide salt (I).In this process, by solidifying surfactant peptides salt (I), to realize the surfactant peptides salt in liquid phase
(I) reduction of amount.That is, the amount of surfactant in liquid phase can be reduced by this process, even if will obtain in this process as a result,
The liquid phase obtained is discharged into environment, can also inhibit its influence to environment, and be easy to wastewater treatment.Further, it is also possible to will
Surfactant peptides obtained by recycling are recycled.
Conventional surfactant is difficult to be cured as solid from its solution.However, the inventors discovered that, by by multivalence
Metal ion is added in the solution of surfactant peptides salt, and surfactant peptides salt can be made to solidify.
Polyvalent metal ion refers to the metal ion of divalent or more.As polyvalent metal ion, such as magnesium ion can be enumerated
With the alkaline-earth metals ion such as calcium ion；The trivalent metal ions such as aluminium.
In addition, convenience is higher when using polyvalent metal ion in a salt form.As this salt, such as can enumerate
The halide salts such as chloride, bromide, sulfate, carbonate etc..In addition, being easy to add the aqueous solution of the salt of polyvalent metal ion
It is added in reaction solution.
The usage amount of polyvalent metal ion, appropriate adjustment in the range of surfactant peptides salt can sufficiently solidify,
Such as relative to used surfactant peptides salt more than equimolar amounts to add.On the other hand, the upper limit does not limit especially
System, such as about 20 times moles or less in the ratio.
Temperature when surfactant peptides solidify is not particularly limited, appropriate adjustment, for example, be preferably set to 5 DEG C or more and
50 DEG C or less.
(5) separation process of surfactant peptides salt
Surfactant peptides salt obtained by curing process solidification by the surfactant peptides salt, can be with liquid phase separation.
The surfactant peptides salt as surfactant is removed from resulting liquid phase, content significantly reduces.Therefore, by this process
The liquid phase of acquisition can be expelled directly out or its processing is also very easy to.In addition, by utilizing for example a large amount of alkali metal ion
Or quaternary ammonium ion is handled, it can be made solubilized again, and recycled.
As the method that the surfactant peptides salt that will be had cured is separated from liquid phase, can be used it is described as polymer and
The separation method of liquid phase and the method enumerated.
(6) manufacturing process of macromolecule membrane
In this process, macromolecule membrane is obtained by granular polymer.As long as macromolecule membrane is to constitute bead polymerization
The polymer of object makees film as main component, is not particularly limited.For example, as described above, working as the polymerization process
Whens the reaction solution of middle acquisition is directly used as adhesive, coating, coating material etc., after being coated the reaction solution, pass through steaming
The material layer that distillation is removed solvent and formed is also contained in macromolecule membrane.Furthermore, it is possible to simultaneously by granular polymer heating melting
Pressurization film forming, or its solution can be manufactured and pass through casting film, the granular polymer are as follows: obtain from emulsion polymerization process
Reaction solution set out, by filter, be centrifugated etc. be separately separated obtained by granular polymer, by dry same reaction liquid
Obtained by granular polymer or the granular polymer refined.Any macromolecule membrane can be by suitably using known
Technology manufactures.
The application went out to be willing to No. 2016-103524 based on the Japanese Patent submitted on May 24 in 2016, it is desirable that priority
Equity.The Japanese Patent submitted on May 24 goes out to be willing to the full content of No. 2016-103524 specification within 2016, draws
To the reference as the application.
Embodiment
Hereinafter, embodiment will be enumerated, the present invention will be described in more detail, but the present invention is not limited by the following examples,
And modification appropriate can be carried out in the range of meeting aforementioned and aftermentioned main points, and these be included in it is of the invention
In technical scope.
Embodiment 1
(1) emulsion polymerization
In the removable flask of 200mL for being provided with anchor formula stirring blade, pure water 67g is added as solvent, sodium bicarbonate
0.14g is used as emulsifier, and makes it dissolve as pH adjusting agent, surfactant peptides sodium 0.6g (being 8mM relative to reaction solution).This
Outside, styrene 12g is added, and reacting liquid temperature is risen to 70 DEG C in a water bath, is then replaced in removable flask with nitrogen
Gas phase adds the potassium peroxydisulfate 0.2g that is dissolved in pure water 5g as polymerization initiator, and by the reaction of composition shown in table 1
Polymerization 12 hours is carried out while liquid is stirred with 240rpm.Meanwhile styrene 12g is additional three times with 1.5 hours intervals, make
It is 40 mass % that styrene, which is obtained, relative to the concentration of reaction solution.
[table 1]
(2) filming
The reaction solution obtained in (1) described in drying at 80 DEG C using baking oven is to obtain powder.As in the powder by obtained by
About 0.1g melted under conditions of 170 DEG C, 6MPa compacting 1 minute, manufacture thickness be about 200 μm polystyrene film.
Comparative example 1
In addition to the surfactant peptides sodium for being used as emulsifier is changed into lauryl sodium sulfate (SDS), and shown in table 2
Composition carry out emulsion polymerization except, manufacture film in a manner of identical with the embodiment 1.It should be noted that working as SDS
Concentration and the embodiment 1 when being also set up as 8mM, monomer can agglomerate, thus by SDS with its 10 times amounts be 80mM into
It exercises and uses.
[table 2]
Test example 1: emulsion intercalation method
The stability of reaction solution obtained by emulsion polymerization by the embodiment 1 and comparative example 1 is tested.Tool
For body, the condensation product for including in the lotion obtained after polymerization is separated by 160 μm of mesh of sieve, and is existed with baking oven
Heat drying 12 hours or more at 80 DEG C, its weight is measured, and calculates it relative to the solids by weight for including in lotion
Ratio.As a result as shown in Figure 1.
As shown in Figure 1, the cohesion amount of granular polymer is 19% in the case where using the SDS of 80mM as emulsifier.
It should be noted that cohesion quantitative change is 100% when the SDS concentration in reaction solution is down to 40mM.
In contrast, in the case where using the SFNa of 8mM as emulsifier, cohesion amount is suppressed to 9%, and lotion is steady
Fixed.It, can also be more even if increasing the monomer concentration in reaction solution if using surfactant peptides as emulsifier in this wise
Stable lotion is obtained under few emulsifier concentration.
Test example 2: the water absorption test of film
The polystyrene film obtained in the embodiment 1 and comparative example 1 is immersed in the water, and stands 8 days at 25 DEG C.?
After dipping beginning 18 hours, after 45 hours, after 90 hours and after 190 hours, it is taken out and dried from water, is being shot outside it
While sight, its quality is measured.Appearance photo is as shown in Fig. 2, the variation of water absorption is as shown in Figure 3.
It is as shown in Figures 2 and 3 as a result, passing through leaching using polystyrene film made from SDS (in Fig. 2, the right side of each photo)
Enter in water and absorb water, and transparency passage at any time and reduce.On the other hand, using polystyrene film made from SFNa
The water absorption rate of (in Fig. 2, the left side of each photo), which is suppressed to, about uses 1/2 of polystyrene film made from SDS, and transparent
Degree is also not easy to reduce.It is demonstrated experimentally that there is low water absorbable using film made from SFNa in this way.
Embodiment 2
In the removable flask of 200mL for being provided with anchor formula stirring blade, pure water 79g is added as solvent, sodium bicarbonate
0.1g is used as emulsifier, and makes it dissolve as pH adjusting agent, surfactant peptides sodium 0.1g (being 1.2mM relative to reaction solution).
And n-BMA 36g (being 30 mass % relative to reaction solution) is added, and in a water bath by reacting liquid temperature liter
To 70 DEG C, the gas phase in removable flask then is replaced with nitrogen, adds the potassium peroxydisulfate 0.15g conduct being dissolved in pure water 5g
Polymerization initiator, and polymerization 12 hours is carried out while stirring with 240rpm.
[table 3]
Obtained reaction solution is dried at 80 DEG C to obtain powder with baking oven.By the about 0.1g in gained powder 90
DEG C, melting compacting 10 minutes under 6MPa, to manufacture the Vinalac 5920 film that thickness is about 200 μm.
Comparative example 2
In addition to the surfactant peptides sodium for being used as emulsifier is changed into lauryl sodium sulfate (SDS), and shown in table 4
Composition carry out emulsion polymerization except, manufacture film in a manner of identical with the embodiment 2.
[table 4]
Comparative example 3
In the removable flask of 200mL for being provided with anchor formula stirring blade, pure water 103g is added as solvent, sodium bicarbonate
0.035g makes it dissolve as pH adjusting agent.And it (is 10 matter relative to reaction solution that n-BMA 12g, which is added,
Measure %), and reacting liquid temperature is risen to 70 DEG C in a water bath, the gas phase in removable flask then is replaced with nitrogen, is added molten
Potassium peroxydisulfate 0.05g of the solution in pure water 5g carries out polymerization 12 as polymerization initiator while stirring with 240rpm
Hour.From obtained reaction solution, Vinalac 5920 film is manufactured in a manner of identical with the embodiment 2.
[table 5]
Test example 3: emulsion intercalation method
In a manner of identical with the test example 1, the emulsion polymerization by embodiment 3 and comparative example 2 is obtained anti-
The stability of liquid is answered to be tested.As a result as shown in Figure 4.
As shown in figure 4, the cohesion amount of granular polymer is 18.3% when using 12mM SDS as emulsifier.It needs
Illustrate, when the SDS concentration in reaction solution is down to 4mM, cohesion quantitative change is 50%.In addition, when without using emulsifier into
When row polymerization, monomer concentration is there are the limit of 10 mass %, and under the concentration more than it, granular polymer agglomerates completely.
In contrast, when using 1.2mM SFNa as emulsifier, though the amount of emulsifier be 1/10, cohesion amount also by
It is suppressed to 7.5%, and lotion is stable.If using surfactant peptides as emulsifier in this wise, even if increasing reaction
Monomer concentration in liquid can also obtain stable lotion under less emulsifier concentration.
Test example 4: the water absorption test of film
About the Vinalac 5920 film obtained in the embodiment 3 and comparative example 2,3, in addition in Xiang Shuizhong
Dipping start 4 hours after, after 18 hours, after 24 hours, after 90 hours, after 190 hours, it is taken out from water, and it is dry
Except quality measurement, water imbibition is tested in a manner of identical with the test example 3.The variation of water absorption is as shown in Figure 5.
It is as shown in Figure 5 as a result, using Vinalac 5920 film made from SFNa and using poly- first made from SDS
Base n-butyl acrylate film is compared, and water absorption rate is significantly suppressed, and the water absorption rate with without using poly- first made from emulsifier
Base n-butyl acrylate film is suitable.It is demonstrated experimentally that there is low water absorbable using film made from SFNa in this way.
Claims (5)
1. a kind of manufacturing method of macromolecule membrane, this method include at least:
In surfactant peptides salt, the monomer with vinyl, polymerization initiator and the aqueous solvent indicated containing following formula (I)s
In reaction solution, the process that makes the monomer polymerization to obtain granular polymer；And
The process that macromolecule membrane is obtained by the granular polymer,
Wherein, the concentration of monomer described in the reaction solution is set as 10 mass % or more and 60 mass % hereinafter,
In formula,
X indicates the amino acid residue selected from leucine, isoleucine and valine；
R indicates C9-18Alkyl；
M+ indicates alkali metal ion or quaternary ammonium ion.
2. according to the method described in claim 1, wherein,
The concentration of the surfactant peptides salt (I) in the reaction solution is 10mM or less.
3. according to the method described in claim 1, wherein,
The surfactant peptides salt (I) is 1.5 below the mass relative to the ratio of 100 mass parts of monomer.
4. manufacturing method described in any one of claim 1 to 3, further include:
By obtained granular polymer from the process of the liquid phase separation of the reaction solution；
Polyvalent metal ion is added into liquid phase so that the cured process of surfactant peptides salt；And
The process that the surfactant peptides salt having cured is separated.
5. manufacturing method according to claim 4, wherein
It further include by adding alkali into polymerization liquid after polymerization process and before the separation process of granular polymer
Metal ion makes the cured process of granular polymer.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015573A (en) * | 2003-06-24 | 2005-01-20 | Mitsubishi Engineering Plastics Corp | Antistatic resin composition |
| JP2005015353A (en) * | 2003-06-24 | 2005-01-20 | Saitama Daiichi Seiyaku Kk | Aqueous emulsion pressure-sensitive adhesive for medical percutaneous absorption tape and medical percutaneous absorption tape pharmaceutaical praepation and method for producing the same |
| CN102580609A (en) * | 2011-12-29 | 2012-07-18 | 华东理工大学 | Surfactant and preparation method thereof |
| CN105051074A (en) * | 2013-03-14 | 2015-11-11 | 株式会社钟化 | Polymer production method |
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| JP2000327722A (en) * | 1999-05-24 | 2000-11-28 | Clariant Internatl Ltd | Particulate emulsion and its production |
| JP4589608B2 (en) * | 2003-06-24 | 2010-12-01 | ニプロパッチ株式会社 | Pressure sensitive adhesive tape |
| JPWO2016129596A1 (en) * | 2015-02-13 | 2017-11-24 | 株式会社カネカ | Method for producing particulate polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015573A (en) * | 2003-06-24 | 2005-01-20 | Mitsubishi Engineering Plastics Corp | Antistatic resin composition |
| JP2005015353A (en) * | 2003-06-24 | 2005-01-20 | Saitama Daiichi Seiyaku Kk | Aqueous emulsion pressure-sensitive adhesive for medical percutaneous absorption tape and medical percutaneous absorption tape pharmaceutaical praepation and method for producing the same |
| CN102580609A (en) * | 2011-12-29 | 2012-07-18 | 华东理工大学 | Surfactant and preparation method thereof |
| CN105051074A (en) * | 2013-03-14 | 2015-11-11 | 株式会社钟化 | Polymer production method |
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| SAGHEER A. ONAIZI ET AL.: ""Adsorption and thermodynamics of biosurfactant, surfactin, monolayers at the air-buffered liquid interface"", 《COLLOID AND POLYMER SCIENCE》 * |
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