WO2022097718A1 - Polymère à base d'alcool vinylique modifié - Google Patents

Polymère à base d'alcool vinylique modifié Download PDF

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Publication number
WO2022097718A1
WO2022097718A1 PCT/JP2021/040762 JP2021040762W WO2022097718A1 WO 2022097718 A1 WO2022097718 A1 WO 2022097718A1 JP 2021040762 W JP2021040762 W JP 2021040762W WO 2022097718 A1 WO2022097718 A1 WO 2022097718A1
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mol
vinyl alcohol
modified vinyl
polymer
based polymer
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Japanese (ja)
Inventor
由貴 清水
啓之 小西
佐和子 小林
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Kuraray Co Ltd
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Kuraray Co Ltd
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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
    • C08F216/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or 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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to a modified vinyl alcohol polymer having excellent viscosity stability, biodegradability and oxygen gas barrier property.
  • PVA Vinyl alcohol-based polymer
  • the partially saponified PVA Since the melting point and the thermal decomposition temperature of the completely saponified PVA are very close to each other, it was impossible to thermally melt and mold the PVA. On the other hand, since the partially saponified PVA has a lower melting point than the fully saponified PVA, the partially saponified PVA is superior in heat melt moldability to the fully saponified PVA. However, since the partially saponified PVA has poor thermal stability, there is a problem that an acetic acid odor is generated during thermal melt molding. For the above reasons, it is difficult to achieve both water solubility and melt moldability, and attempts have been made to lower the melting point by adding a plasticizer or modifying PVA.
  • the oxygen gas barrier property which is one of the characteristics of PVA, is greatly related to the crystallinity of PVA, and the fully saponified PVA exhibits excellent oxygen gas barrier property.
  • PVA has a high barrier property in a dry atmosphere, it is known that when the relative humidity is about 70% or more, PVA violently absorbs moisture and the barrier property tends to decrease.
  • a method for reducing the hygroscopicity of PVA a method using an ethylene-vinyl alcohol copolymer having an ethylene unit content of 20 mol% or more (hereinafter, may be abbreviated as "EVOH" is adopted. ..
  • Patent Document 1 describes PVA containing 2 to 19 mol% of ethylene units, and the PVA is excellent in thermal stability, water resistance, gas barrier property, water vapor barrier property, low temperature standing stability of aqueous solution and biodegradability. It is described as. It is considered that by containing a relatively small amount of ethylene unit, the crystallinity is lowered while ensuring the water solubility, and as a result, the above-mentioned effect is obtained. However, as the ethylene content increases, the water solubility and viscosity stability deteriorate. Therefore, gelation was observed when the PVA was stored in winter or for a long period of time. Furthermore, the biodegradability of PVA correlates with water solubility, and PVA with a high ethylene content also has low biodegradability.
  • Patent Document 2 proposes a modified vinyl alcohol-based polymer obtained by copolymerizing vinyl acetate or ethylene with a predetermined comonomer and then saponifying the polymer. It is described that the modified vinyl alcohol polymer having a 1,3-diol structure in the main chain was excellent in water solubility and water resistance of the film, and was also excellent in thermoforming property. However, the polymer has insufficient melt moldability, oxygen gas barrier property, or water solubility, and it is difficult to satisfy all of them. Moreover, when used as a coating agent, the solid content concentration is high. In some cases it was difficult to increase.
  • Patent Document 3 describes a modified vinyl alcohol-based resin obtained by melt-kneading a modified vinyl alcohol-based polymer having a 1,2-diol structural unit in the side chain and a compound having a heterofunctional group such as ⁇ -caprolactone.
  • the resin is described as having excellent barrier properties, water solubility, and biodegradability.
  • the number of steps for producing the resin is increased, and the resin has insufficient barrier properties. Met.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide a modified vinyl alcohol-based polymer having excellent oxygen gas barrier properties, viscosity stability and biodegradability.
  • the above-mentioned problem is represented by the following formula (I), and the content a (mol%), b (mol%) and c (mol%) of each monomer unit with respect to all the monomer units is the following formula (1).
  • the solution is to provide a modified vinyl alcohol-based polymer that satisfies the above (3). 1 ⁇ a ⁇ 10 (1) 3 ⁇ c ⁇ 15 (2) [100- (a + c)] ⁇ 0.9 ⁇ b ⁇ [100- (a + c)] (3)
  • X, Y and Z each independently represent a hydrogen atom, a formyl group or an alkanoyl group having 2 to 10 carbon atoms.
  • the number average degree of polymerization of the modified vinyl alcohol polymer is preferably 200 to 5000.
  • a and c satisfy the following formula (4). a + 5c ⁇ 18 (4)
  • X, Y and Z are independently hydrogen atoms or acetyl groups.
  • the degree of saponification of the modified vinyl alcohol polymer is 80 to 99.99 mol%.
  • the above problem is also solved by providing a composition containing a modified vinyl alcohol-based polymer and sodium acetate in an amount of 0.01 to 2% by mass.
  • the modified vinyl alcohol polymer of the present invention is excellent in oxygen gas barrier property, viscosity stability and biodegradability.
  • the coating agent using the modified vinyl alcohol polymer is excellent in productivity at the time of coating, and the formed film maintains high oxygen gas barrier properties.
  • the modified vinyl alcohol polymer of the present invention is represented by the following formula (I).
  • X, Y and Z each independently represent a hydrogen atom, a formyl group or an alkanoyl group having 2 to 10 carbon atoms.
  • the modified vinyl alcohol polymer of the present invention contains an ethylene unit [unit shown at the left end of formula (I)].
  • the ethylene unit can impart a high oxygen gas barrier property to the polymer, and can impart a high oxygen gas barrier property particularly even under high humidity.
  • the modified vinyl alcohol-based polymer of the present invention is a monomer unit containing X in the side chain [unit shown in the center of formula (I)] (hereinafter, may be referred to as “monomer unit containing X”). Contains.
  • the monomer unit containing X can impart water solubility and oxygen gas barrier property to the polymer.
  • the modified vinyl alcohol-based polymer of the present invention is a monomer unit containing Y and Z in the side chain [unit shown at the right end of the formula (I)] (hereinafter, referred to as "monomer unit containing Y and Z". May contain).
  • monomer unit containing Y and Z the crystallinity of the polymer is lowered, so that the handleability such as water solubility, viscosity stability and melt moldability is improved.
  • the modified vinyl alcohol polymer of the present invention can maintain the oxygen gas barrier property, especially even under high humidity. Maintains high oxygen gas barrier properties.
  • the monomer unit containing Y and Z contains one quaternary carbon constituting the main chain of the modified vinyl alcohol polymer, so that the mobility is low, and Y and Y in the monomer unit It is considered that this is due to the high hydrogen bonding force derived from Z.
  • X, Y and Z each independently represent a hydrogen atom, a formyl group or an alkanoyl group having 2 to 10 carbon atoms.
  • the formula (I) has a hydroxyl group
  • X, Y or Z is a formyl group or an alkanoyl group
  • the formula (I) has an ester group. ..
  • the alkanoyl group an alkanoyl group having 2 to 5 carbon atoms is preferable, and an acetyl group, a propanoyl group, a butanoyl group and the like are exemplified as suitable ones. Of these, the acetyl group is particularly suitable. It is preferable that X, Y and Z are all hydrogen atoms or contain hydrogen atoms.
  • the monomer unit containing X is usually obtained by saponifying the vinyl ester unit in the polymer. It is preferable that the modified vinyl alcohol polymer contains a vinyl alcohol unit in which X is a hydrogen atom as the monomer unit containing X. Further, it is also preferable that the modified vinyl alcohol polymer contains a vinyl ester unit in which X is a formyl group or an alkanoyl group having 2 to 10 carbon atoms as the monomer unit containing X. Further, as the monomer unit in which the modified vinyl alcohol polymer contains X, both a vinyl alcohol unit in which X is a hydrogen atom and a vinyl ester unit in which X is a formyl group or an alkanoyl group having 2 to 10 carbon atoms are used. It is more preferable to include it.
  • the vinyl acetate unit is preferable as the vinyl ester unit in consideration of the availability of the monomer and the production cost.
  • a weight containing both a vinyl alcohol unit in which X is a hydrogen atom and a vinyl acetate unit in which X is an acetyl group is used as a monomer unit containing X. You can get coalescence.
  • the content of the vinyl alcohol unit in the modified vinyl alcohol polymer is preferably 80 to 99.99 mol% with respect to the total amount of the monomer unit containing X.
  • the content is more preferably 90 mol% or more, still more preferably 95 mol% or more.
  • the content is more preferably 99.95 mol% or less, further preferably 99.90 mol% or less.
  • the content of the vinyl ester unit in the modified vinyl alcohol polymer is preferably 0.01 to 20 mol% with respect to the total amount of the monomer unit containing X.
  • the content is more preferably 0.05 mol% or more, still more preferably 0.10 mol% or more.
  • the content is more preferably 10 mol% or less, further preferably 5 mol% or less.
  • the monomer unit containing Y and Z can also be produced by copolymerizing an unsaturated monomer having a 1,3-diester structure and then saponifying it, or an unsaturated monomer having a 1,3-diol structure. It can also be produced by copolymerizing the weights. It is preferable that the modified vinyl alcohol-based polymer contains a unit of a hydrogen atom in Y and Z as a monomer unit containing Y and Z. As the monomer unit containing Y and Z, the modified vinyl alcohol polymer preferably contains a unit in which Y is a hydrogen atom and Z is a formyl group or an alkanoyl group having 2 to 10 carbon atoms.
  • the modified vinyl alcohol polymer contains a unit in which Y and Z are a formyl group or an alkanoyl group having 2 to 10 carbon atoms as the monomer unit containing Y and Z.
  • Y and Z are hydrogen atom units
  • Y is a hydrogen atom
  • Z is a formyl group or an alkanoyl group having 2 to 10 carbon atoms. It is more preferable to include all the units in which Y and Z are a formyl group or an alkanoyl group having 2 to 10 carbon atoms.
  • a monomer unit containing Y and Z is obtained through saponification, for example, when a polymer having 1,3-diacetoxy-2-methylenepropane (DAMP) units is partially saponified, a monomer containing Y and Z is obtained.
  • DAMP 1,3-diacetoxy-2-methylenepropane
  • a monomer containing Y and Z is obtained.
  • a polymer containing a unit in which Y and Z are hydrogen atoms, a unit in which Y is a hydrogen atom and Z is an acetyl group, and a unit in which Y and Z are acetyl groups can be obtained.
  • the content of the hydrogen atom among Y and Z in the modified vinyl alcohol polymer with respect to the total amount of Y and Z is preferably 80 to 99.99 mol%.
  • the content is more preferably 90 mol% or more, still more preferably 95 mol% or more.
  • the content is more preferably 99.95 mol% or less, further preferably 99.90 mol% or less.
  • the total content of Y and Z having a formyl group and an alkanoyl group having 2 to 10 carbon atoms is 0.01 to 20 mol% with respect to the total amount of Y and Z. Is preferable.
  • the content is more preferably 0.05 mol% or more, still more preferably 0.10 mol% or more.
  • the content is more preferably 10 mol% or less, further preferably 5 mol% or less.
  • each monomer unit represented by the formula (I) is not particularly limited, and the modified vinyl alcohol-based polymer of the present invention may be a random copolymer or a block copolymer. , A graft copolymer may be used, but a random copolymer is preferable from the viewpoint of easy production.
  • the contents a (mol%), b (mol%) and c (mol%) of each monomer unit with respect to all the monomer units in the modified vinyl alcohol polymer are the following formulas (1) to It is necessary to satisfy (3).
  • a in the above formulas (1) and (3) is the content of ethylene units (mol%) with respect to all the monomer units.
  • the content rate a is 1 mol% or more and less than 10 mol%.
  • the content a is preferably 2 mol% or more, more preferably 3 mol% or more, further preferably 4 mol% or more, particularly preferably 5 mol% or more, and most preferably. 6 mol% or more.
  • the content a is preferably 9.9 mol% or less, more preferably 9.7 mol% or less, and particularly preferably 9.5 mol% or less.
  • the contents a, b and c can be determined by a nuclear magnetic resonance (NMR) method.
  • C in the above formulas (2) and (3) is the content ratio (mol%) of the monomer units including Y and Z with respect to all the monomer units.
  • the content c is 3 to 15 mol%.
  • the content c is 3 mol% or more, the water solubility and biodegradability of the modified vinyl alcohol polymer are enhanced.
  • the viscosity stability of the aqueous solution containing the modified vinyl alcohol polymer is improved, and the aqueous solution is less likely to foam.
  • the modified vinyl alcohol polymer can be melt-molded at a low temperature, it is easy to suppress decomposition during thermoforming. Furthermore, the strength of the obtained film under high humidity is improved.
  • the content c is preferably 3.2 mol% or more, more preferably 3.5 mol% or more, still more preferably 3.7 mol% or more, and particularly preferably 4 mol%.
  • the above is the most preferably 4.2 mol% or more.
  • the content c exceeds 15 mol%, the polymerization rate is remarkably lowered, and it tends to be difficult to synthesize industrially.
  • the content c is preferably 12 mol% or less, and more preferably 10 mol% or less.
  • b is the content rate (mol%) of the monomer unit containing X with respect to all the monomer units. That is, according to the above formula (3), in the modified vinyl alcohol polymer of the present invention, 90 mol% or more of the monomer units other than the ethylene unit and the monomer unit containing Y and Z is X. It becomes a monomer unit containing. Examples of the monomer unit containing X include a vinyl alcohol unit and a vinyl ester unit. If the formula (3) is not satisfied, the water solubility and the oxygen gas barrier property become insufficient. The following formula (3') is more preferably satisfied, and the following formula (3 ") is more preferably satisfied.
  • a and c satisfy the following formula (4). This further enhances the melt moldability of the modified vinyl alcohol polymer. This is because when the formula (4) is satisfied, the melting point of the modified vinyl alcohol-based copolymer is sufficiently lowered, and melt molding becomes possible at a lower temperature.
  • the number average degree of polymerization of the modified vinyl alcohol polymer of the present invention is preferably 200 to 5000.
  • the number average degree of polymerization is more preferably 300 or more, still more preferably 350 or more.
  • the number average degree of polymerization is 5000 or less, the viscosity of the solution of the modified vinyl alcohol-based polymer does not become too high, so that the handleability is improved.
  • the number average degree of polymerization is more preferably 4000 or less, still more preferably 3000 or less.
  • the number average degree of polymerization is measured by gel permeation chromatography (GPC).
  • the number average degree of polymerization can be obtained by the method described in Examples. At this time, measurement is carried out at 40 ° C. using monodisperse polymethylmethacrylate (PMMA) as a standard and hexafluoroisopropanol (HFIP) containing 20 mmol / liter sodium trifluoroacetate as a mobile phase.
  • PMMA monodisperse polymethylmethacrylate
  • HFIP hexafluoroisopropanol
  • the number average degree of polymerization can be adjusted, for example, by adjusting the amount of solvent in the case of producing a polymer by radical polymerization or the addition of a chain transfer agent.
  • the saponification degree of the modified vinyl alcohol polymer of the present invention is not particularly limited, but is preferably 80 to 99.99 mol%. If the degree of saponification is less than 80 mol%, sufficient oxygen gas barrier property may not be obtained.
  • the degree of saponification is more preferably 90 mol% or more, further preferably 95 mol% or more. On the other hand, those having a saponification degree of more than 99.99 mol% may be difficult to obtain industrially.
  • the degree of saponification is more preferably 99.95 mol% or less, further preferably 99.90 mol% or less.
  • the saponification degree is defined by the DS represented by the following formula (5), and specifically, it is calculated from the measurement result of NMR.
  • the method for producing the modified vinyl alcohol polymer of the present invention is not particularly limited.
  • ethylene, a vinyl ester represented by the following formula (II), and a modified ethylene-vinyl ester copolymer represented by the following formula (IV) by radically polymerizing an unsaturated monomer represented by the following formula (III). After obtaining it, there is a method of quenching it.
  • the bonding format of each monomer unit in the modified ethylene-vinyl ester copolymer represented by the following formula (IV) is not particularly limited, and the copolymer may be a random copolymer or a block copolymer. It may be a graft copolymer or a graft copolymer, but it is preferably a random copolymer from the viewpoint of easy production.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.
  • the alkyl group preferably has 1 to 4 carbon atoms.
  • Examples of the vinyl ester represented by the formula (II) include vinyl formic acid, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatic acid, vinyl caproate and the like. Vinyl acetate is particularly preferred from an economic point of view.
  • R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.
  • the alkyl group preferably has 1 to 4 carbon atoms.
  • Examples of the unsaturated monomer represented by the formula (III) include 1,3-diacetoxy-2-methylenepropane (DAMP), 1,3-dipropionyloxy-2-methylenepropane, and 1,3-dibutyronyloxy. -2-Methylenepropane and the like. Of these, 1,3-diacetoxy-2-methylenepropane (DAMP) is preferably used because it is easy to produce.
  • DAMP 1,3-diacetoxy-2-methylenepropane
  • R 1 , R 2 and R 3 are the same as in formulas (II) and (III).
  • a represents the content of ethylene units (mol%)
  • b represents the content of vinyl ester-derived units represented by formula (II) (mol%)
  • c represents the content of formula (III). The content rate (mol%) of the unit derived from the unsaturated monomer represented by is shown.
  • the polymerization method for producing the above may be any of batch polymerization, semi-batch polymerization, continuous polymerization and semi-continuous polymerization. Further, as the polymerization method, known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be adopted. A bulk polymerization method or a solution polymerization method in which the polymerization proceeds in a solvent such as no solvent or alcohol is usually adopted. When obtaining a modified ethylene-vinyl ester copolymer having a high degree of polymerization, the adoption of an emulsion polymerization method is one of the options.
  • the solvent used in the solution polymerization method is not particularly limited, but alcohol is preferably used, and for example, lower alcohols such as methanol, ethanol and propanol are more preferably used.
  • the amount of the solvent used in the polymerization reaction solution may be selected in consideration of the viscosity average degree of polymerization of the target modified vinyl alcohol-based polymer and the chain transfer of the solvent, and the solvent contained in the reaction solution and all the monomers may be selected.
  • the mass ratio with and (solvent / total monomer) is selected from the range of 0.01 to 10, preferably the range of 0.05 to 3.
  • the polymerization initiator used when copolymerizing ethylene, the vinyl ester represented by the above formula (II), and the unsaturated monomer represented by the above formula (III) is a known polymerization initiator, for example. It is selected from an azo-based initiator, a peroxide-based initiator, and a redox-based initiator according to the polymerization method.
  • the azo-based initiator include 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), and 2,2-azobis (4-methoxy-2,4-dimethylvalero). Nitrile).
  • peroxide-based initiator examples include percarbonate-based compounds such as diisopropylperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethylperoxydicarbonate; t-butylperoxyneodecanate, ⁇ . -Perester compounds such as cumylperoxyneodecanete and acetyl peroxide; acetylcyclohexylsulfonyl peroxides; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate and the like.
  • percarbonate-based compounds such as diisopropylperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethylperoxydicarbonate
  • t-butylperoxyneodecanate ⁇ .
  • -Perester compounds such as cumylperoxyneodecanete and ace
  • Potassium persulfate, ammonium persulfate, hydrogen peroxide and the like may be used in combination with the above initiator.
  • the redox-based initiator is, for example, a polymerization initiator in which the above-mentioned peroxide-based initiator is combined with a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, and longalit.
  • the amount of the polymerization initiator used varies depending on the polymerization catalyst and cannot be unconditionally determined, but is adjusted according to the polymerization rate.
  • the amount of the polymerization initiator used is preferably 0.01 to 0.2 mol%, more preferably 0.02 to 0.15 mol% with respect to the vinyl ester represented by the above formula (II).
  • the polymerization temperature is not particularly limited, but is appropriately about room temperature to about 150 ° C., preferably 40 ° C. or higher and lower than the boiling point of the solvent used.
  • the chain is long as long as the effect of the present invention is not impaired.
  • Copolymerization may be carried out in the presence of a transfer agent.
  • the chain transfer agent include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; and phosphinates such as sodium phosphinate monohydrate. .. Of these, aldehydes and ketones are preferably used.
  • the amount of the chain transfer agent added to the polymerization reaction solution is determined according to the chain transfer coefficient of the chain transfer agent and the degree of polymerization of the target modified ethylene-vinyl ester copolymer, but is generally determined by the above formula (II). 0.1 to 10 parts by mass is preferable with respect to 100 parts by mass of the indicated vinyl ester.
  • the modified ethylene-vinyl ester copolymer thus obtained can be saponified to obtain the modified vinyl alcohol-based polymer of the present invention.
  • the vinyl ester unit derived from the vinyl ester represented by the formula (II) in the copolymer is converted into a vinyl alcohol unit.
  • the ester bond derived from the unsaturated monomer represented by the formula (III) is also hydrolyzed at the same time and converted into a 1,3-diol structure. In this way, different types of ester groups can be simultaneously hydrolyzed by a single saponification reaction.
  • the saponification reaction is usually carried out in a solution of alcohol or hydrous alcohol.
  • the alcohol preferably used at this time is a lower alcohol such as methanol or ethanol, and particularly preferably methanol.
  • the alcohol or hydrous alcohol used in the saponification reaction may contain other solvents such as acetone, methyl acetate, ethyl acetate and benzene as long as it is 40% by mass or less by mass.
  • the catalyst used for saponification is, for example, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an alkali catalyst such as sodium methylate, or an acid catalyst such as mineral acid.
  • the temperature at which saponification is carried out is not limited, but is preferably in the range of 20 to 120 ° C.
  • the product can be pulverized, washed and dried to obtain a modified vinyl alcohol-based polymer.
  • the modified vinyl alcohol-based polymer of the present invention contains ethylene, a vinyl ester represented by the above formula (II), and an unsaturated monomer represented by the above formula (III) as long as the effects of the present invention are not impaired. It may contain structural units derived from other ethylenically unsaturated monomers that are copolymerizable with. Examples of such ethylenically unsaturated monomers include ⁇ -olefins such as propylene, n-butene, isobutylene, and 1-hexene; allylic acid and salts thereof; unsaturated monomers having an allylic acid ester group.
  • Methacrylic acid and its salts Unsaturated monomers having a methacrylic ester group; acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamide propanesulfonic acid and its salts, Acrylamidepropyldimethylamine and its salts (eg, quaternary salts); methacrylamide, N-methylmethacrylate, N-ethylmethacrylate, methallylamide propanesulfonic acid and its salts, methacrylamidepropyldimethylamine and its salts (eg, quaternary).
  • the modified vinyl alcohol polymer of the present invention may have a carboxyl group, a sulfonic acid group, an amino group or a salt thereof at the side chain or the molecular terminal as long as the performance of the present invention is not impaired.
  • the modification amount is usually 0.05 to 10 mol% with respect to all the monomer units of the modified vinyl alcohol-based polymer of the present invention.
  • the modified vinyl alcohol-based polymer of the present invention may be used alone, but it can also be used as a composition by blending other copolymers and additives.
  • copolymers include polyvinyl alcohol and ethylene-vinyl alcohol copolymers that do not contain monomer units containing Y and Z.
  • additives include inorganic salts, organic salts, cross-linking agents, solvents, ultraviolet absorbers, antioxidants, antistatic agents, plasticizers, fungicides, preservatives and the like. Two or more of these may be used in combination.
  • the composition examples include a composition containing the modified vinyl alcohol-based polymer of the present invention and sodium acetate.
  • the content of sodium acetate in the composition at this time is preferably 0.01 to 2% by mass, more preferably 0.02 to 1% by mass, still more preferably 0.03 to 0.5% by mass. Most preferably, it is 0.35 to 0.45% by mass. When the content is in such a range, the oxygen gas barrier property is further improved.
  • the modified vinyl alcohol-based polymer of the present invention and sodium acetate may be mixed to form a composition, or the sodium acetate produced in the saponification step during the production of the modified vinyl alcohol-based polymer of the present invention may be left and used. ..
  • the composition examples include a composition containing the modified vinyl alcohol-based polymer of the present invention and a known cross-linking agent. Water resistance can be imparted to the composition by including a cross-linking agent.
  • the cross-linking agent include epoxy compounds, isocyanate compounds, aldehyde compounds, silica compounds, aluminum compounds, boron compounds, zirconium compounds and the like, and colloidal silica, silica compounds such as alkyl silicates and zirconium compounds are preferably used.
  • the content of the cross-linking agent in the composition is not particularly limited as long as it does not impair the characteristics of the present invention, but is usually 1 to 60 parts by mass with respect to 100 parts by mass of the modified polyvinyl alcohol-based polymer. If the content of the cross-linking agent exceeds 60 parts by mass, the oxygen gas barrier property may be adversely affected.
  • the cross-linking agent may coexist with the above-mentioned sodium acetate.
  • the content of the modified vinyl alcohol polymer in the composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more.
  • composition is a coating agent.
  • the coating agent is a coating agent containing the modified vinyl alcohol-based polymer and the solvent of the present invention, wherein the solvent comprises at least one of water or an aliphatic alcohol having 1 to 4 carbon atoms.
  • the concentration of the modified vinyl alcohol polymer in the coating agent is not particularly limited, but is preferably 5 to 50% by mass. If the concentration is less than 5% by mass, the drying load may increase. The concentration is more preferably 8% by mass or more, further preferably 10% by mass or more. On the other hand, when the concentration exceeds 50% by mass, the viscosity becomes too high and the handleability may become a problem.
  • the aliphatic alcohol is not particularly limited as long as it is water-soluble, but methanol, ethanol, isopropyl alcohol, n-propyl alcohol and the like are preferably used.
  • the solvent used for the coating agent is water or a mixed solution of water and the fatty alcohol.
  • the upper limit of the ratio of the aliphatic alcohol to the total solvent in the coating agent is preferably 50% by mass, more preferably 40% by mass, still more preferably 20% by mass, and particularly. It is preferably 10% by mass.
  • the lower limit of the content is not particularly limited, but is preferably 0.5% by mass, more preferably 1% by mass, still more preferably 2% by mass. Is.
  • the coating agent may contain additives other than the modified vinyl alcohol polymer and the solvent.
  • additives include surfactants, leveling agents and the like.
  • the content of the modified vinyl alcohol polymer and the components other than the solvent in the coating agent is usually 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less.
  • the temperature of the coating agent at the time of coating is preferably 20 ° C to 80 ° C.
  • known methods such as a gravure roll coating method, a reverse gravure coating method, a reverse roll coating method, and a Meyer bar coating method are preferably used.
  • a modified vinyl alcohol-based polymer aqueous solution having a concentration of 10% by mass was prepared, and the mixture was filtered and centrifuged to remove foreign substances and bubbles.
  • the surface of the base material PET film having a thickness of 12 ⁇ m is coated with the modified vinyl alcohol-based polymer aqueous solution obtained above at room temperature, and dried with a hot air dryer at 60 ° C. to obtain the base material PET.
  • a multilayer film composed of a film (12 ⁇ m) and a modified vinyl alcohol-based polymer layer (about 20 ⁇ m) was obtained. The obtained multilayer film was conditioned for 5 days at a temperature of 20 ° C.
  • oxygen permeation of the multilayer film was permeated using an oxygen gas permeation measuring device OX-TRAN 2/21 (manufactured by Mocon).
  • OX-TRAN 2/21 manufactured by Mocon.
  • the value A [cc / (m 2 ⁇ day ⁇ atm)] was measured as the amount (OTR).
  • the film thickness of the multilayer film after the measurement was measured using an electromagnetic film thickness meter SAMAC-PR Why the obtained thickness was defined as T ( ⁇ m).
  • the value B [cc /) is used as the oxygen permeation amount (OTR) of the modified vinyl alcohol polymer layer when the thickness of the modified vinyl alcohol polymer layer is 20 ⁇ m. ( M2 ⁇ day ⁇ atm)] was obtained.
  • OTR oxygen permeation amount
  • Biodegradability Using a powder of a modified vinyl alcohol-based polymer having a uniform particle size by pulverization and classification (using a sieve with an opening of 300 ⁇ m), it conforms to the biodegradability test method described in ISO14851 and is biodegradable. Was evaluated. The test conditions are shown below. The biodegradation rate (% by mass) was calculated based on the theoretical oxygen demand calculated from the polymer composition. It can be said that the larger the value of the biodegradability, the higher the biodegradability.
  • a modified vinyl alcohol-based polymer aqueous solution having a concentration of 10% by mass is prepared, cast on a PET film, dried at 20 ° C. for 1 week, further dried in a vacuum dryer for 16 hours, and peeled off from the PET film.
  • a single-layer film having a thickness of 100 ⁇ m was obtained.
  • 100 mL of ion-exchanged water was added to a 100 mL beaker and the temperature was controlled to 60 ° C.
  • the elution rate of the modified vinyl alcohol polymer in water after immersing the film (size: 30 mm ⁇ 40 mm, thickness 100 ⁇ m) in the ion-exchanged water for 1 hour without stirring was measured and evaluated in the following three stages. .. It can be said that A has the highest water solubility.
  • C The elution rate was less than 30%.
  • Example 1 Manufacturing of modified vinyl alcohol polymer
  • 1.2 kg of vinyl acetate, 1.4 kg of methanol and 1,3-diacetoxy-2-methylenepropane in a 5 L pressurized reaction vessel equipped with a stirrer, nitrogen inlet, ethylene inlet, initiator addition port and solution feed port ( 0.049 kg of DAMP) was charged, the temperature was raised to 60 ° C., and then nitrogen was substituted in the system by nitrogen bubbling for 30 minutes.
  • ethylene was introduced into the pressurized reaction vessel so that the reaction vessel pressure was 0.3 MPa.
  • 120 mL of the above-mentioned initiator solution was injected to initiate polymerization.
  • the polymerization temperature was maintained at 60 ° C., and a methanol solution of DAMP was fed to carry out the polymerization.
  • the mixture was cooled to terminate the polymerization.
  • the total feed amount of the methanol solution of DAMP (concentration 42 g / L) until the polymerization was stopped was 860 mL.
  • modified PVAc modified ethylene-vinyl acetate copolymer
  • a mixed solvent of 900 g of methanol and 100 g of water was added to the saponified product of a white solid obtained by filtration, and the mixture was allowed to stand at room temperature for 3 hours for washing. After repeating the above washing operation three times, the saponified product obtained by centrifugal deflation was left in a dryer at 70 ° C. for 2 days to obtain a dried modified vinyl alcohol polymer.
  • the average degree of polymerization Pn is 420, the degree of saponification is 99.0 mol%, the content a of ethylene units is 3.2 mol%, and units derived from DAMP (including Y and Z).
  • the content c of the monomer unit) was 6.5 mol%, and the content of sodium acetate was 0.028% by mass.
  • the total content b of the vinyl acetate unit (monomer unit containing X) and the vinyl alcohol unit (monomer unit containing X) was 90.3 mol%.
  • the oxygen gas barrier property, biodegradability, water solubility, viscosity stability of the aqueous solution, and melt moldability of the modified vinyl alcohol polymer were evaluated. The results are shown in Table 2.
  • Table 1 shows the polymerization conditions such as the amount of vinyl acetate and methanol charged, the ethylene pressure during polymerization, the amount of comonomer added during polymerization, and the molar ratio of sodium hydroxide to vinyl acetate units during saponification.
  • Various modified vinyl alcohol-based polymers were produced by the same method as in Example 1 except that the polymer was changed to.
  • the content a of the ethylene unit is in the range of 1 to less than 10 mol%, and the content of the content c of the monomer unit (unit derived from DAMP) containing Y and Z is in the range of 3 to 15 mol%.
  • the modified vinyl alcohol-based polymers of the present invention (Examples 1 to 6) had high water solubility and viscosity stability, and the obtained film showed excellent oxygen gas barrier properties and biodegradability. Further, the modified vinyl alcohol-based polymer can be melt-molded at a low temperature, and there is no problem of decomposition.
  • unmodified polyvinyl alcohol (Comparative Example 1) has a low oxygen gas barrier property and a high temperature at which melt molding is possible, resulting in decomposition. Furthermore, the aqueous solution containing unmodified polyvinyl alcohol also had low viscosity stability.
  • the ethylene-vinyl alcohol copolymer (Comparative Example 2) having an ethylene unit content a of 9.1 mol% and not containing a monomer unit containing Y and Z (a unit derived from DAMP) is a water-soluble film. Although the properties were deteriorated as compared with Comparative Example 1, the oxygen gas barrier property and the melt moldability were improved as compared with Comparative Example 1.
  • the modified vinyl alcohol-based polymer (Comparative Example 3), which does not contain ethylene units and contains monomer units (units derived from DAMP) containing Y and Z but is less than 3 mol%, has a low oxygen gas barrier property. .. In addition, the temperature at which melt molding was possible was high, and decomposition occurred. In addition, although the water solubility was not low, the viscosity stability of the aqueous solution was low, and thickening was observed when stored at a low temperature.
  • the content c of the unit derived from DAMP is in the range of 3 to 15 mol%, but the modified vinyl alcohol-based polymer (Comparative Example 5) having the content a of the ethylene unit of 10 mol% or more has an oxygen gas barrier property.
  • the biodegradability was low.
  • a modified vinyl alcohol-based copolymer (Comparative Example 6) containing no ethylene unit and having a DAMP-derived unit (c) content of 10 mol% or more is used, the oxygen gas barrier property is extremely poor and the viscosity is extremely poor. It was difficult to achieve both stability and biodegradability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne un polymère à base d'alcool vinylique modifié qui est représenté par la formule (I) et dans lequel les teneurs a (% en moles), b (% en moles) et c (% en moles) des différents motifs monomères par rapport à tous les motifs monomères satisfont les expressions (1) à (3). Ce polymère à base d'alcool vinylique modifié présente d'excellentes propriétés de barrière contre l'oxygène gazeux, de stabilité de sa viscosité et de biodégradabilité.　(1) : 1 ≤ a ≤ 10 ; (2) : 3 ≤ c ≤ 15 ; (3) : [100 - (a + c)] × 0,9 ≤ b ≤ [100 - (a + c)]. Dans la formule (I), X, Y et Z représentent chacun indépendamment un atome d'hydrogène, un groupe formyle ou un groupe alcanoyle comportant de 2 à 10 atomes de carbone.]
PCT/JP2021/040762 2020-11-06 2021-11-05 Polymère à base d'alcool vinylique modifié Ceased WO2022097718A1 (fr)

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WO2026071156A1 (fr) * 2024-09-27 2026-04-02 株式会社クラレ Structure multicouche et utilisation de celle-ci

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JP2015034263A (ja) * 2013-08-09 2015-02-19 株式会社クラレ 水性エマルジョン組成物及び乳化重合用安定剤
JP2015034262A (ja) * 2013-08-09 2015-02-19 株式会社クラレ 変性ビニルアルコール系重合体
JP2015151428A (ja) * 2014-02-12 2015-08-24 株式会社クラレ 樹脂組成物及びその製造方法
US20200207052A1 (en) * 2018-12-26 2020-07-02 Kuraray Co., Ltd. Multilayer article suitable for use as a fuel container
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JP2007023286A (ja) * 2005-07-19 2007-02-01 Cryovac Inc ガスバリア性樹脂組成物
JP2015034263A (ja) * 2013-08-09 2015-02-19 株式会社クラレ 水性エマルジョン組成物及び乳化重合用安定剤
JP2015034262A (ja) * 2013-08-09 2015-02-19 株式会社クラレ 変性ビニルアルコール系重合体
JP2015151428A (ja) * 2014-02-12 2015-08-24 株式会社クラレ 樹脂組成物及びその製造方法
US20200207052A1 (en) * 2018-12-26 2020-07-02 Kuraray Co., Ltd. Multilayer article suitable for use as a fuel container
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WO2025009506A1 (fr) * 2023-07-04 2025-01-09 株式会社クラレ Corps moulé, film, matériau de masquage, matériau de revêtement par transfert soluble dans l'eau pour la formation d'une couche de matériau de revêtement présentant une structure irrégulière, matériau de support pour moulage, et procédé d'utilisation du corps moulé
WO2025009505A1 (fr) * 2023-07-04 2025-01-09 株式会社クラレ Polymère d'alcool polyvinylique modifié, film hydrosoluble, fibre hydrosoluble et matériau d'emballage barrière

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