WO2008059763A1 - Procédé de fabrication d'un copolymère monoxyde de carbone-alcool vinylique, copolymère monoxyde de carbone-alcool vinylique, et composition résistante à l'eau utilisant le copolymère - Google Patents

Procédé de fabrication d'un copolymère monoxyde de carbone-alcool vinylique, copolymère monoxyde de carbone-alcool vinylique, et composition résistante à l'eau utilisant le copolymère Download PDF

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Publication number
WO2008059763A1
WO2008059763A1 PCT/JP2007/071794 JP2007071794W WO2008059763A1 WO 2008059763 A1 WO2008059763 A1 WO 2008059763A1 JP 2007071794 W JP2007071794 W JP 2007071794W WO 2008059763 A1 WO2008059763 A1 WO 2008059763A1
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Prior art keywords
carbon monoxide
water
copolymer
viscosity
alcohol copolymer
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PCT/JP2007/071794
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English (en)
Japanese (ja)
Inventor
Shinsuke Nii
Takeshi Kusudou
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Kuraray Co., Ltd.
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Priority to JP2008544120A priority Critical patent/JP5009302B2/ja
Publication of WO2008059763A1 publication Critical patent/WO2008059763A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds

Definitions

  • the present invention relates to a method for producing a carbon monoxide / bull alcohol-based copolymer containing a unit based on carbon monoxide and a bull alcohol unit, and a carbon monoxide / bull alcohol-based copolymer and water resistance using the same.
  • the present invention relates to a sex composition.
  • a method for producing a carbon monoxide / bulule alcohol copolymer which saponifies a carbon monoxide / bulule ester copolymer obtained by copolymerization of carbon monoxide and a bullet ester monomer
  • the present invention relates to a carbon monoxide butyl alcohol copolymer obtained by saponifying the carbon monoxide bulle ester copolymer, and a water-resistant composition using the same.
  • a method is known in which PVA is crosslinked with darioxar, gnoretanolenodehydride, dialdehyde starch, a water-soluble epoxy compound, a methylol compound, or the like.
  • long-term heat treatment at a high temperature of 100 ° C or higher, particularly 120 ° C or higher is necessary to sufficiently make PVA water resistant by this method.
  • a method of making an aqueous composition of strong acidity for example, pH 2 or less
  • the viscosity stability of the aqueous composition is improved.
  • a method in which a diacetone group-containing PVA in which a carbonyl group is introduced into a side chain is crosslinked with a hydrazine or a hydrazide compound by utilizing the reactivity between a carbonyl group and a hydrazine compound.
  • the obtained modified PVA exhibits excellent water resistance without special treatment such as heat treatment or addition of strong acid.
  • hydrazine compounds used for crosslinking are superior in safety compared to other crosslinking agents such as aldehydes and isocyanates.
  • oxidized PVA synthesized by oxidation of PVA is a modified PVA having a carbonyl group in the main chain and having high! / Water resistance by reaction with hydrazine or a hydrazide compound. And force S.
  • Oxidized PVA also has a carbonyl group in the main chain, so the reaction with hydrazine or hydrazide compounds proceeds more slowly than PVA with a carbonyl group in the side chain, resulting in an aqueous composition.
  • the viscosity rises slowly and force, making handling easier.
  • problems such as the oxidant residue used in the synthesis of oxidized PVA adversely affecting the physical properties of PVA, and so far this method has not been put to practical use.
  • One of the objects of the present invention is a carbon monoxide butyl alcohol copolymer (CO-modified PVA) having a carbonyl group in the main chain, which has good water solubility and has an aqueous composition.
  • the present invention is to provide a novel CO-modified PVA that has excellent viscosity stability when made into a product and a method for producing the same.
  • Another object of the present invention is to provide a novel water-resistant composition containing CO-modified PVA that is excellent in viscosity stability as an aqueous composition and excellent in water resistance of a formed film. It is in.
  • a method for producing a CO-modified PVA of the present invention is a method for producing a carbon monoxide-bule alcohol copolymer comprising a unit based on carbon monoxide and a bull alcohol unit. Copolymerization with an ester monomer is carried out in an atmosphere containing carbon monoxide, without solvent, or in an alcohol solvent, and the carbon monoxide bull ester copolymer obtained by the copolymerization is obtained. This is a method in which saponification is performed to obtain a carbon monoxide butyl alcohol copolymer.
  • the CO-modified PVA of the present invention is a carbon monoxide / bull alcohol-based copolymer containing a unit based on carbon monoxide and a bull alcohol unit, and a unit content based on carbon monoxide (CO (Modified amount) is 0.0;! To 8 mol%, saponification degree is 60 to 99.99 mol%, and the viscosity when an aqueous solution with a concentration of 4 wt% is 2.0 to 150. OmPa's It is.
  • the water-resistant composition of the present invention includes a carbon monoxide / bull alcohol-based copolymer containing carbon monoxide-based units and a bull alcohol unit, and a polyfunctional hydrazide compound having two or more hydrazide groups in the molecule.
  • the content of the unit based on carbon monoxide (CO modification amount) is 0.;! To 8 mol%, and the degree of saponification is The viscosity is 85 to 99.99 mol%, and the viscosity of the aqueous solution having a concentration of 4% by weight is 2.0 to 150.OmPa's.
  • the composition has good water solubility and has a stable viscosity when an aqueous composition is obtained.
  • CO-modified PVA with excellent properties can be manufactured.
  • CO-modified PVA exhibiting high water resistance and high water resistance can be produced by reaction with a crosslinking agent.
  • the CO-modified PVA of the present invention has good water solubility, and is excellent in viscosity stability when it is used as an aqueous composition.
  • the reaction with the crosslinking agent CO-modified PVA showing high water resistance can be obtained.
  • Copolymerization of carbon monoxide (CO) and butyl ester monomer is carried out without solvent in an atmosphere containing carbon monoxide, or in an alcohol solvent in an atmosphere containing carbon monoxide. To do.
  • the copolymerization is preferably carried out at a CO partial pressure of 0.0;! To 8 MPa.
  • the partial pressure of CO is less than 0. OlMPa, the desired properties may not be obtained because the amount of CO modification in the obtained CO-modified PVA becomes too small.
  • the partial pressure of CO exceeds 8 MPa, the amount of CO modification in the obtained CO-denatured PVA exceeds 8 mol%, and its water solubility decreases. That is, by setting the partial pressure of CO during copolymerization within the above range, it is possible to more reliably obtain a CO modified PVA with good water solubility.
  • the copolymerization is preferably performed in a CO atmosphere.
  • CO is performed in a pressurized atmosphere (CO pressure is 0. IMPa or more, provided that the upper limit of CO pressure is preferably 8 MPa). It is particularly preferable.
  • CO-based units CO units can be introduced more efficiently, and a carbon monoxide bule ester copolymer can be more reliably formed.
  • the copolymerization method is not particularly limited as long as it can be carried out without a solvent or in an alcohol solvent.
  • any polymerization such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used.
  • the method can be used.
  • a solvent-free bulk polymerization method and a solution polymerization method using an alcohol solvent can be suitably employed.
  • an emulsion polymerization method may be employed.
  • the method of copolymerization is not particularly limited, and examples thereof include batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization.
  • the alcohol solvent is not particularly limited.
  • methanol, ethanol, propyl alcohol, and the like can be used alone or in admixture of two or more.
  • methanol is particularly preferable. That is, it is preferable to carry out the copolymerization in methanol!
  • the temperature for carrying out the copolymerization is preferably 0 to 200 ° C, more preferably 30 to 140 ° C.
  • the temperature force is lower than SO ° C, a sufficient polymerization rate may not be obtained.
  • the temperature is higher than 200 ° C., the amount of CO dissolved in the solvent decreases, and a CO-modified PVA having the desired CO-modified amount cannot be obtained! /.
  • the method for controlling the temperature at which the copolymerization is carried out is not particularly limited. For example, by controlling the polymerization rate, a method for balancing the heat generated by the polymerization with the heat release from the surface of the polymerization reactor, And a method of controlling by an external jacket using an appropriate heating medium. The latter method is preferable from the viewpoint of safety.
  • the polymerization initiator used for the copolymerization may be appropriately selected from known initiators such as azo initiators, peroxide initiators, and reddot initiators, depending on the polymerization method.
  • azo initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4 dimethylvaleronitrile), 2,2 'azobis (4 methoxy-1,2,4). Dimethyl valeronitrile).
  • peroxide-based initiators include percarbonate compounds such as diisopropinoreperoxydicarbonate, di-2-ethylhexyloleperoxydicarbonate, diethoxyethylberoxydicarbonate; Perester compounds such as oxyneodecanate, a cuminoleperoxyneodecanate, t-butyl baroxide, etc .; acetyl cyclohexylsulfonyl peroxide; 2, 4, 4 trimethylpentyl-2-peroxyphenoxyacetate Etc. These initiators can be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like to form an initiator.
  • the redox initiator examples include an initiator in which the above-described peroxide is combined with a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-scorbic acid, or longalite. CO and vinyl
  • a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-scorbic acid, or longalite.
  • CO and vinyl When the copolymerization with the ester ester monomer is carried out at a high temperature, the PVA may be colored due to decomposition of the butyl ester monomer S, in which case the coloring is prevented.
  • an antioxidant such as tartaric acid can be added to the polymerization system to the extent of 1 ⁇ ;! OOppm (based on the bull ester monomer)! /.
  • the butyl ester monomer to be copolymerized with CO is not particularly limited, and examples thereof include vinyl formate, butyl acetate, butyl propionate, butyl butyrate, butyl isobutyrate, vinyl bisvalinate, varistic acid butyl, Caproic acid bull, strong prillic acid bull, lauric acid bull, palmitate bull, stearate bull, oleate bull, benzoate bull, etc. Of these, butyl acetate is preferred.
  • Another monomer (A) may be copolymerized within a range not impairing the gist of the present invention.
  • Monomers (A) that can be used include, for example, ⁇ -olefins such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and its salts; methyl acrylate, ethyl acrylate, ⁇ -propyl acrylate, acrylic Acrylates such as i-propyl acid, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and its salts; Methyl methacrylate, Ethyl methacrylate, n-propyl methacrylate, i-propyl
  • the chain transfer agent is used within the range not impairing the gist of the present invention. You may carry out in presence.
  • the chain transfer agent include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methylethylketone; mercaptans such as 2-hydroxyethanethiol; halogens such as trichloroethylene and perchloroethylene Among them, aldehydes and ketones can be preferably used.
  • the amount of chain transfer agent to be added may be determined according to the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the target bull ester polymer. 0.;! ⁇ 10% by weight is desirable.
  • the saponification method of the carbon monoxide bule ester copolymer obtained by copolymerization of CO and the butyl ester monomer is not particularly limited, and a known method may be used.
  • a saponification method based on an alcoholysis or hydrolysis reaction using a basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, or an acidic catalyst such as p-toluenesulfonic acid can be applied. a basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, or an acidic catalyst such as p-toluenesulfonic acid can be applied. .
  • Examples of the solvent that can be used in this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone: aromatic hydrocarbons such as benzene and toluene These can be used alone or in combination of two or more. Of these, it is convenient and preferable to saponify the carbon monoxide butyl ester copolymer using methanol or a methanol / methyl acetate mixed solution as a solvent and sodium hydroxide as a catalyst.
  • alcohols such as methanol and ethanol
  • esters such as methyl acetate and ethyl acetate
  • ketones such as acetone and methyl ethyl ketone
  • aromatic hydrocarbons such as benzene and toluene
  • the CO-modified PVA of the present invention comprises units based on carbon monoxide (CO units) and bull alcohol.
  • the CO modified PVA of the present invention has a CO unit content (CO modified amount) of 0.01 to 8 mol%. If the amount of CO modification exceeds 8 mol%, CO-modified PVA—the proportion of hydrophobic groups contained in the molecule increases and the water solubility of the PVA decreases. On the other hand, when the CO modification amount is less than 0.01 mol%, the CO-modified PVA is excellent in water solubility, but since the number of carbonyl groups contained in the PVA is small, the characteristics based on CO modification do not appear.
  • CO-modified PVA of the present invention when used as a component of water-resistant composition of the present invention, the CO-modified amount is required to be 0.1 mole 0/0 or more, 0.5 mole 0/0 or preferred signaling 0.9 mole 0/0 or more and 1-0 mole 0/0 or more forward, more preferred.
  • the following formula (I) relating to the upper limit of the CO modification amount is preferably satisfied.
  • the CO-modified PVA has better water solubility.
  • X is the viscosity average degree of polymerization of CO-modified PVA (hereinafter, also simply referred to as “polymerization degree”) measured according to JIS—K6726
  • Y is CO-modified in CO-modified PVA. Amount (mol%).
  • the polymerization degree X and the CO modification amount Y preferably satisfy the following formula (I).
  • the amount of CO modification Y in CO-modified PVA can be determined by proton NMR measurement of a carbon monoxide-vinyl ester copolymer that is a precursor of the PVA. Specifically, it may be determined as follows: n After reprecipitation and purification of the carbon monoxide butyl ester copolymer with a hexane / acetone mixed solution three or more times, then reduce the pressure at 50 ° C. Dry for 2 days to make a copolymer for analysis. Next, the copolymer is dissolved in CDC1, and a proton NMR profile at room temperature is obtained (in the examples, G X-500 manufactured by JEOL was used).
  • the peak ⁇ (chemical shift is 4 ⁇ 7 to 5 ⁇ 2 ppm) derived from methine (one CH—) in the main chain of the butyl ester and the methylene (one CH—) adjacent to the carbonyl group.
  • the peak derived from / 3 (with a chemical shift of 2 ⁇ 2 to 3 ⁇ Oppm) is discriminated, and the amount of CO modification can be evaluated by the following formula (II).
  • the viscosity average polymerization degree P of CO-modified PVA is measured according to JIS-K6726.
  • the intrinsic viscosity measured in water at 30 ° C [7]] can be evaluated by the following formula (III).
  • the degree of polymerization of the CO-modified PVA is preferably 200-3500. When the degree of polymerization exceeds 3500,
  • the aqueous composition of CO-modified PVA includes an aqueous solution of CO-modified PVA.
  • the CO-modified PVA of the present invention is used as a component of the water-resistant composition of the present invention, its polymerization degree (500-3500 power ⁇ preferably, more preferably 800-3500 power. If it is less than 500, the water resistance of the water resistant composition will not be manifested!
  • the viscosity of the CO-modified PVA of the present invention (viscosity when it is an aqueous solution having a concentration of 4% by weight: hereinafter, also simply referred to as "4% rice occupancy") is 2.0-150. OmPa's. is there. If the 4% rice occupancy is less than 2 ⁇ OmPa's, the production of the PVA becomes difficult, which is not practical. When the 4% viscosity exceeds 150 mPa's, the viscosity stability as an aqueous composition is lowered.
  • the viscosity of the aqueous solution here refers to the viscosity measured according to JIS-K6726.
  • the CO-modified PVA of the present invention is used as a component of the water-resistant composition of the present invention, its 4% viscosity is preferably 5.0-150. OmPa's. The water resistance of can be improved.
  • the CO-modified PVA of the present invention satisfies the above formula (I)
  • its 4% viscosity is preferably 140 mPa-s or less. In this case, the water solubility of the PVA can be improved. In addition, when the 4% viscosity is 11 OmPa's or less, the viscosity stability of the PVA as an aqueous composition can be improved.
  • the saponification degree of the CO-modified PVA of the present invention is 60 to 99.99 mol%.
  • the degree of saponification is less than 60 mol%, the water solubility of CO-modified PVA decreases, making it difficult to obtain an aqueous composition of PVA.
  • the degree of saponification exceeds 99.99 mol%, the production of the PVA becomes difficult, which is not practical.
  • the CO-modified PVA of the present invention is used as a component of water-resistant composition of the present invention, the degree of saponification, 85-99. Should be 99 mole 0/0, 95 mole 0/0 or preferably tool 95-99. 9 Monore 0/0, and 98 to 99.9 preferably by Monore 0/0 J injection. When the strength strength is less than 5 mol%, the water resistance of the composition tends to decrease.
  • This structure is generated by the progress of a deacetic acid reaction or a dehydration reaction using sodium hydroxide or the like as a catalyst when saponifying a carbon monoxide butyl ester copolymer. Further, this structure may become a gen or trien structure due to dehydration of the bull alcohol unit adjacent to the structure during the drying step after saponification.
  • the water-resistant composition of the present invention contains CO-modified PVA and a polyfunctional hydrazide compound having two or more hydrazide groups in the molecule.
  • This CO-modified PVA satisfies the above-mentioned numerical range according to the amount of CO modification, 4% viscosity and saponification degree.
  • the CO-modified PVA contained in the water-resistant composition of the present invention preferably satisfies the degree of polymerization X, the amount of CO modification Y, and the force (I). In this case, the water resistance of the composition can be improved.
  • the CO-modified PVA contained in the water-resistant composition of the present invention preferably satisfies the above-mentioned numerical range regarding the degree of polymerization.
  • the polyfunctional hydrazide compound is not particularly limited as long as it is a compound having two or more hydrazide groups in the molecule. Examples thereof include adipic acid dihydrazide, polyacrylic acid hydrazide, itaconic acid dihydrazide, fumaric acid dihydrazide, Maleic acid dihydrazide, sebacic acid dihydrazide, gnoretanolic acid dihydrazide, succinic acid dihydrazide, malonic acid dihydrazide, oxalic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, phthalic acid dihydrazide, pimelic acid dihydrazide, pimelic acid dihydrazide Azelaic acid dihydrazide, hexadecandi Hydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, ethylenediamine tetra
  • the content of the polyfunctional hydrazide compound in the water-resistant composition of the present invention is not particularly limited, but it is preferably 1 to 15 parts by weight with respect to 100 parts by weight of CO-modified PVA, more preferably 2 to 8 parts by weight. preferable.
  • the content of the polyfunctional hydrazide compound is less than the above numerical range, crosslinking does not proceed sufficiently, and the water resistance of the composition tends to decrease.
  • the content exceeds the above numerical range the unreacted polyfunctional hydrazide compound is eluted and the water resistance of the composition tends to decrease.
  • the use of the water-resistant composition of the present invention is not particularly limited.
  • a clear coating agent for example, a pigment coating agent, an internal sizing agent, an overcoat binder used for thermal paper, and other paper coating agents.
  • it can be applied to various uses such as various binders, adhesives, fiber pastes, surface treatment agents, and films, particularly those requiring water resistance.
  • the CO-modified PVA obtained in the following production examples was evaluated for its solubility in water (water solubility) and viscosity stability when it was used as an aqueous solution. Further, the water resistance of a film formed by casting an aqueous composition obtained by mixing a PVA aqueous solution prepared using the CO-modified PVA and a crosslinking agent (polyfunctional hydrazide compound) was evaluated.
  • the pure content b (%) is a value obtained from the following equation (V).
  • Pure content b (%) Weight of CO-denatured PVA after drying for 3 hours at 105 ° C (g) / Weight of CO-denatured PVA before drying (g) (V)
  • the solubility of CO-modified PVA in water was determined according to the following criteria based on the calculated insoluble content.
  • the solubility of PVA in water becomes better in the order of D C B A.
  • a CO-modified PVA aqueous solution with a concentration of 10% was prepared, and the prepared aqueous solution was kept at 10 ° C in a constant temperature bath.
  • the viscosity of the aqueous solution at the time when the temperature of the aqueous solution reached 1 ° C (initial Viscosity) 1 and the viscosity n 2 of the aqueous solution after being held at 10 ° C. for 7 days were measured.
  • the viscosity of the aqueous solution was measured by the method described above.
  • a 4% concentration of CO-modified PVA aqueous solution was prepared, and 5 parts of adipic acid dihydrazide as a polyfunctional hydrazide compound was added to the CO-modified PVA, and then the resulting aqueous composition was run at 20 ° C.
  • a film with a thickness of 40 m was formed.
  • the obtained film was cut into a size of 5 cm in length and 5 cm in width to prepare a test piece.
  • the prepared test piece was immersed in distilled water at 90 ° C. for 30 minutes and then collected. The moisture adhering to the surface of the test piece was wiped off with gauze, and its weight A was measured.
  • After the weight-measured test piece was further dried at 105 ° C. for 16 hours, its weight B was measured.
  • the water resistance of the film was determined according to the following criteria by determining the value of weight A / weight B from the measured weight A and weight B and using this as the degree of swelling. The water resistance of the film becomes better in the order of D, C, B, A.
  • a 1 L internal pressure reactor equipped with a stirrer, nitrogen inlet, CO inlet and polymerization initiator addition is charged with 275 g of butyl acetate monomer, 225 g of methanol and 10 mg of tartaric acid, and the contents are 60 °
  • nitrogen substitution was performed in the reaction system by nitrogen publishing for 30 minutes.
  • CO substitution in the reaction system was performed by CO publishing for 30 minutes, CO was introduced so that the pressure in the reaction vessel became 1. OMPa, and then 2, 2′-azobis was used as a polymerization initiator.
  • 25 g of isobutyronitrile (AIBN) O. was injected into the tank to initiate copolymerization of butyl acetate monomer and CO.
  • the pressure in the reaction vessel was maintained at 1.0 MPa by pressurizing CO, and the polymerization temperature was maintained at 60 ° C.
  • the polymerization rate reached 35%, 30 mg of sorbic acid was added to the reaction system, and the polymerization was stopped by cooling.
  • exhaust gas line power provided in the reaction tank and CO in the tank were discharged, CO in the reaction system was completely degassed by publishing nitrogen gas.
  • depressurize the reaction vessel Unreacted butylacetate monomer remaining in the reaction system was removed, and a methanol solution of CO-denatured polyacetate butyrate (CO-denatured PVAc) was obtained.
  • the formed gel was taken out from the reaction vessel and pulverized by a pulverizer, and allowed to stand at 40 ° C for 1 hour to further promote saponification. Then, 200 g of methyl acetate was added to neutralize the alkali remaining in the gel. After confirming the completion of neutralization with a phenolphthalein indicator, the white solid obtained by filtration was put into methanol 100 g and allowed to stand at room temperature for 3 hours for washing. Next, the filtration and the washing operation of adding the white solid obtained by the filtration into methanol were repeated three times, and then the white solid obtained by centrifugation was placed in a drier kept at 65 ° C.
  • the degree of polymerization, degree of saponification, CO modification amount and 4% viscosity of the obtained PVA1 were evaluated by the above-mentioned method. As a result, the degree of polymerization was 860, the degree of saponification was 98.4 mol%, and the amount of CO modification was 0.9 %, 4% viscosity was 8.5 mPa's.
  • Polymerization conditions such as charging amount of butyl acetate monomer and methanol, CO pressure during polymerization ("Polymerization CO pressure" in Table 1), concentration of CO-modified PVA c during saponification, hydroxylation to butyl acetate units
  • Various CO-modified PVA (PVA2-30) were prepared in the same manner as in Production Example 1, except that the saponification conditions such as the molar ratio of sodium (“NaOH molar ratio” in Table 1) were changed as shown in Table 1 below. ) Was manufactured.
  • Table 2 shows the results of the solubility test and the viscosity stability test of the aqueous solution for the PVA produced as described above !-31.
  • Table 2 shows the polymerization degree, CO modification amount (mol%), saponification degree (mol%), and 4% viscosity (mPa's) of each CO-modified PVA.
  • Comparative Example 5 (PVA31) using cyclohexane as a solvent at the time of polymerization had a high solubility of 4% aqueous solution when dissolved in water as low as 1.5 mPa's. It was inferior.
  • Tables 3 to 5 below show the results of the water resistance tests performed on PVA1, 2, 4, 9-11, 14-18, and 29.
  • the carbon monoxide bulal alcohol copolymer of the present invention has good water solubility, and is excellent in viscosity stability when it is made into a water-based composition. Furthermore, by combining with a polyfunctional hydrazide compound having two or more hydrazide groups in the molecule, it is possible to develop excellent water resistance. For this reason, the carbon monoxide butyl alcohol copolymer of the present invention is a paper coating agent such as a clear coating agent, a pigment coating agent, an internal sizing agent, and an overcoat binder used for thermal paper. It can be suitably used for various uses such as various binders, adhesives, fiber pastes, surface treatment agents, and films, particularly those requiring water resistance.

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Abstract

L'invention concerne un nouveau copolymère monoxyde de carbone-alcool vinylique (PVA CO-modifié) comprenant un groupement carbonyle dans sa chaîne principale, ledit copolymère ayant une bonne solubilité dans l'eau et pouvant être préparé sous forme d'une composition aqueuse ayant une excellente stabilité à la viscosité. L'invention concerne également un procédé de fabrication du PVA CO-modifié. Le procédé comprend les étapes consistant à copolymériser du monoxyde de carbone et un monomère d'ester vinylique sans aucun solvant ou dans un solvant à base d'alcool dans une atmosphère contenant du monoxyde de carbone pour obtenir un copolymère monoxyde de carbone-ester vinylique, et à saponifier le copolymère, pour obtenir ainsi le PVA CO-modifié. Le PVA CO-modifié a une teneur en un monomère dérivé du monoxyde de carbone de 0,01 à 8 % en moles et un degré de saponification de 60 à 99,99 % en moles. Lorsque le PVA CO-modifié est préparé en une solution aqueuse à 4 % en poids, la solution aqueuse a une viscosité de 2,0 à 150,0 mPa•s.
PCT/JP2007/071794 2006-11-15 2007-11-09 Procédé de fabrication d'un copolymère monoxyde de carbone-alcool vinylique, copolymère monoxyde de carbone-alcool vinylique, et composition résistante à l'eau utilisant le copolymère WO2008059763A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
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