JPH09235317A - Production of both modified polyvinyl alcohol and its powder - Google Patents
Production of both modified polyvinyl alcohol and its powderInfo
- Publication number
- JPH09235317A JPH09235317A JP4453696A JP4453696A JPH09235317A JP H09235317 A JPH09235317 A JP H09235317A JP 4453696 A JP4453696 A JP 4453696A JP 4453696 A JP4453696 A JP 4453696A JP H09235317 A JPH09235317 A JP H09235317A
- Authority
- JP
- Japan
- Prior art keywords
- pva
- vinyl compound
- michael addition
- polyvinyl alcohol
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 46
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 46
- 239000000843 powder Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- -1 vinyl compound Chemical class 0.000 claims abstract description 27
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 20
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 9
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 9
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 9
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000004048 modification Effects 0.000 description 15
- 238000012986 modification Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 238000007278 cyanoethylation reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HQSMEHLVLOGBCK-UHFFFAOYSA-N 1-ethenylsulfinylethene Chemical compound C=CS(=O)C=C HQSMEHLVLOGBCK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- 238000007696 Kjeldahl method Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリビニルアルコ
ール（以下、「ＰＶＡ」という）変性体の製造方法、及
び変性ＰＶＡ粉末品の製造方法に関し、詳しくはビニル
化合物をＰＶＡ不溶性の溶媒懸濁系でＰＶＡに、もしく
はＰＶＡ不溶性溶媒中でポリ酢酸ビニルをけん化しなが
らマイケル付加することを特徴とするＰＶＡ変性体の製
造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a modified product of polyvinyl alcohol (hereinafter referred to as “PVA”) and a method for producing a modified PVA powder product, and more specifically, a vinyl compound in a PVA-insoluble solvent suspension system. The present invention relates to a method for producing a modified PVA, which comprises adding polyvinyl acetate to PVA or in a PVA insoluble solvent while saponifying polyvinyl acetate.
【０００２】ここでいう「溶媒懸濁系」とはＰＶＡにビ
ニル化合物をマイケル付加反応させて変性ＰＶＡを製造
するにおいて、前記ＰＶＡをＰＶＡ不溶性の溶媒に反応
を通して溶解させることなく（溶解しても極僅かで）懸
濁分散させ、固形の状態（粉末の状態）を維持したまま
前記ビニル化合物との化学反応を進行させ、当該ＰＶＡ
を変性させる反応系のことをいう。尚、反応に用いるビ
ニル化合物は固体、液体どちらでも良く、必要に応じ水
等の溶媒に溶解して使用することもできる。The term "solvent suspension system" as used herein means that when PVA is subjected to a Michael addition reaction with a vinyl compound to produce a modified PVA, the PVA is not dissolved in a PVA-insoluble solvent through the reaction (even if dissolved). The PVA is suspended and dispersed, and a chemical reaction with the vinyl compound proceeds while maintaining a solid state (powder state).
It means a reaction system for denaturing. The vinyl compound used in the reaction may be solid or liquid, and may be dissolved in a solvent such as water before use.
【０００３】本発明で得られるＰＶＡ変性体は優れた分
散性を有し、分散剤や掘削用泥水調整剤として有用であ
るほか、紙用添加剤、土木用薬剤、水溶性フィルム等、
接着剤等種々の用途に利用できる。The PVA modified product obtained by the present invention has excellent dispersibility and is useful as a dispersant and a mud adjusting agent for excavation, as well as an additive for paper, an agent for civil engineering, a water-soluble film, etc.
It can be used for various purposes such as adhesives.
【０００４】また粉末品は、物流コストの削減、貯蔵の
面および品質保持の点でメリットがある。Further, the powdered product has advantages in terms of reduction of physical distribution cost, storage and quality maintenance.
【０００５】[0005]
【従来の技術】上記変性ＰＶＡの製造方法としては、例
えば、「工業化学雑誌」第６３巻第２号（１９６０）第
１４２〜１４５頁やＵＳＰ ５，１０４，９３３等に記
載の方法が公知であるが、これらはいずれもＰＶＡの水
溶液中でマイケル付加反応させる方法である。2. Description of the Related Art As a method for producing the above-mentioned modified PVA, for example, a method described in "Industrial Chemistry Magazine", Vol. 63, No. 2, (1960), pages 142-145 and USP 5,104,933 is known. However, all of these are methods of performing a Michael addition reaction in an aqueous solution of PVA.
【０００６】[0006]
【発明が解決しようとする課題】このような従来の技術
において粉末のＰＶＡ変性体を得ようとした場合、溶媒
の水を蒸留によって除くかもしくは、多量のメタノール
やイソプロピルアルコール等で精製する必要があり、工
業的には非常にコストが高くつくため不利である。In order to obtain a powdered PVA modified product by the conventional technique as described above, it is necessary to remove water as a solvent by distillation or to purify it with a large amount of methanol, isopropyl alcohol or the like. However, it is disadvantageous because it is industrially very expensive.
【０００７】また、低濃度で反応させるため反応率（ビ
ニル化合物の有効利用率）が低く、例えば、「工業化学
雑誌」第６３巻第２号（１９６０）第１４２〜１４５頁
に記載の内容によれば、１５時間反応しても反応率は２
０％にも満たない結果となっている。尚、このときの変
性率は１８モル％である。Further, since the reaction is carried out at a low concentration, the reaction rate (effective utilization rate of vinyl compound) is low. For example, in the contents described in "Industrial Chemistry Magazine" Vol. 63 No. 2 (1960) pp. 142-145. Therefore, the reaction rate is 2 even after reacting for 15 hours.
The result is less than 0%. The modification rate at this time was 18 mol%.
【０００８】[0008]
【課題を解決するための手段】上記問題を解決するた
め、本発明者等はＰＶＡをＰＶＡ不溶の溶媒に懸濁させ
た状態でビニル化合物をマイケル付加反応させたとこ
ろ、短時間で４５％以上という高い反応率のものが得ら
れた。さらにはこのような溶媒懸濁系で、ＰＶＡの前駆
体であるポリ酢酸ビニルのけん化と同時にビニル化合物
をマイケル付加反応させても、４０％以上の高い反応率
で目的とするＰＶＡ変性体が得られることを見出し本発
明に至った。また、これらを濾過した後乾燥するだけで
容易に粉末品を得ることができる。In order to solve the above problems, the present inventors carried out a Michael addition reaction of a vinyl compound in a state where PVA was suspended in a solvent insoluble in PVA, and it was 45% or more in a short time. A high reaction rate was obtained. Furthermore, in such a solvent suspension system, even if a vinyl compound is subjected to a Michael addition reaction simultaneously with saponification of polyvinyl acetate which is a precursor of PVA, a desired PVA modified product can be obtained with a high reaction rate of 40% or more. The present invention has been found to be achieved. Further, a powder product can be easily obtained only by filtering these and then drying.
【０００９】請求項１記載の変性ＰＶＡの製造方法は、
ビニル化合物を溶媒懸濁系でＰＶＡにマイケル付加させ
ることを特徴とする。The method for producing a modified PVA according to claim 1 is
It is characterized in that the vinyl compound is subjected to Michael addition to PVA in a solvent suspension system.
【００１０】請求項２記載の変性ＰＶＡの製造方法は、
ポリ酢酸ビニルをＰＶＡ不溶性溶媒中でけん化しなが
ら、ビニル化合物をマイケル付加させることを特徴とす
る。A method for producing a modified PVA according to claim 2 is
It is characterized in that a vinyl compound is subjected to Michael addition while saponifying polyvinyl acetate in a PVA insoluble solvent.
【００１１】請求項３記載の変性ＰＶＡの製造方法は、
請求項１又は２記載の製造方法において、前記ビニル化
合物がアクリルアミドおよび／または２−アクリルアミ
ド−２−メチルプロパンスルホン酸あるいはその塩であ
ることを特徴とする。The method for producing a modified PVA according to claim 3 is
The production method according to claim 1 or 2, wherein the vinyl compound is acrylamide and / or 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof.
【００１２】請求項４記載の変性ＰＶＡの製造方法は、
請求項３記載の製造方法において、アクリルアミドをマ
イケル付加した後、またはアクリルアミド及び２−アク
リルアミド−２−メチルプロパンスルホン酸あるいはそ
の塩をマイケル付加した後加水分解することを特徴とす
る。The method for producing the modified PVA according to claim 4 is:
In the production method according to claim 3, hydrolysis is carried out after Michael addition of acrylamide or Michael addition of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof.
【００１３】請求項５記載の変性ＰＶＡの製造方法は、
請求項１〜４のいずれか１項に記載の方法により製造さ
れた変性ＰＶＡを濾過した後、直接乾燥するかあるいは
少量の有機溶媒で精製したのち乾燥することを特徴とす
る。The method for producing a modified PVA according to claim 5 is
It is characterized in that the modified PVA produced by the method according to any one of claims 1 to 4 is filtered and then directly dried or purified with a small amount of an organic solvent and then dried.
【００１４】[0014]
【発明の実施の形態】本発明に用いられるＰＶＡ、もし
くはポリ酢酸ビニルの重合度に特に限定はないが、５０
〜８，０００のものが良く、入手の容易さの点で好まし
くは３００〜６，０００である。BEST MODE FOR CARRYING OUT THE INVENTION The degree of polymerization of PVA or polyvinyl acetate used in the present invention is not particularly limited, but 50
˜8,000 is preferable, and 300 to 6,000 is preferable from the viewpoint of easy availability.
【００１５】上記ＰＶＡの他に、カルボキシ変性、スル
ホン基変性、カチオン基変性およびシリル基変性等の変
性ＰＶＡを出発物質として用いることもできる。この場
合、原料として使用するＰＶＡの変性率としては、例え
ば０．５〜１０モル％である。In addition to the above PVA, modified PVA such as carboxy-modified, sulfone-group-modified, cation-group-modified, and silyl-group-modified can also be used as a starting material. In this case, the modification rate of PVA used as a raw material is, for example, 0.5 to 10 mol%.
【００１６】本発明のうち、ＰＶＡを出発物質として反
応を行う場合の特徴は、ＰＶＡを予め溶解することなく
固形のままで反応に供することである。このときのＰＶ
Ａは、粉末状（顆粒状、細粒状等これに類する形態を含
む）であり、平均粒径としては１，０００μｍ以下であ
ることが好ましい。１，０００μｍを超える場合、触
媒、ビニル化合物が浸透しにくいという問題が発生する
可能性がある。In the present invention, the feature of carrying out the reaction using PVA as a starting material is that the PVA is used as a solid without being dissolved in advance. PV at this time
A is in the form of powder (including forms similar to these such as granules and fine particles), and the average particle size is preferably 1,000 μm or less. If it exceeds 1,000 μm, there is a possibility that the catalyst and the vinyl compound may not easily permeate.
【００１７】本発明に用いられるビニル化合物としては
アクリロニトリル、アクリルアミド、アクリル酸または
その塩、アクリル酸エステル、２−アクリルアミド−２
−メチルプロパンスルホン酸またはその塩（カリウム
塩、ナトリウム塩、アンモニウム塩など）、ビニルスル
ホン酸またはその塩、ビニルスルホオキサイド、ビニル
スルホン、マレイン酸、マレイン酸ジエステル等のノニ
オン、アニオン性ビニル化合物の他にＮ，Ｎ−ジメチル
アミノエチルアクリレートまたはその四級塩、Ｎ，Ｎ−
ジメチルアミノプロピルアクリルアミドまたはその四級
塩等のカチオン性ビニル化合物が挙げられる。また、こ
れらを２種以上組み合わせて使用することもできる。こ
のうち、反応性が高いという理由でアクリルアミド、ア
クリロニトリル、２−アクリルアミド−２−メチルプロ
パンスルホン酸またはその塩が好ましい。これらはその
まま用いることはもちろんのこと、水等の溶媒に希釈あ
るいは溶解して使用することもできる。As the vinyl compound used in the present invention, acrylonitrile, acrylamide, acrylic acid or its salt, acrylic ester, 2-acrylamide-2.
-Methyl propane sulfonic acid or its salts (potassium salt, sodium salt, ammonium salt, etc.), vinyl sulfonic acid or its salts, nonionics such as vinyl sulfoxide, vinyl sulfone, maleic acid, maleic acid diester, and anionic vinyl compounds To N, N-dimethylaminoethyl acrylate or a quaternary salt thereof, N, N-
Examples thereof include cationic vinyl compounds such as dimethylaminopropyl acrylamide or a quaternary salt thereof. Moreover, these can also be used in combination of 2 or more types. Of these, acrylamide, acrylonitrile, 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof is preferable because of its high reactivity. These may be used as they are, or may be diluted or dissolved in a solvent such as water before use.
【００１８】ＰＶＡを懸濁させる溶媒、すなわちＰＶＡ
不溶性溶媒としては、ベンゼン、トルエン、キシレン、
ヘキサン、アセトン、メチルエチルケトン、テトラヒド
ロフラン、ジオキサン、メタノール、エタノール、イソ
プロパノール、ブタノール、酢酸メチル等が好適であ
る。反応は不均一系で進行するので、均一に反応が進む
よう充分撹拌しながら行うことが好ましい。Solvent for suspending PVA, ie PVA
Insoluble solvents include benzene, toluene, xylene,
Hexane, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, butanol, methyl acetate and the like are preferable. Since the reaction proceeds in a heterogeneous system, it is preferable to perform the reaction with sufficient stirring so that the reaction proceeds uniformly.
【００１９】前記溶媒のうち、反応性が良好であるとい
う点で、炭素数１〜４のアルコールあるいはメチルエチ
ルケトンが好ましい。また、この溶媒の使用量は、ＰＶ
Ａ１重量部に対して５〜２０重量部である。５重量部未
満では系が、懸濁状ではなくスラリー状になりやすく、
２０重量部を超えるとコスト的にアップし、また反応率
も上がらない傾向にある。Among the above solvents, alcohols having 1 to 4 carbon atoms or methyl ethyl ketone are preferable because they have good reactivity. The amount of this solvent used is PV
It is 5 to 20 parts by weight with respect to A1 part by weight. If it is less than 5 parts by weight, the system tends to be a slurry rather than a suspension,
If it exceeds 20 parts by weight, the cost tends to increase and the reaction rate tends not to increase.
【００２０】また、ポリ酢酸ビニルをけん化しながらビ
ニル化合物をマイケル付加させる場合のＰＶＡ不溶性溶
媒の使用量は、ポリ酢酸ビニル１重量部に対して５〜２
０重量部である。The amount of the PVA insoluble solvent used when Michael-adding a vinyl compound while saponifying polyvinyl acetate is 5 to 2 parts by weight per 1 part by weight of polyvinyl acetate.
0 parts by weight.
【００２１】配合の手順としては、懸濁させる溶媒にＰ
ＶＡとＮａＯＨ、ＫＯＨ、トリエチルアミン等の触媒、
次いで、ビニル化合物を添加するが添加順序に特に限定
はない。反応に使用する触媒の量としては、ＰＶＡに対
し０．５〜１００モル％、ビニル化合物の量としては１
〜２００モル％の範囲が好適である。The compounding procedure is as follows.
VA and catalyst such as NaOH, KOH, triethylamine, etc.,
Next, a vinyl compound is added, but the order of addition is not particularly limited. The amount of catalyst used in the reaction is 0.5 to 100 mol% relative to PVA, and the amount of vinyl compound is 1
The range of ˜200 mol% is preferred.
【００２２】マイケル付加反応を行うための適当な温度
は５〜１２０℃の範囲であり、好ましくは２０〜７０℃
の範囲である。マイケル付加反応の時間としては３０分
〜１０時間が好適である。ビニル化合物の種類（例え
ば、アクリルアミド、アクリロニトリル）によっては、
この後アルカリ等を添加し加水分解を行うこともでき
る。この場合、用途に応じて部分的に加水分解したり、
完全に加水分解することもできる。加水分解物について
も本発明の変性ＰＶＡに該当する。加水分解には、Ｎａ
ＯＨ、ＫＯＨ、ＬｉＯＨ、Ｎａ２ＣＯ３、ＮＨ２ＯＨ等
のアルカリ薬剤のほか、ジメチルアミン等のアルキルア
ミン類、モノエタノールアミン等のアルカノールアミン
類も使用できる。Suitable temperatures for carrying out the Michael addition reaction are in the range 5 to 120 ° C, preferably 20 to 70 ° C.
Range. The time for the Michael addition reaction is preferably 30 minutes to 10 hours. Depending on the type of vinyl compound (eg, acrylamide, acrylonitrile),
After this, hydrolysis can be carried out by adding an alkali or the like. In this case, it may be partially hydrolyzed depending on the application,
It can also be completely hydrolyzed. The hydrolyzate also corresponds to the modified PVA of the present invention. For hydrolysis, Na
In addition to alkali agents such as OH, KOH, LiOH, Na 2 CO 3 and NH 2 OH, alkylamines such as dimethylamine and alkanolamines such as monoethanolamine can be used.
【００２３】けん化と同時にマイケル付加反応を行う場
合は、イソプロパノール等のＰＶＡ不溶性溶媒中で公知
の方法で酢酸ビニルを重合した後、けん化に使うアルカ
リおよびビニル化合物を加える。その他は前記と同様の
方法で行うことができる。けん化に使うアルカリとして
はＮａＯＨかＫＯＨが良く、これはマイケル付加反応の
触媒としても作用する。When the Michael addition reaction is carried out simultaneously with saponification, vinyl acetate is polymerized by a known method in a PVA insoluble solvent such as isopropanol, and then an alkali and a vinyl compound used for saponification are added. Others can be performed by the same method as described above. The alkali used for saponification is preferably NaOH or KOH, which also acts as a catalyst for the Michael addition reaction.
【００２４】最終生成物は濾過した後乾燥するだけで、
容易に粉末品（平均粒径１５０〜１，０００μｍ）とな
る（乾燥は公知の方法を利用できる）。また、必要に応
じて変性ＰＶＡ生成物１重量部に対し１〜５重量部とい
った少量のメタノール等で精製することでさらに純度の
高いものが得られる。The final product is simply filtered and dried,
A powder product (average particle size 150 to 1,000 μm) is easily obtained (drying can use a known method). Further, if necessary, a product with higher purity can be obtained by purifying with a small amount of methanol or the like such as 1 to 5 parts by weight per 1 part by weight of the modified PVA product.
【００２５】このようにして得られたＰＶＡ変性体の変
性率は、ＮＭＲやＩＲにより求めることができる。本検
討で得られた変性ＰＶＡの変性率は０．５〜４０モル％
であった。また、その他の変性率を求める手段として
は、アニオンあるいはカチオン基変性についてはコロイ
ド滴定が、また、窒素を含む化合物による変性ではセミ
ミクロケルダール法等が挙げられる。The modification ratio of the PVA modified product thus obtained can be determined by NMR or IR. The modified PVA obtained in this study has a modification rate of 0.5 to 40 mol%.
Met. Examples of other means for determining the modification rate include colloid titration for modification with anion or cation group, and semi-micro Kjeldahl method for modification with a compound containing nitrogen.
【００２６】本検討で得られた変性ＰＶＡの重量平均分
子量をＧＰＣにより測定したところ７，０００〜３６
０，０００の範囲であった。尚、溶離液として０．１規
定ＮａＣｌ水溶液を用い、東ソー（株）製カラム４本
（ＴＳＫｇｅｌＧ２５００ＰＷ、Ｇ３０００ＰＷ、Ｇ４
０００ＰＷ、Ｇ５０００ＰＷ）を直列につないで測定し
た。The weight average molecular weight of the modified PVA obtained in this study was measured by GPC to be 7,000 to 36.
It was in the range of 10,000. In addition, using 0.1N NaCl aqueous solution as an eluent, four columns (TSKgel G2500PW, G3000PW, G4, manufactured by Tosoh Corporation) were used.
000PW, G5000PW) were connected in series and measured.
【００２７】[0027]
【実施例】以下、実施例により本発明をさらに詳しく説
明する。The present invention will be described in more detail with reference to the following examples.
【００２８】実施例１ １リットル容のセパラブルフラスコに、完全けん化で重
合度が５００のＰＶＡ（クラレＰＶＡ−１０５）４４
ｇ、１０％−ＮａＯＨ水溶液１２ｇ、アクリロニトリル
２６ｇ、イソプロパノール５００ｇを加え、５０℃で８
時間撹拌した。得られた生成物を濾過した後乾燥し、白
色の粉末６５ｇ（平均粒径５５０μｍ）を得た。得られ
た粉末をＮＭＲで分析したところ、シアノエチル化度
（変性率）は４０モル％、反応率は８２％であった。ま
た、ＧＰＣにより重量平均分子量を測定したところ、２
１，０００であった。 Example 1 PVA (Kuraray PVA-105) 44 having a degree of polymerization of 500 when completely saponified was placed in a separable flask having a volume of 1 liter.
g, 10% -NaOH aqueous solution 12 g, acrylonitrile 26 g, and isopropanol 500 g were added, and the mixture was heated at 50 ° C. for 8 hours.
Stirred for hours. The obtained product was filtered and then dried to obtain 65 g of white powder (average particle size: 550 μm). When the obtained powder was analyzed by NMR, the degree of cyanoethylation (modification rate) was 40 mol% and the reaction rate was 82%. Further, when the weight average molecular weight was measured by GPC, it was 2
It was 1,000.
【００２９】実施例２ １リットル容のセパラブルフラスコに、完全けん化で重
合度が１，７００のＰＶＡ（クラレＰＶＡ−１１７）４
４ｇ、３０％−ＮａＯＨ水溶液４０ｇ、５０％−アクリ
ルアミド水溶液４３ｇ、アセトン５００ｇを加え、２０
℃で４時間撹拌した。得られた生成物を濾過した後乾燥
し、白色の粉末６０ｇ（平均粒径５１０μｍ）を得た。
得られた粉末をＮＭＲで分析したところ、カルバモイル
エチル化度（変性率）は２１モル％、反応率は７０％で
あった。また、ＧＰＣにより重量平均分子量を測定した
ところ、８２，０００であった。 Example 2 PVA (Kuraray PVA-117) 4 having a polymerization degree of 1,700 after complete saponification was placed in a separable flask having a capacity of 1 liter.
4g, 30% -NaOH aqueous solution 40g, 50% -acrylamide aqueous solution 43g, and acetone 500g were added, and
Stirred at C for 4 hours. The obtained product was filtered and dried to obtain 60 g of white powder (average particle size: 510 μm).
When the obtained powder was analyzed by NMR, the carbamoylethylation degree (modification rate) was 21 mol% and the reaction rate was 70%. Moreover, the weight average molecular weight was 82,000 as measured by GPC.
【００３０】実施例３ １リットル容のセパラブルフラスコに、完全けん化で重
合度が２，４００のＰＶＡ（クラレＰＶＡ−１２４）４
４ｇ、３０％−ＮａＯＨ水溶液２０ｇ、５０％−アクリ
ルアミド水溶液２８ｇ、トルエン６００ｇを加え、４０
℃で７時間撹拌した。次いで５０％−ＮａＯＨ５ｇを加
え、９０℃で１時間加水分解を行った。得られた生成物
を濾過した後、少量（１５０ｇ）のメタノールで精製
し、乾燥することにより白色の粉末５５ｇ（平均粒径６
５０μｍ）を得た。得られた粉末をＮＭＲで分析したと
ころ、カルバモイルエチル化度（変性率）は２モル％、
カルボキシエチル化度は１３モル％（トータル変性率は
１５モル％）、反応率は７５％であった。また、ＧＰＣ
により重量平均分子量を測定したところ、１２３，００
０であった。 Example 3 PVA (Kuraray PVA-124) 4 having a polymerization degree of 2,400 when completely saponified was placed in a 1-liter separable flask.
4 g, 30% -NaOH aqueous solution 20 g, 50% -acrylamide aqueous solution 28 g, and toluene 600 g were added, and 40
Stirred at C for 7 hours. Next, 5 g of 50% -NaOH was added and hydrolysis was performed at 90 ° C. for 1 hour. The product obtained was filtered, purified with a small amount (150 g) of methanol and dried to give 55 g of a white powder (average particle size 6
50 μm) was obtained. When the obtained powder was analyzed by NMR, the degree of carbamoylethylation (modification rate) was 2 mol%,
The degree of carboxyethylation was 13 mol% (total modification ratio was 15 mol%), and the reaction ratio was 75%. Also, GPC
The weight average molecular weight was measured by
It was 0.
【００３１】実施例４ １リットル容のセパラブルフラスコに、けん化度８８％
で重合度が１，７００のＰＶＡ（クラレＰＶＡ−２１
７）４９ｇ、５０％−ＮａＯＨ水溶液２８ｇ、５０％の
２−アクリルアミド−２−メチルプロパンスルホン酸水
溶液８３ｇ、メチルエチルケトン６００ｇを加え、６０
℃で５時間撹拌した。得られた生成物を濾過した後乾燥
し、白色の粉末７５ｇ（平均粒径４８０μｍ）を得た。
ＮＭＲ分析の結果、得られた粉末のスルホン基変性率は
１０モル％、反応率は５０％であった。また、ＧＰＣに
より重量平均分子量を測定したところ、１１０，０００
であった。 Example 4 A 1-liter separable flask was charged with a saponification degree of 88%.
With a polymerization degree of 1,700 (Kuraray PVA-21
7) 49 g, 50% -NaOH aqueous solution 28 g, 50% 2-acrylamido-2-methylpropanesulfonic acid aqueous solution 83 g, and methyl ethyl ketone 600 g were added, and 60
Stirred at C for 5 hours. The obtained product was filtered and then dried to obtain 75 g of white powder (average particle size: 480 μm).
As a result of NMR analysis, the modified powder had a sulfo group modification rate of 10 mol% and a reaction rate of 50%. Moreover, when the weight average molecular weight was measured by GPC, it was 110,000.
Met.
【００３２】実施例５ １リットル容のセパラブルフラスコに酢酸ビニル８６
ｇ、酢酸メチル４００ｇを加え、公知の方法により重合
反応を行った。次いで５０％−ＮａＯＨ水溶液１００
ｇ、２−アクリルアミド−２−メチルプロパンスルホン
酸４１ｇを加え、５０℃で８時間撹拌した。得られた生
成物を濾過した後、少量（２００ｇ）のメタノールで精
製し、乾燥することにより白色の粉末５３ｇ（平均粒径
５５０μｍ）を得た。ＮＭＲ分析の結果、得られた粉末
のスルホン基変性率は９．０モル％、反応率は４５％で
あった。また、ＧＰＣにより重量平均分子量を測定した
ところ、４０，０００であった。 EXAMPLE 5 Vinyl acetate 86 in a 1 liter separable flask.
g and 400 g of methyl acetate were added, and a polymerization reaction was performed by a known method. Then 50% -NaOH aqueous solution 100
g, 2-acrylamido-2-methylpropanesulfonic acid 41 g, and the mixture was stirred at 50 ° C. for 8 hours. The obtained product was filtered, purified with a small amount (200 g) of methanol, and dried to obtain 53 g of white powder (average particle size: 550 μm). As a result of NMR analysis, the modified powder had a sulfo group modification ratio of 9.0 mol% and a reaction ratio of 45%. The weight average molecular weight was 40,000 as measured by GPC.
【００３３】実施例６ 原料ＰＶＡに、カルボキシ変性ＰＶＡ（酢酸ビニルと無
水マレイン酸共重合体のけん化物、カルボキシ変性率２
モル％、重合度５００）を用いた以外、実施例１と同様
の反応を行い、白色の粉末６０ｇ（平均粒径６６０μ
ｍ）を得た。得られた粉末をＮＭＲで分析したところ、
シアノエチル化度は３８モル％、カルボキシ化度は２モ
ル％、反応率は７８％であった。また、ＧＰＣにより重
量平均分子量を測定したところ、２２，０００であっ
た。 Example 6 As a raw material PVA, carboxy-modified PVA (saponified product of vinyl acetate and maleic anhydride copolymer, carboxy modification rate 2
The same reaction as in Example 1 was carried out except that the mol% and the degree of polymerization of 500 were used, and 60 g of white powder (average particle size: 660 μ) was used.
m). When the obtained powder was analyzed by NMR,
The cyanoethylation degree was 38 mol%, the carboxylation degree was 2 mol%, and the reaction rate was 78%. The weight average molecular weight measured by GPC was 22,000.
【００３４】比較例１（水溶液中での反応例） ５００ミリリットル容のセパラブルフラスコに、完全け
ん化で重合度が１，７００のＰＶＡ（クラレＰＶＡ−１
１７）２０ｇ、および水３００ｇを加え、８０℃に昇温
しＰＶＡを完全に溶解させた。次いで、５０％−ＮａＯ
Ｈ水溶液２ｇおよびアクリルアミド１０ｇを加え、４０
℃で１０時間撹拌した。得られた反応溶液を多量（５，
０００ｇ）のメタノールに投入し、ミキサーで剪断する
ことによりようやく粉末品を得ることができた。得られ
た粉末をＮＭＲで分析したところ、カルバモイルエチル
化度（変性率）は４モル％、反応率は１３％と大変低い
ものであった。 Comparative Example 1 (Example of Reaction in Aqueous Solution ) A PVA (Kuraray PVA-1 ) having a polymerization degree of 1,700 and completely saponified was placed in a 500 ml separable flask.
17) 20 g and 300 g of water were added, and the temperature was raised to 80 ° C. to completely dissolve PVA. Then 50% -NaO
2 g of H aqueous solution and 10 g of acrylamide were added to 40
Stirred at C for 10 hours. A large amount of the obtained reaction solution (5, 5
It was finally possible to obtain a powdered product by adding it to 000 g) of methanol and shearing it with a mixer. When the obtained powder was analyzed by NMR, the degree of carbamoylethylation (modification rate) was 4 mol% and the reaction rate was 13%, which were very low.
【００３５】[0035]
【発明の効果】本発明の変性ＰＶＡの製造方法により、
ＰＶＡへのビニル化合物のマイケル付加反応において反
応率、すなわちビニル化合物の有効利用率を高めること
ができる。またこれにより、変性ＰＶＡの大量生産が可
能となる。According to the method for producing the modified PVA of the present invention,
In the Michael addition reaction of a vinyl compound to PVA, the reaction rate, that is, the effective utilization rate of the vinyl compound can be increased. Further, this enables mass production of the modified PVA.
【００３６】また、前記製造方法により得られた変性Ｐ
ＶＡは、濾過後そのまま乾燥するかあるいは少量のメタ
ノールで精製した後乾燥することにより、従来は非常に
困難であった粉末品を得ることができる。The modified P obtained by the above-mentioned production method
VA can be obtained as a powder product, which has been very difficult in the past, by filtering and then drying as it is, or by purifying with a small amount of methanol and then drying.
Claims (5)
ルコールにマイケル付加させることを特徴とする変性ポ
リビニルアルコールの製造方法。1. A method for producing a modified polyvinyl alcohol, which comprises adding a vinyl compound to a polyvinyl alcohol by Michael addition in a solvent suspension system.
溶性溶媒中でけん化しながら、ビニル化合物をマイケル
付加させることを特徴とする変性ポリビニルアルコール
の製造方法。2. A method for producing a modified polyvinyl alcohol, which comprises adding a vinyl compound by Michael while saponifying polyvinyl acetate in a polyvinyl alcohol insoluble solvent.
／または２−アクリルアミド−２−メチルプロパンスル
ホン酸あるいはその塩である請求項１または２記載の製
造方法。3. The production method according to claim 1, wherein the vinyl compound is acrylamide and / or 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof.
たはアクリルアミド及び２−アクリルアミド−２−メチ
ルプロパンスルホン酸あるいはその塩をマイケル付加し
た後加水分解することを特徴とする請求項３記載の製造
方法。4. The production method according to claim 3, wherein the hydrolysis is carried out after Michael addition of acrylamide or after Michael addition of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof.
により製造された変性ポリビニルアルコールを濾過した
後、直接乾燥するかあるいは少量の有機溶媒で精製した
のち乾燥することを特徴とする変性ポリビニルアルコー
ル粉末品の製造方法。5. The modified polyvinyl alcohol produced by the method according to any one of claims 1 to 4 is filtered and then directly dried or purified with a small amount of an organic solvent and then dried. A method for producing a modified polyvinyl alcohol powder product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4453696A JPH09235317A (en) | 1996-03-01 | 1996-03-01 | Production of both modified polyvinyl alcohol and its powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4453696A JPH09235317A (en) | 1996-03-01 | 1996-03-01 | Production of both modified polyvinyl alcohol and its powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09235317A true JPH09235317A (en) | 1997-09-09 |
Family
ID=12694238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4453696A Pending JPH09235317A (en) | 1996-03-01 | 1996-03-01 | Production of both modified polyvinyl alcohol and its powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09235317A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004269687A (en) * | 2003-03-07 | 2004-09-30 | Nippon Shokubai Co Ltd | Polyvinyl acetal compound and method for producing the same |
| KR101113040B1 (en) * | 2006-11-03 | 2012-02-13 | 주식회사 엘지화학 | Method for producing polyvinyl alcohol having high degree of saponification and high degree of purity, and polyvinyl alcohol produced using the same |
| KR102030501B1 (en) * | 2018-09-18 | 2019-10-10 | 주식회사 서한안타민 | Methods of increasing solubility of polyvinylalcohol |
-
1996
- 1996-03-01 JP JP4453696A patent/JPH09235317A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004269687A (en) * | 2003-03-07 | 2004-09-30 | Nippon Shokubai Co Ltd | Polyvinyl acetal compound and method for producing the same |
| KR101113040B1 (en) * | 2006-11-03 | 2012-02-13 | 주식회사 엘지화학 | Method for producing polyvinyl alcohol having high degree of saponification and high degree of purity, and polyvinyl alcohol produced using the same |
| KR102030501B1 (en) * | 2018-09-18 | 2019-10-10 | 주식회사 서한안타민 | Methods of increasing solubility of polyvinylalcohol |
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