JP2008274181A - Polyvinyl alcohol-polyvinyl pyrrolidone graft copolymer and method for producing the same - Google Patents
Polyvinyl alcohol-polyvinyl pyrrolidone graft copolymer and method for producing the same Download PDFInfo
- Publication number
- JP2008274181A JP2008274181A JP2007122236A JP2007122236A JP2008274181A JP 2008274181 A JP2008274181 A JP 2008274181A JP 2007122236 A JP2007122236 A JP 2007122236A JP 2007122236 A JP2007122236 A JP 2007122236A JP 2008274181 A JP2008274181 A JP 2008274181A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- hydrogen peroxide
- graft copolymer
- polymerization
- graft
- 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.)
- Granted
Links
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 29
- 229920000036 polyvinylpyrrolidone Polymers 0.000 title claims abstract description 22
- 239000001267 polyvinylpyrrolidone Substances 0.000 title claims abstract description 22
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 36
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 30
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 238000000746 purification Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 238000006392 deoxygenation reaction Methods 0.000 description 5
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
Description
本発明は、ポリビニルアルコール−ポリビニルピロリドングラフトコポリマー及びその製造方法に関し、特にグラフト効率の高いグラフトコポリマー、及びそれを得るための製造方法に関する。 The present invention relates to a polyvinyl alcohol-polyvinylpyrrolidone graft copolymer and a method for producing the same, and more particularly to a graft copolymer having a high grafting efficiency and a method for producing the same.
ポリビニルアルコールは水溶性の高分子であり、繊維加工剤、紙加工剤、接着剤、無機物のバインダー等、広範囲で利用されている。ポリビニルアルコールは、また、インクの吸収性が良好であるためインクジェット記録媒体にも使用され、例えば特許文献１（特開２００１−１１３８１８号公報）には、ポリビニルアルコールと、ポリビニルピロリドンと、ポリビニルアルコールを選択的に架橋する架橋剤と、ポリビニルアルコール−ポリエステル共重合体と、カチオン樹脂とを含有するインク受容層を形成することが開示されている。 Polyvinyl alcohol is a water-soluble polymer, and is widely used for fiber processing agents, paper processing agents, adhesives, inorganic binders, and the like. Polyvinyl alcohol is also used in ink jet recording media because of its good ink absorptivity. For example, Patent Document 1 (Japanese Patent Laid-Open No. 2001-113818) includes polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl alcohol. It is disclosed to form an ink receiving layer containing a crosslinking agent that selectively crosslinks, a polyvinyl alcohol-polyester copolymer, and a cationic resin.
しかし、ポリビニルアルコールは水に溶解させるときに、熱水にて溶解させる必要があり、しかも溶解に長時間を要するという問題があった。 However, when polyvinyl alcohol is dissolved in water, it needs to be dissolved in hot water, and it takes a long time to dissolve.
これに対し、ポリビニルアルコールにポリビニルピロリドンをグラフトさせたグラフトコポリマーが優れた水溶性を有することが見出され、このようなグラフトコポリマーはポリビニルアルコール溶液中でビニルピロリドンをラジカル重合する方法により得られることが開示されている（特許文献２，３）。 On the other hand, a graft copolymer obtained by grafting polyvinyl pyrrolidone to polyvinyl alcohol has been found to have excellent water solubility, and such a graft copolymer can be obtained by a method of radical polymerization of vinyl pyrrolidone in a polyvinyl alcohol solution. Are disclosed (Patent Documents 2 and 3).
しかし、従来技術で開示された製造方法ではグラフト効率が２０％以下のものしか得られないのが実情であった。グラフト効率が２０％程度では、上記のような優れた水溶性等の特性を有するグラフトコポリマーを得るためには精製が必要であり、コスト増加につながっていた。 However, the manufacturing method disclosed in the prior art is that the graft efficiency is only 20% or less. When the graft efficiency is about 20%, purification is necessary to obtain the graft copolymer having the above-mentioned excellent water solubility and the like, leading to an increase in cost.
従って、より高いグラフト効率を有するグラフトコポリマー、及び精製工程なしで優れた特性を有するグラフトコポリマーが容易に得られる製造方法が求められている。
本発明は上記に鑑みてなされたものであり、高いグラフト効率を有し、水溶性に優れたポリビニルアルコール−ポリビニルピロリドングラフトコポリマー、及びそのグラフトコポリマーが精製工程なしに容易に得られる製造方法を提供することを目的とする。 The present invention has been made in view of the above, and provides a polyvinyl alcohol-polyvinylpyrrolidone graft copolymer having high graft efficiency and excellent water solubility, and a production method for easily obtaining the graft copolymer without a purification step. The purpose is to do.
本発明者は、ポリビニルアルコール溶液にビニルピロリドンを配合し、開始剤として過酸化水素を使用する製造方法において、高度にグラフト化する手法を鋭意検討した結果、過酸化水素の添加量を調整すること、あるいは重合時のｐＨを８〜９に保持することで、これまでにないグラフト効率の高いグラフトコポリマーが得られ、それにより上記課題を解決し得ることを見出し、本発明の完成に至った。 As a result of intensive studies on a highly grafting method in a production method using vinyl pyrrolidone in a polyvinyl alcohol solution and using hydrogen peroxide as an initiator, the present inventors have adjusted the amount of hydrogen peroxide added. Or, by maintaining the pH during polymerization at 8 to 9, it was found that a graft copolymer having a high graft efficiency that has never been obtained so that the above-mentioned problems can be solved, and the present invention has been completed.
本発明のポリビニルアルコール−ポリビニルピロリドングラフトコポリマーは、ポリビニルアルコールにビニルピロリドンがグラフト重合したものであり、グラフト効率が４０％以上であるものである。 The polyvinyl alcohol-polyvinylpyrrolidone graft copolymer of the present invention is obtained by graft polymerization of polyvinyl pyrrolidone to polyvinyl alcohol, and has a graft efficiency of 40% or more.
上記本発明のポリビニルアルコール−ポリビニルピロリドングラフトコポリマーを得るために、ポリビニルアルコール溶液にビニルピロリドンを配合し、開始剤として過酸化水素を使用して反応を行う製造方法であって、重合中の反応系の過酸化水素濃度が６００ｐｐｍ以下に保持されるように過酸化水素を連続的または断続的に添加する方法を用いる。 In order to obtain the polyvinyl alcohol-polyvinylpyrrolidone graft copolymer of the present invention, a production method in which vinylpyrrolidone is blended in a polyvinyl alcohol solution and the reaction is performed using hydrogen peroxide as an initiator, the reaction system during polymerization A method is used in which hydrogen peroxide is continuously or intermittently added so that the concentration of hydrogen peroxide is maintained at 600 ppm or less.
あるいは、ポリビニルアルコール溶液にビニルピロリドンを配合し、開始剤として過酸化水素を使用して反応を行う製造方法であって、重合中の反応系のｐＨを８〜９に保持する方法を用いる。 Alternatively, it is a production method in which vinyl pyrrolidone is blended in a polyvinyl alcohol solution and the reaction is carried out using hydrogen peroxide as an initiator, and a method of maintaining the pH of the reaction system during polymerization at 8 to 9 is used.
さらに、ポリビニルアルコール溶液にビニルピロリドンを配合し、開始剤として過酸化水素を使用するポリビニルアルコール−ポリビニルピロリドングラフトコポリマーの製造方法において、重合中の反応系の過酸化水素濃度が６００ｐｐｍ以下となるように過酸化水素を連続的または断続的に添加し、かつ重合中のｐＨを８〜９に保持することにより、グラフト効率が６０％以上であるポリビニルアルコール−ポリビニルピロリドングラフトコポリマーを得ることもできる。 Furthermore, in the method for producing a polyvinyl alcohol-polyvinylpyrrolidone graft copolymer using vinyl pyrrolidone in a polyvinyl alcohol solution and using hydrogen peroxide as an initiator, the hydrogen peroxide concentration in the reaction system during polymerization is 600 ppm or less. By adding hydrogen peroxide continuously or intermittently and maintaining the pH during polymerization at 8-9, a polyvinyl alcohol-polyvinylpyrrolidone graft copolymer having a graft efficiency of 60% or more can also be obtained.
本発明のポリビニルアルコール−ポリビニルピロリドングラフトコポリマーは、高いグラフト効率を有するため、水溶性に優れたものとなる。 Since the polyvinyl alcohol-polyvinylpyrrolidone graft copolymer of the present invention has high grafting efficiency, it has excellent water solubility.
本発明の製造方法によれば、グラフト効率が４０％以上、さらには６０％以上と高いグラフトコポリマーが容易に得られ、精製せずに使用しても所望の効果が得られるため、製造工程が簡略化でき、コストダウンも可能となる。 According to the production method of the present invention, a graft copolymer having a graft efficiency as high as 40% or more, more preferably 60% or more can be easily obtained, and a desired effect can be obtained even if used without purification. It can be simplified and the cost can be reduced.
本発明で用いるポリビニルアルコール（以下、ＰＶＡと表記する場合もある）は重合度が４０００以下であることが好ましい。４０００を超えると水への溶解に要する時間が長くなる傾向がある。 The polyvinyl alcohol (hereinafter sometimes referred to as PVA) used in the present invention preferably has a polymerization degree of 4000 or less. If it exceeds 4000, the time required for dissolution in water tends to increase.
また、ケン化度は７０〜１００モル％であることが好ましい。ケン化度が７０モル％未満であると水に均一に溶解しにくくなる。 The saponification degree is preferably 70 to 100 mol%. When the saponification degree is less than 70 mol%, it becomes difficult to uniformly dissolve in water.
ビニルピロリドン（Ｎ−ビニル−２−ピロリドン、以下、ＮＶＰと表記する場合もある）の量は、ポリビニルアルコールに対して５〜９００重量％であることが好ましい。５重量％未満であると本発明の目的とする効果が十分に得られず、９００重量％を超えるとポリビニルアルコールに由来する特性が得難くなる。 The amount of vinylpyrrolidone (N-vinyl-2-pyrrolidone, hereinafter sometimes referred to as NVP) is preferably 5 to 900% by weight with respect to polyvinyl alcohol. If it is less than 5% by weight, the intended effect of the present invention cannot be sufficiently obtained, and if it exceeds 900% by weight, it is difficult to obtain the characteristics derived from polyvinyl alcohol.
本発明においては、開始剤として過酸化水素を用い、上記したように重合中の反応系の過酸化水素濃度が６００ｐｐｍ以下に保持されるように連続的または断続的に添加する。濃度がこの範囲内でさえあれば、添加は規則的であっても不規則的であってもよい。ここで「重合中」とは、重合開始から好ましくは重合率が９０％に達するまでを言い、より好ましくは９９％に達するまでをいう。 In the present invention, hydrogen peroxide is used as an initiator, and is added continuously or intermittently so that the hydrogen peroxide concentration in the reaction system during polymerization is maintained at 600 ppm or less as described above. As long as the concentration is within this range, the addition may be regular or irregular. Here, “during polymerization” means from the start of polymerization until the polymerization rate reaches 90%, more preferably until 99%.
または、重合中の反応系のｐＨを８〜９に維持する。ここでの「重合中」も上記と同じである。ｐＨをこの範囲内に保持するには例えばアンモニア水を連続的または断続的に添加すればよい。 Alternatively, the pH of the reaction system during polymerization is maintained at 8-9. The “polymerization” here is the same as above. In order to keep the pH within this range, for example, ammonia water may be added continuously or intermittently.
これら過酸化水素濃度の調整及びｐＨの調整のいずれかを行うことにより、グラフト効率を４０％以上に向上させることが可能となり、また双方を行うことにより、グラフト効率を６０％以上に向上させることも可能となる。ここで「グラフト効率」とは、ビニルピロリドンの仕込量に対する消費量（グラフト重合した量）の割合である。 By either adjusting the hydrogen peroxide concentration or adjusting the pH, the graft efficiency can be improved to 40% or more, and by performing both, the graft efficiency can be improved to 60% or more. Is also possible. Here, the “grafting efficiency” is the ratio of the consumption amount (the amount of graft polymerization) to the charged amount of vinylpyrrolidone.
上記以外の反応方法及び反応条件については、一般的なラジカル重合の例に従って適宜選択すればよい。 What is necessary is just to select suitably about reaction methods and reaction conditions other than the above according to the example of general radical polymerization.
以下、本発明を実施例により、より具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.
なお、以下の実施例及び比較例において、過酸化水素濃度及びグラフト効率の測定は次の方法により行った。 In the following examples and comparative examples, the hydrogen peroxide concentration and graft efficiency were measured by the following methods.
［過酸化水素定量法］
重合中の反応液を１時間毎に採取し、以下の操作を行うことで過酸化水素濃度が６００ｐｐｍ以下か越えているかを確認した。
[Quantification method for hydrogen peroxide]
The reaction solution during the polymerization was collected every hour, and the following operation was performed to confirm whether the hydrogen peroxide concentration was 600 ppm or less.
測定サンプルを１０倍量に希釈し、試料溶液とする。試料溶液２５ｍＬに塩化チタン・硫酸試薬２ｍＬを加え３０分放置する。この液につき、試料溶液２５ｍＬに１３％硫酸試薬２ｍＬを加えた液を対照とし、波長４０５ｎｍにおける吸光度を測定する。同様にして６００ｐｐｍ過酸化水素水を測定サンプルとして吸光度を測定し、重合中の反応液の値がそれ以下か越えているかを確認する。 The measurement sample is diluted 10 times to make a sample solution. Add 2 mL of titanium chloride / sulfuric acid reagent to 25 mL of the sample solution and leave it for 30 minutes. For this solution, the absorbance at a wavelength of 405 nm is measured using a solution obtained by adding 2 mL of 13% sulfuric acid reagent to 25 mL of the sample solution. Similarly, the absorbance is measured using 600 ppm hydrogen peroxide solution as a measurement sample, and it is confirmed whether the value of the reaction solution during polymerization is lower or higher.
［グラフト効率算出法］
１０％のポリマー水溶液５ｇを１５０ｍＬのｔ−ブチルアルコールに沈殿させ、沈殿物を遠心分離により分離した後、減圧乾燥機にて乾燥し、得られた乾燥物の重量を測定した。この沈殿物重量と仕込みＰＶＡ重量と仕込みＮＶＰ重量とから次式によりグラフト効率を計算した。
After 5 g of 10% polymer aqueous solution was precipitated in 150 mL of t-butyl alcohol, the precipitate was separated by centrifugation, and then dried in a vacuum dryer, and the weight of the obtained dried product was measured. The graft efficiency was calculated by the following equation from the precipitate weight, the charged PVA weight, and the charged NVP weight.
［実施例１］
純水８００ｇにＰＶＡ（クラレ製、ＰＶＡ−１１７）１００ｇを溶解させ、次いでＮＶＰ１００ｇを添加、混合し、窒素パージにより脱酸素を行った。続いて、反応系を７０℃に温度調節した。これに１重量％硫酸銅１０ｍｇ、２８重量％アンモニア水１．０ｇ及び３０重量％過酸化水素水１．５ｇ（濃度４５０ｐｐｍ対系）を添加し、重合を開始させた。重合中は温度を７０〜８０℃、アンモニアによりｐＨ５．５〜６．５に維持し、３０重量％過酸化水素水１．５ｇを１５分おきに１０回添加することで重合率は９０％以上となった。この間、過酸化水素濃度は６００ｐｐｍ以下であった。続いて残存ＮＶＰ処理工程として３０重量％過酸化水素水４ｇを添加し、アンモニア水によりｐＨ５以上に保持しながら合計２１０分間反応させ、ＰＶＰ変性ＰＶＡの水溶液を得た。
[Example 1]
100 g of PVA (manufactured by Kuraray, PVA-117) was dissolved in 800 g of pure water, and then 100 g of NVP was added and mixed, followed by deoxygenation by nitrogen purge. Subsequently, the temperature of the reaction system was adjusted to 70 ° C. To this was added 10 mg of 1 wt% copper sulfate, 1.0 g of 28 wt% aqueous ammonia and 1.5 g of 30 wt% aqueous hydrogen peroxide (concentration 450 ppm vs. system) to initiate polymerization. During polymerization, the temperature is maintained at 70 to 80 ° C. and pH 5.5 to 6.5 with ammonia, and the polymerization rate is 90% or more by adding 1.5 g of 30 wt% hydrogen peroxide water every 15 minutes. It became. During this time, the hydrogen peroxide concentration was 600 ppm or less. Subsequently, 4 g of 30 wt% hydrogen peroxide water was added as a residual NVP treatment step, and reacted for a total of 210 minutes while maintaining the pH at 5 or higher with aqueous ammonia to obtain an aqueous solution of PVP-modified PVA.
得られた水溶液をスプレー乾燥して粉末状重合物を得た。この試料の１３Ｃ−ＮＭＲ測定により、ポリビニルアルコール主鎖の水酸基及びエステル基に結合する炭素にグラフトすることによって生成した４級炭素のピークを化学シフト５３ｐｐｍ及び５８ｐｐｍ付近に確認することにより、ポリビニルアルコールにビニルピロリドンがグラフト重合したものであることが確認された。 The obtained aqueous solution was spray-dried to obtain a powdery polymer. By confirming the peak of the quaternary carbon generated by grafting to the carbon bonded to the hydroxyl group and ester group of the polyvinyl alcohol main chain by 13C-NMR measurement of this sample, the chemical shift was confirmed to be around 53 ppm and 58 ppm. It was confirmed that vinyl pyrrolidone was graft polymerized.
［実施例２］
純水８００ｇにＰＶＡ（クラレ製、ＰＶＡ−１１７）１００ｇを溶解させ、次いでＮＶＰ１００ｇを添加、混合し、窒素パージにより脱酸素を行った。続いて、反応系を７０℃に温度調節した。これに１重量％硫酸銅１０ｍｇ、２８重量％アンモニア水１．０ｇ及び３０重量％過酸化水素水６ｇ（濃度０．１４％対系）を添加し、重合を開始させた。重合中は温度を７０〜８０℃、アンモニアによりｐＨ８〜９に維持し、重合率が９０％以上になるまで重合した。続いて残存ＮＶＰ処理工程として３０重量％過酸化水素水４ｇを添加し、アンモニア水によりｐＨ５以上に保持しながら合計２１０分間反応させ、ＰＶＰ変性ＰＶＡの水溶液を得た。
[Example 2]
100 g of PVA (manufactured by Kuraray, PVA-117) was dissolved in 800 g of pure water, and then 100 g of NVP was added and mixed, followed by deoxygenation by nitrogen purge. Subsequently, the temperature of the reaction system was adjusted to 70 ° C. To this was added 10 mg of 1 wt% copper sulfate, 1.0 g of 28 wt% aqueous ammonia and 6 g of 30 wt% aqueous hydrogen peroxide (concentration 0.14% vs. system) to initiate polymerization. During the polymerization, the temperature was maintained at 70 to 80 ° C. and pH 8 to 9 with ammonia, and polymerization was performed until the polymerization rate reached 90% or more. Subsequently, 4 g of 30 wt% hydrogen peroxide water was added as a residual NVP treatment step, and reacted for a total of 210 minutes while maintaining the pH at 5 or higher with aqueous ammonia to obtain an aqueous solution of PVP-modified PVA.
上記と同様、１３Ｃ−ＮＭＲ測定により、ポリビニルアルコールにビニルピロリドンがグラフト重合したものであることが確認した。 Similarly to the above, it was confirmed by 13C-NMR measurement that vinylpyrrolidone was graft-polymerized with polyvinyl alcohol.
［実施例３］
純水８００ｇにＰＶＡ（クラレ製、ＰＶＡ−１１７）１００ｇを溶解させ、次いでＮＶＰ１００ｇを添加、混合し、窒素パージにより脱酸素を行った。続いて、反応系を７０℃に温度調節した。これに１重量％硫酸銅１０ｍｇ、２８重量％アンモニア水１．０ｇ及び３０重量％過酸化水素水１．５ｇ（濃度４５０ｐｐｍ対系）を添加し、重合を開始させた。重合中は温度を７０〜８０℃、アンモニアによりｐＨ８〜９に維持し、３０重量％過酸化水素水１．５ｇを１５分おきに１０回添加することで重合率は９０％以上となった。この間、過酸化水素濃度は６００ｐｐｍ以下であった。続いて残存ＮＶＰ処理工程として３０重量％過酸化水素水４ｇを添加し、アンモニア水によりｐＨ５以上に保持しながら合計２１０分間反応させ、ＰＶＰ変性ＰＶＡの水溶液を得た。
[Example 3]
100 g of PVA (manufactured by Kuraray, PVA-117) was dissolved in 800 g of pure water, and then 100 g of NVP was added and mixed, followed by deoxygenation by nitrogen purge. Subsequently, the temperature of the reaction system was adjusted to 70 ° C. To this was added 10 mg of 1 wt% copper sulfate, 1.0 g of 28 wt% aqueous ammonia and 1.5 g of 30 wt% aqueous hydrogen peroxide (concentration 450 ppm vs. system) to initiate polymerization. During the polymerization, the temperature was maintained at 70 to 80 ° C. and pH 8 to 9 with ammonia, and 1.5 g of 30 wt% hydrogen peroxide solution was added 10 times every 15 minutes, whereby the polymerization rate became 90% or more. During this time, the hydrogen peroxide concentration was 600 ppm or less. Subsequently, 4 g of 30 wt% hydrogen peroxide water was added as a residual NVP treatment step, and reacted for a total of 210 minutes while maintaining the pH at 5 or higher with aqueous ammonia to obtain an aqueous solution of PVP-modified PVA.
上記と同様、１３Ｃ−ＮＭＲ測定により、ポリビニルアルコールにビニルピロリドンがグラフト重合したものであることが確認した。 Similarly to the above, it was confirmed by 13C-NMR measurement that vinylpyrrolidone was graft-polymerized with polyvinyl alcohol.
［比較例１］
純水８００ｇにＰＶＡ（クラレ製、ＰＶＡ−１１７）１００ｇを溶解させ、次いでＮＶＰ１００ｇを添加、混合し、窒素パージにより脱酸素を行った。続いて、反応系を７０℃に温度調節した。これに１重量％硫酸銅１０ｍｇ、２８重量％アンモニア水１．０ｇ及び３０重量％過酸化水素水６ｇ（濃度０．１４％対系）を添加し、重合を開始させた。重合中は温度を７０〜８０℃、アンモニアによりｐＨ５．５〜６．５に維持し、重合率９０％以上まで重合した。過酸化水素濃度は反応当初は６００ｐｐｍを越え、その後６００ｐｐｍ以下に低下した。続いて、残存ＮＶＰ処理工程として３０重量％過酸化水素水４ｇを添加し、アンモニア水によりｐＨ５以上に保持しながら合計２１０分間反応させ、ＰＶＰ変性ＰＶＡの水溶液を得た。
[Comparative Example 1]
100 g of PVA (manufactured by Kuraray, PVA-117) was dissolved in 800 g of pure water, and then 100 g of NVP was added and mixed, followed by deoxygenation by nitrogen purge. Subsequently, the temperature of the reaction system was adjusted to 70 ° C. To this was added 10 mg of 1 wt% copper sulfate, 1.0 g of 28 wt% aqueous ammonia and 6 g of 30 wt% aqueous hydrogen peroxide (concentration 0.14% vs. system) to initiate polymerization. During the polymerization, the temperature was maintained at 70 to 80 ° C. and pH 5.5 to 6.5 with ammonia, and polymerization was performed to a polymerization rate of 90% or more. The hydrogen peroxide concentration exceeded 600 ppm at the beginning of the reaction and then decreased to 600 ppm or less. Subsequently, 4 g of 30 wt% aqueous hydrogen peroxide was added as a residual NVP treatment step, and the reaction was carried out for a total of 210 minutes while maintaining the pH at 5 or higher with aqueous ammonia to obtain an aqueous solution of PVP-modified PVA.
［比較例２］
純水８００ｇにＰＶＡ（クラレ製、ＰＶＡ−１１７）１００ｇを溶解させ、次いでＮＶＰ１００ｇを添加、混合し、窒素パージにより脱酸素を行った。続いて、反応系を７０℃に温度調節した。これに１重量％硫酸銅１０ｍｇ、２８重量％アンモニア水１．０ｇ及び３０重量％過酸化水素水６ｇ（濃度０．１４％対系）を添加し、重合を開始させた。重合中は温度を７０〜８０℃、アンモニアによりｐＨ５．５〜６．５に維持し、３０重量％過酸化水素水６ｇ（濃度０．１４％対系）を１５分おきに１０回添加した。この間、過酸化水素濃度は６００ｐｐｍを越えていた。続いて残存ＮＶＰ処理工程として３０重量％過酸化水素水４ｇを添加し、アンモニア水によりｐＨ５以上に保持しながら合計２１０分間反応させ、ＰＶＰ変性ＰＶＡの水溶液を得た。
[Comparative Example 2]
100 g of PVA (manufactured by Kuraray, PVA-117) was dissolved in 800 g of pure water, and then 100 g of NVP was added and mixed, followed by deoxygenation by nitrogen purge. Subsequently, the temperature of the reaction system was adjusted to 70 ° C. To this was added 10 mg of 1 wt% copper sulfate, 1.0 g of 28 wt% aqueous ammonia and 6 g of 30 wt% aqueous hydrogen peroxide (concentration 0.14% vs. system) to initiate polymerization. During the polymerization, the temperature was maintained at 70 to 80 ° C. and pH 5.5 to 6.5 with ammonia, and 6 g of 30 wt% aqueous hydrogen peroxide (concentration 0.14% vs. system) was added 10 times every 15 minutes. During this time, the hydrogen peroxide concentration exceeded 600 ppm. Subsequently, 4 g of 30 wt% hydrogen peroxide water was added as a residual NVP treatment step, and reacted for a total of 210 minutes while maintaining the pH at 5 or higher with aqueous ammonia to obtain an aqueous solution of PVP-modified PVA.
上記実施例及び比較例により得られたグラフトコポリマーのグラフト効率の測定を次の方法により行った。結果を表１に示す。
表に示されたように、反応系の過酸化水素の濃度条件を満たす実施例１、ｐＨ条件を満たす実施例２ではグラフト効率は比較例に比べ大幅に増加し、さらに両条件を満たす実施例３ではグラフト効率は６０％を超えるのが確認された。 As shown in the table, in Example 1 that satisfies the concentration condition of the hydrogen peroxide in the reaction system and Example 2 that satisfies the pH condition, the grafting efficiency is greatly increased as compared with the comparative example, and the examples that satisfy both conditions. 3, it was confirmed that the grafting efficiency exceeded 60%.
本発明のポリビニルアルコール−ポリビニルピロリドングラフトコポリマーは、水溶性フィルムなどに好適に用いられる。 The polyvinyl alcohol-polyvinylpyrrolidone graft copolymer of the present invention is suitably used for water-soluble films and the like.
Claims (4)
重合中の反応系の過酸化水素濃度が６００ｐｐｍ以下に保持されるように過酸化水素を連続的または断続的に添加することにより、請求項１に記載のポリビニルアルコール−ポリビニルピロリドングラフトコポリマーを得ることを特徴とする製造方法。 A method for producing a polyvinyl alcohol-polyvinylpyrrolidone graft copolymer in which vinyl pyrrolidone is blended in a polyvinyl alcohol solution and the reaction is performed using hydrogen peroxide as an initiator,
The polyvinyl alcohol-polyvinylpyrrolidone graft copolymer according to claim 1 is obtained by adding hydrogen peroxide continuously or intermittently so that the hydrogen peroxide concentration of the reaction system during polymerization is maintained at 600 ppm or less. The manufacturing method characterized by this.
重合中の反応系のｐＨを８〜９に保持することにより、請求項１に記載のポリビニルアルコール−ポリビニルピロリドングラフトコポリマーを得ることを特徴とする製造方法。 A method for producing a polyvinyl alcohol-polyvinylpyrrolidone graft copolymer in which vinyl pyrrolidone is blended in a polyvinyl alcohol solution and the reaction is performed using hydrogen peroxide as an initiator,
The manufacturing method characterized by obtaining the polyvinyl alcohol-polyvinylpyrrolidone graft copolymer of Claim 1 by hold | maintaining the pH of the reaction system during superposition | polymerization to 8-9.
グラフト効率が６０％以上である
ことを特徴とする、請求項１に記載のポリビニルアルコール−ポリビニルピロリドングラフトコポリマー。 In a method for producing a polyvinyl alcohol-polyvinylpyrrolidone graft copolymer using vinyl pyrrolidone in a polyvinyl alcohol solution and using hydrogen peroxide as an initiator, the hydrogen peroxide concentration in the reaction system during polymerization is 600 ppm or less. Obtained by continuously or intermittently adding hydrogen and maintaining the pH during polymerization at 8-9,
The polyvinyl alcohol-polyvinylpyrrolidone graft copolymer according to claim 1, wherein the graft efficiency is 60% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007122236A JP4971867B2 (en) | 2007-05-07 | 2007-05-07 | Method for producing polyvinyl alcohol-polyvinylpyrrolidone graft copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007122236A JP4971867B2 (en) | 2007-05-07 | 2007-05-07 | Method for producing polyvinyl alcohol-polyvinylpyrrolidone graft copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008274181A true JP2008274181A (en) | 2008-11-13 |
| JP4971867B2 JP4971867B2 (en) | 2012-07-11 |
Family
ID=40052572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007122236A Active JP4971867B2 (en) | 2007-05-07 | 2007-05-07 | Method for producing polyvinyl alcohol-polyvinylpyrrolidone graft copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4971867B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010084896A1 (en) * | 2009-01-21 | 2010-07-29 | 日本パーカライジング株式会社 | Hydrophilizing agent for aluminum-containing metal material, hydrophilizing method, and hydrophilized aluminum-containing metal material |
| TWI488689B (en) * | 2012-03-07 | 2015-06-21 | Dai Ichi Kogyo Seiyaku Co Ltd | A dispersant containing a polyvinyl acetal-polyester graft copolymer, a solid particle dispersion using the same, and a composition containing solid particles |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61132377A (en) * | 1984-11-30 | 1986-06-19 | Lion Corp | Ink jet recording sheet |
| JP2006508231A (en) * | 2002-11-27 | 2006-03-09 | アイエスピー インヴェストメンツ インコーポレイテッド | Tough polymer |
| JP2006213840A (en) * | 2005-02-04 | 2006-08-17 | Dai Ichi Kogyo Seiyaku Co Ltd | Polyvinyl alcohol-modified graft polymer, method for producing the same and inkjet recording medium containing the same |
| JP2007084461A (en) * | 2005-09-20 | 2007-04-05 | Dai Ichi Kogyo Seiyaku Co Ltd | Cosmetic composition |
-
2007
- 2007-05-07 JP JP2007122236A patent/JP4971867B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61132377A (en) * | 1984-11-30 | 1986-06-19 | Lion Corp | Ink jet recording sheet |
| JP2006508231A (en) * | 2002-11-27 | 2006-03-09 | アイエスピー インヴェストメンツ インコーポレイテッド | Tough polymer |
| JP2006213840A (en) * | 2005-02-04 | 2006-08-17 | Dai Ichi Kogyo Seiyaku Co Ltd | Polyvinyl alcohol-modified graft polymer, method for producing the same and inkjet recording medium containing the same |
| JP2007084461A (en) * | 2005-09-20 | 2007-04-05 | Dai Ichi Kogyo Seiyaku Co Ltd | Cosmetic composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010084896A1 (en) * | 2009-01-21 | 2010-07-29 | 日本パーカライジング株式会社 | Hydrophilizing agent for aluminum-containing metal material, hydrophilizing method, and hydrophilized aluminum-containing metal material |
| JP5503556B2 (en) * | 2009-01-21 | 2014-05-28 | 日本パーカライジング株式会社 | Hydrophilic treatment agent for aluminum-containing metal material, hydrophilic treatment method, and hydrophilized aluminum-containing metal material |
| TWI488689B (en) * | 2012-03-07 | 2015-06-21 | Dai Ichi Kogyo Seiyaku Co Ltd | A dispersant containing a polyvinyl acetal-polyester graft copolymer, a solid particle dispersion using the same, and a composition containing solid particles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4971867B2 (en) | 2012-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2647599C2 (en) | Porous particles of graft copolymer, the method of their production and adsorbing material, which they apply | |
| JP4086961B2 (en) | Graft polymer | |
| JP6704350B2 (en) | Dispersion stabilizer for suspension polymerization and method for producing vinyl resin | |
| TW201143879A (en) | Macromolecular water-treatment membrane and manufacturing method therefor | |
| JP2007121346A (en) | Coated film forming resin composition | |
| JP4971867B2 (en) | Method for producing polyvinyl alcohol-polyvinylpyrrolidone graft copolymer | |
| JP5501678B2 (en) | Ring structure-containing copolymer, method for producing the same, and ring structure-containing copolymer composition | |
| JP2001213920A (en) | Method for manufacturing crosslinked ion-exchanger on the basis of unsaturated aliphatic nitrile | |
| JP2005097545A (en) | Porous resin bead and method for producing the same | |
| JP2008520821A (en) | Dispersant for producing vinyl chloride resin and method for producing vinyl chloride resin using the same | |
| JP5137080B2 (en) | Process for producing water-soluble polymer of polyamidine | |
| JP6165599B2 (en) | Graft copolymer of ethylene-vinyl alcohol copolymer, process for producing the same, and metal adsorbent using the same | |
| TWI464179B (en) | Polyvinyl alcohol and method for preparing thereof | |
| JP4881518B2 (en) | Method for producing vinyl lactam polymer | |
| JP2001072728A (en) | Block polymer and its production | |
| TWI755520B (en) | Dispersion stabilizer for suspension polymerization of vinyl compound, method for producing the same, and method for producing vinyl polymer | |
| JP2017025331A (en) | Enhanced nvf copolymer process | |
| JP4859613B2 (en) | Method for producing N-pyrrolidone-based graft polymer composition and N-pyrrolidone-based graft polymer composition | |
| WO2019244967A1 (en) | Method for producing vinyl polymer | |
| JP6136214B2 (en) | Process for producing fumaric acid diester polymer particles | |
| JPS59189111A (en) | Production of block copolymer | |
| JP2005272629A (en) | N-vinylamide polymer and method for producing n-vinylamide polymer | |
| JP2003026726A (en) | Modified polyvinyl lactam | |
| WO2015068806A1 (en) | Method for producing vinylamine (co)polymer | |
| JP2003171408A (en) | Method for producing aqueous emulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20091119 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110916 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110927 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111117 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120403 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120406 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150413 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4971867 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |