JP2005306906A - Method for producing vinylpyrrolidone polymer - Google Patents
Method for producing vinylpyrrolidone polymer Download PDFInfo
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- JP2005306906A JP2005306906A JP2004121978A JP2004121978A JP2005306906A JP 2005306906 A JP2005306906 A JP 2005306906A JP 2004121978 A JP2004121978 A JP 2004121978A JP 2004121978 A JP2004121978 A JP 2004121978A JP 2005306906 A JP2005306906 A JP 2005306906A
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- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229920000642 polymer Polymers 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 23
- 239000000243 solution Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000000178 monomer Substances 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- -1 iron ions Chemical class 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical class OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical class C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical class C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical class CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Chemical class 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical class OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical class CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical class C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical class CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical class C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical class C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical class OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical class [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
本発明は、ビニルピロリドン重合体の製造方法に関する。 The present invention relates to a method for producing a vinylpyrrolidone polymer.
通常のポリビニルピロリドンの製造は、「原料仕込み」、「重合」、「残存モノマー処理」及び「反応装置洗浄」の各プロセスからなり、これらを繰り返すことにより連続生産を行うことが多い（例えば、特開２００３−４０９１１号公報参照）。 Ordinary production of polyvinylpyrrolidone consists of the processes of “raw material charging”, “polymerization”, “residual monomer treatment” and “reactor cleaning”, and is often repeated for continuous production (for example, special (See JP 2003-40911).
しかしながらビニルピロリドンは（メタ）アクリル酸系モノマーなどと比べて反応性に乏しく、重合に長時間を要する。また、反応容器表面等との相互作用が大きいため、残存モノマー処理にも時間を要し、さらに洗浄が困難でこの作業にも長時間を要するという問題があった。
本発明は上記に鑑みてなされたものであり、重合時間等が短縮され、また反応容器の洗浄も容易で、製造サイクル全体の所要時間短縮が可能なビニルピロリドン重合体の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 method for producing a vinylpyrrolidone polymer in which the polymerization time and the like are shortened, the reaction vessel is easily cleaned, and the required time of the entire production cycle can be shortened. With the goal.
本発明のビニルピロリドン重合体の製造方法は、水溶液でのラジカル重合にてビニルピロリドン重合体を製造する方法において、上記の課題を解決するために、反応系に接触する部分に鉄含有率６０％以下の金属を使用した反応装置を用いて反応を行うものとする（請求項１）。 The method for producing a vinyl pyrrolidone polymer of the present invention is a method for producing a vinyl pyrrolidone polymer by radical polymerization in an aqueous solution. The reaction is carried out using a reaction apparatus using the following metals (Claim 1).
又は、反応系に接触する部分に金属以外の素材を使用した反応装置を用いて反応を行うものとする（請求項２）。 Alternatively, the reaction is performed using a reaction apparatus using a material other than metal in a portion that contacts the reaction system (claim 2).
後者の場合、反応系に接触する部分が樹脂コーティングされているものを用いることができる（請求項３）。 In the latter case, a resin-coated portion that contacts the reaction system can be used (Claim 3).
もしくは、反応系に接触する部分がグラスライニングされているものを用いることができる（請求項４）。 Alternatively, a glass-lined portion that contacts the reaction system can be used (claim 4).
本発明で用いる反応装置は、反応容積が５００Ｌ以上であることが好ましい（請求項５）。 The reaction apparatus used in the present invention preferably has a reaction volume of 500 L or more (Claim 5).
本発明の方法は、Ｋ値が５０以上であるビニルピロリドン重合体の製造に特に適している（請求項６）。 The method of the present invention is particularly suitable for producing a vinylpyrrolidone polymer having a K value of 50 or more (claim 6).
本発明の製造方法を用いることにより、通常のポリビニルピロリドン製造プロセスである、「原料仕込み」、「重合」、「残存モノマー処理」、「反応装置洗浄」のサイクルをより短時間で繰り返すことができ、生産効率が高くなり、製造コストを削減することができる。具体的には、重合時間及び残存モノマー処理時間が短縮され、洗浄が容易になり、洗浄に必要な時間と水量が大幅に削減できる。本発明の方法は、バッチ式の製造方法で効果が得られることはもちろん、フロー式での製造において、品種切替が多く、洗浄が頻繁に必要な系でも効果が得られる。 By using the production method of the present invention, it is possible to repeat the cycle of “raw material preparation”, “polymerization”, “residual monomer treatment”, and “reactor cleaning”, which are ordinary polyvinylpyrrolidone production processes, in a shorter time. Production efficiency can be increased and manufacturing costs can be reduced. Specifically, the polymerization time and the residual monomer treatment time are shortened, cleaning becomes easy, and the time and amount of water required for cleaning can be greatly reduced. The method of the present invention is effective not only in a batch type manufacturing method, but also in a system in which a variety of types are frequently switched in a flow type manufacturing and washing is frequently required.
本発明においては、反応装置の反応系に接触する部分に鉄含有率６０％以下の金属を使用するか、あるいは金属以外の素材を使用したものを用いて反応を行う。 In the present invention, the reaction is carried out using a metal having an iron content of 60% or less or a material using a material other than metal in the portion of the reactor that contacts the reaction system.
ここで、「反応装置」とは反応容器及び撹拌装置を含む反応に関与する装置全体を言う。また、「反応」とは重合反応及び残存モノマー処理反応を言うが、残存モノマー処理を行わず重合反応のみを行う場合も本発明の範囲に含まれるものとする。 Here, the “reaction apparatus” refers to the entire apparatus involved in the reaction including the reaction vessel and the stirring apparatus. Further, “reaction” refers to a polymerization reaction and a residual monomer treatment reaction, but the case where only the polymerization reaction is performed without performing the residual monomer treatment is also included in the scope of the present invention.
上記反応装置は、そのうち少なくとも反応系に接触する部分を鉄含有率６０％以下の金属又は金属以外の素材で構成し、本発明の効果を最大限に得るためには、反応系に接触する部分全体をこれらの素材で構成することが好ましい。 In the above reaction apparatus, at least a portion that contacts the reaction system is made of a metal having an iron content of 60% or less or a material other than metal, and in order to obtain the maximum effect of the present invention, a portion that contacts the reaction system The whole is preferably composed of these materials.
素材が金属の場合、鉄含有率は６０％以下であるものとし、５０％以下が好ましく、２０％以下がより好ましい。使用可能な鉄以外の金属の例としては、クロム、ニッケル、モリブデン、チタン、ジルコニウム等が挙げられる。 When the material is a metal, the iron content is 60% or less, preferably 50% or less, and more preferably 20% or less. Examples of metals other than iron that can be used include chromium, nickel, molybdenum, titanium, and zirconium.
金属以外の素材としては、四フッ化エチレン（例えばデュポン社製テフロン（登録商標））等の樹脂やガラスが挙げられる。これらの素材の場合は、強度及びコストの面から、金属素材の表面をこれらの樹脂でコーティングしたり、グラスライニングしたりしたものが好適に用いられる。 Examples of materials other than metal include resins such as tetrafluoroethylene (for example, Teflon (registered trademark) manufactured by DuPont) and glass. In the case of these materials, those obtained by coating the surface of a metal material with these resins or glass lining are preferably used from the viewpoint of strength and cost.
反応系に接触する部分に上記のような素材を使用することにより重合時間が短くなる。また、残存モノマー処理では、特に酸を用いて残存モノマー量を低減させる際に時間を短縮できる。さらに、反応装置洗浄が容易となり、従って洗浄に要する時間も短くなり、必要とする水量も大幅に削減できる。 The polymerization time is shortened by using the above-mentioned material in the portion that contacts the reaction system. In the residual monomer treatment, the time can be shortened particularly when the amount of residual monomer is reduced using an acid. Furthermore, the reactor can be easily cleaned, and thus the time required for cleaning is shortened, and the amount of water required can be greatly reduced.
その理由は明らかではないが、重合中に反応系と接触する素材表面に鉄金属もしくは鉄イオンが存在すると成長ラジカルと反応し、ラジカルが不活性化するため、反応速度が小さくなると推察され、上記のように、鉄含量の少ない素材又は鉄を含まない素材を用いることにより、この問題が解決されると考えられる。 The reason for this is not clear, but it is speculated that the reaction rate decreases because the radical reacts with the growth radicals when iron metal or iron ions are present on the surface of the material in contact with the reaction system during polymerization. Thus, it is considered that this problem can be solved by using a material having a low iron content or a material not containing iron.
また、残存モノマー処理中は水溶液の粘度が高くなっており、特にこの水溶液は鉄との相互作用が強い。残存モノマー処理では、重合水溶液に、蟻酸、酢酸、硫酸等の酸を添加し、ｐＨを低下させてビニルピロリドンを加水分解する方法がよく使用されるが、鉄製の反応容器の場合は、撹拌中に蟻酸、硫酸等の酸を添加しても反応容器壁面付近の水溶液と容易に混ざり合うことができず、その結果、反応に長時間を要すると推察される。本発明によれば、四フッ化エチレン等の樹脂やガラスと水溶液との相互作用が小さく、上記混合がより速やかに行われるため、処理時間が短縮されると考えられる。 Further, the viscosity of the aqueous solution is high during the residual monomer treatment, and this aqueous solution has a strong interaction with iron. In the residual monomer treatment, a method of hydrolyzing vinylpyrrolidone by adding an acid such as formic acid, acetic acid or sulfuric acid to the aqueous polymerization solution and lowering the pH is often used. Even if an acid such as formic acid or sulfuric acid is added to the aqueous solution, it cannot be easily mixed with the aqueous solution in the vicinity of the reaction vessel wall. As a result, it is assumed that the reaction takes a long time. According to the present invention, since the interaction between the resin such as tetrafluoroethylene or glass and the aqueous solution is small and the mixing is performed more quickly, the processing time is considered to be shortened.
さらに、反応装置洗浄に関しても、ビニルピロリドン重合体と金属鉄表面との相互作用が強いのに対し、四フッ化エチレン等の樹脂やガラスはビニルピロリドン重合体との相互作用が小さいため、少量の水で洗浄が可能になり、所要時間が短縮されると考えられる。 Furthermore, with regard to reactor cleaning, the interaction between the vinylpyrrolidone polymer and the metallic iron surface is strong, whereas resins and glass such as ethylene tetrafluoride have a small interaction with the vinylpyrrolidone polymer, so a small amount of It can be washed with water, and the required time will be shortened.
本発明で用いる反応装置は、発明の目的を考慮すると、反応容積が５００Ｌ以上であることが好ましく、より好ましくは１０００Ｌ以上である。すなわち、反応容積が小さいと洗浄が比較的容易であるが、反応容積が大きいほど洗浄が困難であるため、本発明による効果がより顕著となる。 In consideration of the object of the invention, the reaction apparatus used in the present invention preferably has a reaction volume of 500 L or more, more preferably 1000 L or more. That is, when the reaction volume is small, cleaning is relatively easy. However, the larger the reaction volume is, the more difficult the cleaning is, so the effect of the present invention becomes more remarkable.
反応装置として上記のものを用いる以外は、本発明の製造方法は公知の方法に準じて行うことができる。すなわち、例えばビニルピロリドンの水溶液に適当なラジカル重合開始剤を加えて重合を行うことができる。 The production method of the present invention can be carried out according to a known method except that the above reactor is used. That is, for example, polymerization can be carried out by adding an appropriate radical polymerization initiator to an aqueous solution of vinylpyrrolidone.
本発明により製造するビニルピロリドン重合体とは、ビニルピロリドン（Ｎ−ビニル−２−ピロリドン、以下、ＶＰとも表記する）の単独重合体又はＶＰと他の単量体との共重合体であり、他の単量体はＶＰと共重合可能なものであればよく、特に限定されないが、例としては、アクリル酸、メタクリル酸、アクリル酸のアルキルエステル（メチルアクリレート、エチルアクリレート等）、メタクリル酸のアルキルエステル（メチルメタクリレート、エチルメタクリレート等）、アクリル酸のアミノアルキルエステル（ジエチルアミノエチルアクリレート等）、メタクリル酸のアミノアルキルエステル、アクリル酸とグリコールとのモノエステル、メタクリル酸とグリコールとのモノエステル（ヒドロキシエチルメタクリレート等）、アクリル酸のアルカリ金属塩、メタクリル酸のアルカリ金属塩、アクリル酸のアンモニウム塩、メタクリル酸のアンモニウム塩、アクリル酸のアミノアルキルエステルの第４級アンモニウム誘導体、メタクリル酸のアミノアルキルエステルの第４級アンモニウム誘導体、ジエチルアミノエチルアクリレートとメチルサルフェートとの第４級アンモニウム化合物、ビニルメチルエーテル、ビニルエチルエーテル、ビニルスルホン酸のアルカリ金属塩、ビニルスルホン酸のアンモニウム塩、スチレンスルホン酸、スチレンスルホン酸塩、アリルスルホン酸、アリルスルホン酸塩、メタリルスルホン酸、メタリルスルホン酸塩、酢酸ビニル、ビニルステアレート、Ｎ−ビニルイミダゾール、Ｎ−ビニルアセトアミド、Ｎ−ビニルホルムアミド、Ｎ−ビニルカプロラクタム、Ｎ−ビニルカルバゾール、アクリルアミド、メタクリルアミド、Ｎ−アルキルアクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ，Ｎ−メチレンビスアクリルアミド、グリコールジアクリレート、グリコールジメタクリレート、ジビニルベンゼン、グリコールジアリルエーテル等がある。 The vinylpyrrolidone polymer produced according to the present invention is a homopolymer of vinylpyrrolidone (N-vinyl-2-pyrrolidone, hereinafter also referred to as VP) or a copolymer of VP and another monomer, Other monomers are not particularly limited as long as they are copolymerizable with VP, and examples thereof include acrylic acid, methacrylic acid, alkyl esters of acrylic acid (such as methyl acrylate and ethyl acrylate), and methacrylic acid. Alkyl esters (such as methyl methacrylate and ethyl methacrylate), aminoalkyl esters of acrylic acid (such as diethylaminoethyl acrylate), aminoalkyl esters of methacrylic acid, monoesters of acrylic acid and glycol, monoesters of methacrylic acid and glycol (hydroxy Ethyl methacrylate), acrylic Alkali metal salt of acid, alkali metal salt of methacrylic acid, ammonium salt of acrylic acid, ammonium salt of methacrylic acid, quaternary ammonium derivative of aminoalkyl ester of acrylic acid, quaternary ammonium derivative of aminoalkyl ester of methacrylic acid Quaternary ammonium compounds of diethylaminoethyl acrylate and methyl sulfate, vinyl methyl ether, vinyl ethyl ether, alkali metal salts of vinyl sulfonic acid, ammonium salts of vinyl sulfonic acid, styrene sulfonic acid, styrene sulfonate, allyl sulfonic acid , Allyl sulfonate, methallyl sulfonic acid, methallyl sulfonate, vinyl acetate, vinyl stearate, N-vinyl imidazole, N-vinyl acetamide, N-vinyl formamide, N-vinyl Caprolactam, N- vinyl carbazole, acrylamide, methacrylamide, N- alkyl acrylamide, N- methylolacrylamide, N, N- methylenebisacrylamide, glycol diacrylate, glycol dimethacrylate, divinyl benzene, glycol diallyl ether.
ＶＰと他の単量体の割合も特に限定されないが、ＶＰの割合が少なすぎると本発明の目的から外れるため、目安としてはＶＰの割合が２０重量％以上であるものとする。 The proportion of VP and other monomers is not particularly limited, but if the proportion of VP is too small, it will be out of the object of the present invention. Therefore, as a guide, the proportion of VP is 20% by weight or more.
ビニルピロリドン重合体のＫ値は５０以上であることが好ましく、より好ましくは７０以上、さらに好ましくは８０以上である。Ｋ値とは、ドイツの化学者フィケンチャーにより提案された重合度を表わす定数であり、Ｋ値が高いほど、本発明による洗浄に必要な水量削減の効果が大きくなる。 The K value of the vinylpyrrolidone polymer is preferably 50 or more, more preferably 70 or more, and still more preferably 80 or more. The K value is a constant representing the degree of polymerization proposed by the German chemist Fikencher. The higher the K value, the greater the effect of reducing the amount of water required for cleaning according to the present invention.
以下に本発明の実施例を示すが、本発明は以下の実施例によって限定されるものではない。 Examples of the present invention are shown below, but the present invention is not limited to the following examples.
以下における評価方法としては、「原料仕込み」「重合」「残存モノマー処理」及び「反応装置洗浄」の一サイクルの総所要時間を測定した。 As an evaluation method below, the total time required for one cycle of “raw material charge”, “polymerization”, “residual monomer treatment” and “reactor cleaning” was measured.
なお、「反応装置洗浄」の終了点は、水洗浄時に発生する排水を１０分おきにサンプリングし、固形分が０．０１％以下となる点とした。 The end point of the “reactor cleaning” was defined as a point at which the waste water generated during water cleaning was sampled every 10 minutes and the solid content was 0.01% or less.
固形分は［１００−（１０５℃×６時間後の乾燥減量）］ｗｔ％にて求めた。 Solid content was calculated | required in [100- (105 degreeC x loss on drying after 6 hours)] wt%.
［実施例１］
窒素置換したグラスライニング製反応釜に、ＶＰ２００ｋｇ、純水８００ｋｇを入れ、窒素パージしながら内温を６５℃に加熱した。次いで２，２’−アゾビス（２−メチル−ブチロニトリル）をＶＰに対して０．１５重量％（３００ｇ）添加し、重合を開始した。５０分後、反応液は反応熱により８５℃となった。以後、重合終了まで反応液が８５〜９０℃に保持されるようにジャケットに温水を流した。反応開始から１．５時間後、さらに２，２’−アゾビス（２−メチル−ブチロニトリル）をＶＰに対して０．１５重量％（３００ｇ）添加した。反応開始から２時間後重合率が９９％を超えたことを確認し、酢酸をＶＰに対して１６００重量ｐｐｍ（３２０ｇ）添加して、反応液のｐＨを４以下にさせ、１．５時間加熱保持した。次にアンモニアによりｐＨ６．８とした。得られたビニルピロリドン重合体は１重量ｐｐｍのＶＰ単量体を含有し、Ｋ値 ８１．９、固形分 １９．８％であった。
[Example 1]
VP200 kg and pure water 800 kg were placed in a glass-lined reaction kettle purged with nitrogen, and the internal temperature was heated to 65 ° C. while purging with nitrogen. Subsequently, 2,2′-azobis (2-methyl-butyronitrile) was added in an amount of 0.15% by weight (300 g) based on VP to initiate polymerization. After 50 minutes, the reaction liquid reached 85 ° C. due to heat of reaction. Thereafter, warm water was passed through the jacket so that the reaction solution was maintained at 85 to 90 ° C. until the polymerization was completed. 1.5 hours after the start of the reaction, 0.15% by weight (300 g) of 2,2′-azobis (2-methyl-butyronitrile) was further added to VP. 2 hours after the start of the reaction, it was confirmed that the polymerization rate exceeded 99%, and 1600 ppm by weight (320 g) of acetic acid was added to VP to reduce the pH of the reaction solution to 4 or less and heated for 1.5 hours. Retained. Next, the pH was adjusted to 6.8 with ammonia. The resulting vinylpyrrolidone polymer contained 1 ppm by weight of VP monomer, had a K value of 81.9 and a solid content of 19.8%.
このビニルピロリドン重合体を取り出した後、釜内を水により洗浄した。水洗浄は、水圧５０ｋｇ／ｃｍ２、２５Ｌ／ｍｉｎにて行った。 After taking out this vinylpyrrolidone polymer, the inside of the kettle was washed with water. Water washing was performed at a water pressure of 50 kg / cm 2 and 25 L / min.
その結果、総所要時間は７．５時間であった。 As a result, the total required time was 7.5 hours.
［実施例２］
窒素置換したテフロン（登録商標）コーティング製反応釜に、ＶＰ４００ｋｇ、純水１６００ｋｇを入れ、窒素パージしながら内温を６５℃に加熱した。次いで２，２’−アゾビス（２−メチル−ブチロニトリル）をＶＰに対して０．１５重量％（６００ｇ）添加し、重合を開始した。５０分後、反応液は反応熱により８５℃となった。以後、重合終了まで反応液が８５〜９０℃に保持されるようにジャケットに温水を流した。反応開始から１．５時間後、さらに２，２’−アゾビス（２−メチル−ブチロニトリル）をＶＰに対して０．１５重量％（６００ｇ）添加した。反応開始から２．５時間後重合率が９９％を超えたことを確認し、酢酸をＶＰに対して１６００重量ｐｐｍ（６４０ｇ）添加して、反応液のｐＨを４以下にさせ、１．５時間加熱保持した。次にアンモニアによりｐＨ６．９とした。得られたビニルピロリドン重合体は２重量ｐｐｍのＶＰ単量体を含有し、Ｋ値 ８０．５、固形分 ２０．１％であった。
[Example 2]
In a Teflon (registered trademark) -coated reaction kettle purged with nitrogen, 400 kg of VP and 1600 kg of pure water were added, and the internal temperature was heated to 65 ° C. while purging with nitrogen. Subsequently, 2,2′-azobis (2-methyl-butyronitrile) was added in an amount of 0.15% by weight (600 g) based on VP to initiate polymerization. After 50 minutes, the reaction liquid reached 85 ° C. due to heat of reaction. Thereafter, warm water was passed through the jacket so that the reaction solution was maintained at 85 to 90 ° C. until the polymerization was completed. 1.5 hours after the start of the reaction, 0.15% by weight (600 g) of 2,2′-azobis (2-methyl-butyronitrile) was further added to VP. After 2.5 hours from the start of the reaction, it was confirmed that the polymerization rate exceeded 99%, and 1600 ppm by weight (640 g) of acetic acid was added to VP to reduce the pH of the reaction solution to 4 or less. Heated for an hour. Next, the pH was adjusted to 6.9 with ammonia. The resulting vinylpyrrolidone polymer contained 2 ppm by weight of VP monomer, had a K value of 80.5 and a solid content of 20.1%.
このビニルピロリドン重合体を取り出した後、釜内を水により洗浄した。水洗浄は、水圧５０ｋｇ／ｃｍ２、２５Ｌ／ｍｉｎにて行った。 After taking out this vinylpyrrolidone polymer, the inside of the kettle was washed with water. Water washing was performed at a water pressure of 50 kg / cm 2 and 25 L / min.
その結果、総所要時間は８時間であった。 As a result, the total time required was 8 hours.
［比較例１］
窒素置換したＳＵＳ３０４製（鉄含有率７１％）反応釜に、ＶＰ２００ｋｇ、純水８００ｋｇを入れ、窒素パージしながら内温を６５℃に加熱した。次いで２，２’−アゾビス（２−メチル−ブチロニトリル）をＶＰに対して０．１５重量％（３００ｇ）添加し、重合を開始した。６０分後反応液は、反応熱により８５℃となった。以後、重合終了まで反応液が８５〜９０℃に保持されるようにジャケットに温水を流した。反応開始から２時間後、さらに２，２’−アゾビス（２−メチル−ブチロニトリル）をＶＰに対して０．１５重量％（３００ｇ）添加した。反応開始から３時間後重合率が９９％を超えたことを確認し、酢酸をＶＰに対して１６００重量ｐｐｍ（３２０ｇ）添加して、反応液のｐＨを４以下にさせ、３時間加熱保持した。次にアンモニアによりｐＨ６．８とした。得られたビニルピロリドン重合体は２重量ｐｐｍのＶＰ単量体を含有し、Ｋ値 ８３．８、固形分 １９．８％であった。
[Comparative Example 1]
SUS200 (iron content 71%) reaction kettle purged with nitrogen was charged with 200 kg of VP and 800 kg of pure water, and the internal temperature was heated to 65 ° C. while purging with nitrogen. Subsequently, 2,2′-azobis (2-methyl-butyronitrile) was added in an amount of 0.15% by weight (300 g) based on VP to initiate polymerization. After 60 minutes, the reaction solution reached 85 ° C. due to heat of reaction. Thereafter, warm water was passed through the jacket so that the reaction solution was maintained at 85 to 90 ° C. until the polymerization was completed. Two hours after the start of the reaction, 2,5′-azobis (2-methyl-butyronitrile) was further added in an amount of 0.15% by weight (300 g) based on VP. After 3 hours from the start of the reaction, it was confirmed that the polymerization rate exceeded 99%, and 1600 wt ppm (320 g) of acetic acid was added to VP to reduce the pH of the reaction solution to 4 or less and kept heated for 3 hours. . Next, the pH was adjusted to 6.8 with ammonia. The resulting vinylpyrrolidone polymer contained 2 wt ppm of VP monomer, had a K value of 83.8 and a solid content of 19.8%.
このビニルピロリドン重合体を取り出した後、釜内を水により洗浄した。水洗浄は、水圧５０ｋｇ／ｃｍ２、２５Ｌ／ｍｉｎにておこなった。 After taking out this vinylpyrrolidone polymer, the inside of the kettle was washed with water. Water washing was performed at a water pressure of 50 kg / cm 2 and 25 L / min.
その結果、総所要時間は１２時間であった。 As a result, the total required time was 12 hours.
本発明の製造方法は、比較的大量のビニルピロリドン重合体を製造する際に特に有用である。 The production method of the present invention is particularly useful when producing a relatively large amount of vinylpyrrolidone polymer.
Claims (6)
反応系に接触する部分に鉄含有率６０％以下の金属を使用した反応装置を用いて反応を行うことを特徴とするビニルピロリドン重合体の製造方法。 In a method for producing a vinylpyrrolidone polymer by radical polymerization in an aqueous solution,
A method for producing a vinylpyrrolidone polymer, characterized in that the reaction is carried out using a reaction apparatus using a metal having an iron content of 60% or less in a portion in contact with the reaction system.
反応系に接触する部分に金属以外の素材を使用した反応装置を用いて反応を行うことを特徴とするビニルピロリドン重合体の製造方法。 In a method for producing a vinylpyrrolidone polymer by radical polymerization in an aqueous solution,
A method for producing a vinylpyrrolidone polymer, characterized in that the reaction is carried out using a reaction apparatus using a material other than a metal at a portion in contact with the reaction system.
The method for producing a vinylpyrrolidone polymer according to any one of claims 1 to 5, wherein a vinylpyrrolidone polymer having a K value of 50 or more is produced.
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