JPS6366205A - Production of water-soluble polymer - Google Patents
Production of water-soluble polymerInfo
- Publication number
- JPS6366205A JPS6366205A JP20910286A JP20910286A JPS6366205A JP S6366205 A JPS6366205 A JP S6366205A JP 20910286 A JP20910286 A JP 20910286A JP 20910286 A JP20910286 A JP 20910286A JP S6366205 A JPS6366205 A JP S6366205A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- acid
- water
- polyvinylformamide
- organic acid
- 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
- 229920003169 water-soluble polymer Polymers 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 81
- 150000007524 organic acids Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 7
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 15
- 239000007864 aqueous solution Substances 0.000 abstract description 13
- 239000003518 caustics Substances 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000006460 hydrolysis reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 235000005985 organic acids Nutrition 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920003176 water-insoluble polymer Polymers 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- -1 formic acid alkali salt Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は水溶性ポリマーの製造法に関するものであり、
詳しくは、ポリビニルホルムアミドの少な（とも一部が
加水分解された水溶性ポリマーを効率的に製造する方法
に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a water-soluble polymer,
Specifically, the present invention relates to a method for efficiently producing a water-soluble polymer in which a small amount (at least a portion of which is partially hydrolyzed) of polyvinylformamide is produced.
ポリビニルホルムアミドの少なくとも一部を加水分解し
て得られる水溶性ポリマーは凝集性能に優れたポリマー
であり１通常、加水分解された構造から「ポリビニルア
ミン」と呼ばれ。A water-soluble polymer obtained by hydrolyzing at least a portion of polyvinylformamide is a polymer with excellent flocculation performance, and is usually called "polyvinylamine" because of its hydrolyzed structure.
凝集剤としての用途が期待されている。また。It is expected to be used as a flocculant. Also.
その他の用途として１紙用薬剤、保護コロイドなどとし
ての利用も考えられ℃いる。このポリマーは１通常、Ｎ
−ビニルホルムアミドを重合して得たポリビニルホルム
アミドを苛性アルカリ又は無機酸の存在下、加水分解す
ることにより製造される（特開昭りｇ−ユ３ｇ０ｑ）。Other possible uses include paper chemicals and protective colloids. This polymer is usually 1N
- Manufactured by hydrolyzing polyvinylformamide obtained by polymerizing vinylformamide in the presence of a caustic alkali or an inorganic acid (Japanese Patent Application Laid-Open No. 2003-130033).
この方法においては、ポリビニルホルムアミドを水酸液
状態にて加水分解する必要があるが。In this method, it is necessary to hydrolyze polyvinylformamide in a hydroxyl solution.
ポリビニルホルムアミド水浴液は粘展が尚く。Polyvinylformamide water bath liquid has a high viscosity.
例えば、１５％以下の水浴液でないと侵拌が困難である
。したがって１通常、ｌ〜７３％水溶液として処理され
るため、得られるポリマーも希薄水浴液となり、このよ
うな水ｍ液では取扱いが面倒な上、流通コストがかかり
不利である。For example, stirring is difficult unless the water bath solution is 15% or less. Therefore, since it is usually processed as a 1 to 73% aqueous solution, the resulting polymer is also a dilute water bath solution, and such an aqueous solution is disadvantageous in that it is troublesome to handle and increases distribution costs.
そこで、ポリマー成分なａルなペースト状又は粉粒体と
して取得することが望ましいが、希薄水ｍ腋からポリマ
ー成分を分離するためには。Therefore, it is desirable to obtain the polymer component in the form of a thin paste or powder, but in order to separate the polymer component from dilute water.
例えば、多量のメタノールなどの有機溶媒を加えること
によりポリマー成分を析出させるか。For example, do polymer components precipitate by adding a large amount of an organic solvent such as methanol?
又は、多大な熱エネルギーにより濃縮する必要があり、
工業的には極めて不利であった。また。Or it needs to be concentrated using a large amount of thermal energy,
This was extremely disadvantageous industrially. Also.
ポリビニルホルムアミドの加水分解自体をメタノールな
どの有機溶媒と水との混合物中で苛性アルカリ又は鉱酸
の存在下、実施する方法も考えられるが、この場合も、
多量の有機溶媒を必要とするので有機溶媒の回収設備が
必要な上。It is also possible to carry out the hydrolysis of polyvinylformamide itself in a mixture of an organic solvent such as methanol and water in the presence of a caustic alkali or a mineral acid, but in this case as well,
Since a large amount of organic solvent is required, organic solvent recovery equipment is required.
反応器の材質面でも問題があり、やはり工業的に有利な
方法とは言えない。There are also problems with the material of the reactor, so it cannot be said to be an industrially advantageous method.
本発明者等は上記実情に艦み、有機溶媒を用いることな
く、水溶液中でポリビニルホルムアミドの刃口水分解を
実施した場合に、生成したポリマー成分を効率的に取得
する方法につき種々検討した結果、７］０水分解後の水
溶液にユ価以上の有機酸を加えるとポリマー成分が水不
扉性となり析出し、また、この析出ポリマーは特定の酸
で処理すると水溶性ポリマーに変化することを見い出し
本発明を完成した。The present inventors have been aware of the above-mentioned circumstances, and have conducted various studies on a method for efficiently obtaining the polymer components produced when polyvinylformamide is subjected to edge water decomposition in an aqueous solution without using an organic solvent. 7] It was discovered that when an organic acid with a U value or higher is added to an aqueous solution after 0 water decomposition, the polymer component becomes water-tight and precipitates, and that this precipitated polymer changes into a water-soluble polymer when treated with a specific acid. The invention has been completed.
すなわち９本発明の要旨は、ポリビニルホルムアミドの
少な（とも一部を加水分解して得たポリマー水浴液に、
コ価以上の有機酸を加えてポリマー成分を析出させ１次
いで、析出したポリマーを分離した後、前記有機酸の第
２ｐＫａ値よりも小さいｐＫａ値を有する７価の有機酸
又は無機酸と接触させることを特徴とする水溶性ポリマ
ーの製造法に存する。In other words, the gist of the present invention is to add a polymer water bath solution obtained by hydrolyzing a small amount (or a part) of polyvinylformamide,
A polymer component is precipitated by adding an organic acid having a covalent value or higher.Next, the precipitated polymer is separated and then contacted with a heptavalent organic acid or inorganic acid having a pKa value smaller than the second pKa value of the organic acid. A method for producing a water-soluble polymer is provided.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で対象となるポリビニルホルムアミドの少な（と
も一部が加水分解されたポリマー水浴液としては１通常
、ポリビニルホルムアミドの水ｍ液を苛性アルカリの存
在下で加水分解して得られるポリマー水浴液が挙げられ
る。この場合のポリビニルホルムアミド水ＫＭの濃度は
通常、／〜／Ｓ％程度であり、また、苛性アルカリとし
ては通常、苛性ソーダ又は苛性カリである。苛性アルカ
リの使用量は通常、ポリマー中のホルムアミド基に対し
て、ｏ、ｉ〜ｉ、ｇ倍モル、好ましくは０．−〜／倍モ
ルである。苛性アルカリの使用量はポリマーの加水分解
率との相関があるが１本発明で対象とするポリマーの加
水分解率（−ＮＨ２基／ −Ｎ ＨＯＨＯ基）としては
１通常、／θ〜ノ００％、好ましくはグθ〜り０％であ
る。加水分解の温度はＯ〜ｉｏｏ℃程度であり１通常、
ポリマー水溶液を攪拌しつつ所定量の苛性アルカリ水溶
液を滴下することにより実施することができる。加水分
解反応により生成するポリマー及び副生ずるギ酸アルカ
リ塩は両方とも水溶性であるので９反応後の混合物は均
一水浴液である。The polymer water bath liquid in which polyvinylformamide is partially hydrolyzed is usually a polymer water bath liquid obtained by hydrolyzing an aqueous solution of polyvinylformamide in the presence of caustic alkali. In this case, the concentration of polyvinylformamide water KM is usually about /~/S%, and the caustic alkali is usually caustic soda or caustic potash.The amount of caustic alkali used is usually about The amount is o, i to i, g times the mole, preferably 0.- to /g times the mole.The amount of caustic alkali to be used is correlated with the hydrolysis rate of the polymer, but it is one of the targets of the present invention. The hydrolysis rate (-NH2 group/-NHOHO group) of the polymer is usually 1/θ~00%, preferably 0~0%.The hydrolysis temperature is about 0~ioo℃. Yes 1 Usually,
This can be carried out by dropping a predetermined amount of a caustic alkaline aqueous solution while stirring the polymer aqueous solution. Since both the polymer produced by the hydrolysis reaction and the formic acid alkali salt produced as a by-product are water-soluble, the mixture after 9 reactions is a homogeneous water bath liquid.
なお、ポリマーの加水分解を苛性アルカリの代りに無機
酸の存在下に実施しても差し支えないが、この場合には
、得られる混合物を中和し。Note that the hydrolysis of the polymer may be carried out in the presence of an inorganic acid instead of caustic alkali, but in this case, the resulting mixture is neutralized.
ポリマー中のアミノ基をフリーの形としてお（必要があ
る。また１本発明によれば加水分解時にメタノールなど
の有機溶媒を用いな（ても。It is necessary to keep the amino groups in the polymer in a free form.Also, according to the present invention, an organic solvent such as methanol is not used during hydrolysis.
後述する処理によって、目的とする水溶性ポリマーをペ
ースト状又は粉粒体として取得できるが、必要に応じて
、有機溶媒を併用しても差し支えない。The desired water-soluble polymer can be obtained in the form of a paste or powder by the treatment described below, but an organic solvent may also be used in combination, if necessary.
本発明は、上述のようなポリマー水浴液にコ価以上の有
機酸を加え、ポリマー成分を析出させることを必須の要
件とするものである。−価以上の有機酸の具体例として
は、シュウ酸、マＶイ：／酸、コハク酸、アジピン酸、
フマル酸すどのλ個有機酸、トリメリット酸、ピロメリ
ット酸、クエン酸などの３価有機酸が挙げられ。The present invention requires that an organic acid having a covalent value or higher be added to the polymer water bath solution as described above to precipitate the polymer component. -Specific examples of organic acids having a value higher than or equal to
Examples include trivalent organic acids such as fumaric acid, trimellitic acid, pyromellitic acid, and citric acid.
なかでも、シュウ酸又はクエン酸が望ましい。Among these, oxalic acid or citric acid is preferred.
また、これらの有機酸の第２ｐｋ７ａ値は後から添加す
る酸との関係から１通常、、３以上であることか好まし
い。これらの有機酸の使用量は対象とするポリマーの刀
り水分解率によっても異なるが１通常、水溶液中に残存
する苛性アルカリの中和相当量を除いて、ポリマー成分
に対し０．０５〜／重量倍、好ましくはｏ、ｉ〜Ｏ１７
重量倍である。本発明では有機酸の添加によりポリマー
水？Ｗｉ中のポリマー成分の実質約合てを不溶化し析出
させることができるが、有機酸の添加量があまり少ない
とポリマー成分を良好に析出させることができず、逆に
、あまり多くても効果に変りはないので経済的でない。Further, the second pk7a value of these organic acids is preferably 1 or more, usually 3 or more, in view of the relationship with the acid added later. The amount of these organic acids to be used varies depending on the water decomposition rate of the target polymer, but is usually 0.05 to 1% of the polymer component, excluding the amount equivalent to neutralizing the caustic alkali remaining in the aqueous solution. Weight times, preferably o, i~O17
It is twice the weight. In the present invention, by adding an organic acid, polymer water can be added. It is possible to insolubilize and precipitate the polymer components in Wi, but if the amount of organic acid added is too small, the polymer components cannot be precipitated well, and conversely, if the amount is too large, the effect is not good. There is no change, so it is not economical.
有機酸の添加操作は通常、室温下でポリマー水浴液に有
機酸を加え、／〜３０分程度、攪拌することにより行な
われる。この工程でポリマー成分が析出する原因は明確
ではないが、ポリマー中のアミノ基が２価以上の有機酸
を介して結合した形となり、その結果、ポリマーが不溶
化し析出するものと推定される。The addition operation of the organic acid is usually carried out by adding the organic acid to the polymer water bath solution at room temperature and stirring for about 30 minutes. The reason why the polymer component precipitates in this step is not clear, but it is presumed that the amino groups in the polymer are bonded via divalent or higher organic acids, and as a result, the polymer becomes insolubilized and precipitates.
析出したポリマー成分は、濾過又は分液などの操作によ
り分離した後、先に添加したコ価以上の有機酸の第２ｐ
Ｋａ値よりも小さく、更に好ましくは第１ ｐＫａ値よ
りも小さい７価の有機酸又は無機酸と接触させることに
より水溶性ポリマーに転換されろ。ここで用いられる酸
としては、スルファミン酸、ジクロロ酢酸、トリクロロ
酢酸などの有機酸、又は、塩酸、臭化水系酸などの無機
酸が挙げられ、なかでも、スルファミン酸が好ましい。The precipitated polymer component is separated by an operation such as filtration or liquid separation, and then added to the second polymer component of the organic acid having a covalent value or higher that has been added previously.
It is converted into a water-soluble polymer by contacting with a heptavalent organic or inorganic acid having a Ka value lower than the first pKa value, more preferably lower than the first pKa value. Examples of acids used here include organic acids such as sulfamic acid, dichloroacetic acid, and trichloroacetic acid, and inorganic acids such as hydrochloric acid and aqueous bromide acids, with sulfamic acid being preferred.
これらの酸の使用量が少ないとポリマーを水溶性に転換
することができず、逆に、あまり多くても効果に変りは
な（。If the amount of these acids used is too small, it will not be possible to convert the polymer to water-soluble; on the other hand, if too much of these acids are used, the effect will not change.
ポリマー純度が低下するので、通常、加水分解前のポリ
マー成分に対して、０．０２〜０．５重量倍、好ましく
は０．０３〜０．３重量倍使用される。Since the purity of the polymer decreases, it is usually used in an amount of 0.02 to 0.5 times, preferably 0.03 to 0.3 times the weight of the polymer component before hydrolysis.
水不溶性のポリマーを１価の酸と接触させることにより
、ポリマーの周囲に水が存在する場合には・、常温で極
めて簡単に水溶性のポリマーに転換される。この理由は
コ価以上の有機酸の塩となっているポリマー中のアミノ
基が１価の酸の塩に変換されるためと推定される。By bringing a water-insoluble polymer into contact with a monovalent acid, if water is present around the polymer, it is very easily converted to a water-soluble polymer at room temperature. The reason for this is presumed to be that the amino groups in the polymer, which are salts of organic acids with covalent or higher valency, are converted to salts of monovalent acids.
上記７価の酸は湿潤状態の水不溶性ポリマーに添刀口接
触させても、また、水不溶性ポリマー＝ ７ ＝
を乾燥した後に添加接触させてもよい。すなわち、得ら
れるポリマーの形態は前者の場合にはペースト状となり
、後者の場合には粉粒体となる。得られる粉粒体状のポ
リマーは水と混合した際に、直ちにペースト状又は浴液
状となる。The heptavalent acid may be brought into contact with the water-insoluble polymer in a wet state, or may be brought into contact with the water-insoluble polymer after drying. That is, the form of the obtained polymer will be in the form of a paste in the former case, and in the form of powder in the latter case. When the obtained powder-like polymer is mixed with water, it immediately becomes a paste or a bath liquid.
したがって、１価の酸を乾燥ポリマーに添加接触させる
場合には、水溶性の固体酸を使用することが望ましい。Therefore, when adding and contacting a monovalent acid with a dry polymer, it is desirable to use a water-soluble solid acid.
なお、湿潤状態のポリマーの含水率は通常。Note that the moisture content of the polymer in a wet state is normal.
ｇｏ−ｑｏ重量係程度であるので、これを乾燥する場合
は、該含水ポリマーを肉挽押出機などの造粒機により粒
径３〜１０７１Ｍ１程度に造粒し。Since it is about go-qo weight ratio, when drying it, the water-containing polymer is granulated to a particle size of about 3 to 1071 M1 using a granulator such as a meat grinder and extruder.
次いで、これをｌｌ０−１００℃の温度で、含水量ＩＯ
重量係以下まで熱風乾燥する方法を採用することにより
有利に乾燥することができる。This is then heated to a temperature of 10-100°C with a moisture content of IO
Advantageous drying can be achieved by employing a method of hot air drying to below the weight ratio.
次に１本発明を実施例により更に詳細に説明するが１本
発明はその要旨を超えない限り、以下の実施例に限定さ
れるものではない。Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
実施例１〜３
−８ ＝
！； ｌ 攪拌容器にＮ−ビニルホルムアミドの重合に
より得たポリビニルホルムアミド（還元粘度ｓ、ｓｄｌ
／１１ ） ３０ ｇを左％水浴液として仕込み。Examples 1 to 3 -8 =! ; l Polyvinylformamide obtained by polymerization of N-vinylformamide (reduced viscosity s, sdl
/11) Prepare 30 g as left% water bath solution.
これにグクチ苛性ソーダ水溶液（ＮａＯＨとしてｏ、ｓ
ｚ３モル、ポリマー中のホルムアミド基の６０モルラな
加水分解できる量）を攪拌下。Add to this aqueous caustic soda solution (o, s as NaOH).
3 mol, the amount that can be hydrolyzed by 60 mol of the formamide group in the polymer) under stirring.
７０℃の温度で３０分間かげて滴下し、ポリマーの加水
分解を行なった。The mixture was added dropwise at a temperature of 70° C. for 30 minutes to hydrolyze the polymer.
この混合物は均一な水溶液であり、混合物中のポリマー
を分析したところ、ホルムアミド基のＳ２モルラがアミ
ノ基に加水分解されていた。This mixture was a homogeneous aqueous solution, and when the polymer in the mixture was analyzed, it was found that the S2 mole of the formamide group was hydrolyzed to an amino group.
更に、この混合物中に第１表に示すコ価の有機酸を３０
℃の温度で添加し、３０分間、攪拌を続はポリマー成分
を析出させた後、これを濾過することにより含水１７０
ｗｔ％の含水ポリマーを分離し１次いで、これに第１表
に示す１価の酸を添力口し均一混合して、ペースト状ポ
リマーを製造した。Furthermore, 30% of the covalent organic acid shown in Table 1 was added to this mixture.
℃ and stirred for 30 minutes to precipitate the polymer component, which was filtered to reduce the water content to 170℃.
A wt % water-containing polymer was separated, and then a monovalent acid shown in Table 1 was added thereto and mixed uniformly to produce a paste polymer.
上記のようにして得た各ペースト状ポリマーは良好な水
溶性を示すものであった。また、この各ポリマーをＯｏ
、２ｗｔ％ポリマー水浴液とし。Each of the paste-like polymers obtained as described above exhibited good water solubility. Also, each polymer is Oo
, 2wt% polymer water bath solution.
これを用いて都市下水に対する凝集性能テストを行なっ
たところ、第２表に示す結果を得た。Using this product, we conducted a flocculation performance test on urban sewage, and the results shown in Table 2 were obtained.
参考例
実施例／の方法において、ポリビニルホルムアミド３％
水浴液とともに、公知法に準じて有機醍媒としてメタノ
ール３０００ｆｌを仕込み、これに同様の苛性ソーダ水
浴液を滴下し加水分解を行なった後、３タチ塩酸！θＩ
を滴下してポリマーの析出を行ない１次いで、析出ポリ
マーを分離して得た水溶性ポリマーにつき、実施例１と
同じ凝集性能テストを行なった場合の結果を第２表に併
記した。Reference Example In the method of Example/3% polyvinylformamide
Along with the water bath liquid, 3000 fl of methanol was added as an organic medium according to a known method, and the same caustic soda water bath liquid was added dropwise to perform hydrolysis, followed by 3 times hydrochloric acid! θI
was added dropwise to precipitate the polymer, and then the precipitated polymer was separated. The resulting water-soluble polymer was subjected to the same flocculation performance test as in Example 1. The results are also shown in Table 2.
第１表
注１） 添加量（重量倍）
加水分解前のポリマー成分に対する重量割合
第−表
−１１〜
注２） ポリマー還元粘度Ｃｄｌ／１１）３％食塩中に
ポリマー濃度がθ、／Ｗｔ（支）となるようにポリマー
を溶解させた溶液を、２３℃の温度でオストワルド粘度
計を用いて測定した。Table 1 Note 1) Addition amount (weight times) Weight ratio to polymer component before hydrolysis Table 11~ Note 2) Polymer reduced viscosity Cdl/11) Polymer concentration in 3% salt is θ, /Wt ( A solution in which the polymer was dissolved so as to give the following properties was measured at a temperature of 23° C. using an Ostwald viscometer.
注３〕濾過速度（ｃｃ／３０ ｓ ｅ ｃ ）下水生汚
泥（固形分３ｗｔ％）に固形分に対してＯ，ｐｗｔ％の
ポリマーを添加し、７０秒後、Ｆ布を用いて自然濾過し
、３０秒後の炉水量を測定した。Note 3] Filtration rate (cc/30 sec) Add O, pwt% of polymer based on the solid content to raw sewage sludge (solid content 3 wt%), and after 70 seconds, filter it naturally using F cloth. The amount of reactor water was measured after 30 seconds.
注４） 汚泥含水率（％）
上記濾過速度の測定で得られたケーキ分をプレス脱水機
によりｓ ｋｇ／ｄの圧力下で処理した後の含水率を示
した。Note 4) Sludge water content (%) The water content after the cake obtained in the above filtration rate measurement was treated with a press dehydrator under a pressure of s kg/d is shown.
比較例１−ユ
実施ｆ！ｌ／の方法において、７価酸としてスルファミ
ン酸の代りに、同量の酢酸（ｐＫａ＝ｐ、７７）又は安
息香酸（ｐＫａ ＝り、２０）を用いて全く同様に処理
したところ、いずれも、得られたポリマーは水不溶性の
ままであり、水溶性ポリマーを得ることができなかった
。Comparative Example 1-U implementation f! When the same amount of acetic acid (pKa=p, 77) or benzoic acid (pKa=ri, 20) was used in place of sulfamic acid as the heptavalent acid in the method of The obtained polymer remained water-insoluble, and a water-soluble polymer could not be obtained.
比較例３
実施例コの方法において、１価酸としてスル７アミノ酸
の代りに、同量の酢酸を用いて全く同様に処理したとこ
ろ、得られたポリマーは水不済性のままであり、水溶性
ポリマーを得ることができなかった。Comparative Example 3 When treated in exactly the same manner as in Example 3 but using the same amount of acetic acid instead of the sul-7 amino acid as the monovalent acid, the resulting polymer remained water-insoluble and was water-soluble. It was not possible to obtain a synthetic polymer.
実施例り
実施例／の方法において、２個有機酸であるシュウ酸を
添加することにより析出した含水ポリマーを分離した後
、これを粒径５籠以下に粉砕し１次いで、６０℃の温度
で７．２０分間、熱風乾燥することにより、含水量３％
の粉状ポリマーを回収し、これに１価の酸であるスルフ
ァミン酸をトライブレンドした。Example In the method of Example/2, the precipitated water-containing polymer was separated by adding oxalic acid, which is an organic acid, and then pulverized to a particle size of 5 or less, and then heated at a temperature of 60°C. 7. Moisture content is 3% by drying with hot air for 20 minutes.
The powdered polymer was collected and triblended with sulfamic acid, which is a monovalent acid.
ここで得た粉状ポリマー組成物を溶解槽において溶解処
理したところ、ポリマーは水に良好に溶解された。この
ようにして、０．２％のポリマー水浴液を自製し、実施
例１と同様な凝集性能テストを実施したところ、沈降速
度は／１０ｇ／ｍｉｎであり、汚泥含水率はｇＯ，７％
であった。When the powdered polymer composition obtained here was subjected to dissolution treatment in a dissolution tank, the polymer was well dissolved in water. In this way, a 0.2% polymer water bath solution was prepared in-house, and the same flocculation performance test as in Example 1 was conducted, and the settling rate was /10 g/min, and the sludge water content was gO, 7%.
Met.
本発明によれば、ポリビニルホルムアミドの刃口水分解
ポリマーを製造するに当り、メタノールなどの有機各課
を用いなくても、加水分解後の混合物から容易にポリマ
ー成分を析出させて分離することが可能であり、更に１
分離したポリマーは簡単に水溶性ポリマーに転換するこ
とが可能である。したがって１本発明では水溶媒単独で
効率的な水溶性ポリマ〜を取得することができるので、
工業的に極めて有利な方法である。また１本発明ではポ
リマーの形態として、ペースト品又は粉粒節のいずれを
も得ることができ、これらのポリマーの凝集性能は従来
のプロセスで得られるポリマーと同様に優れたものであ
る。According to the present invention, when producing a hydrolyzed polymer of polyvinylformamide at the cutting edge, it is possible to easily precipitate and separate polymer components from a mixture after hydrolysis without using organic components such as methanol. Yes, and 1 more
The separated polymer can be easily converted into a water-soluble polymer. Therefore, in the present invention, an efficient water-soluble polymer can be obtained using only a water solvent.
This is an industrially extremely advantageous method. In addition, in the present invention, the polymer can be obtained in either a paste or powder form, and the agglomeration performance of these polymers is as excellent as that of polymers obtained by conventional processes.
Claims (3)
分解して得たポリマー水浴液に、２価以上の有機酸を加
えてポリマー成分を析出させ、次いで、析出したポリマ
ーを分離した後、前記有機酸の第２ｐＫａ値よりも小さ
いｐＫａ値を有する１価の有機酸又は無機酸と接触させ
ることを特徴とする水溶性ポリマーの製造法。(1) A divalent or higher organic acid is added to a polymer water bath solution obtained by hydrolyzing at least a portion of polyvinylformamide to precipitate a polymer component, and then, after separating the precipitated polymer, the organic acid is A method for producing a water-soluble polymer, which comprises contacting with a monovalent organic acid or inorganic acid having a pKa value smaller than a second pKa value.
特許請求の範囲第１項記載の方法。(2) The method according to claim 1, wherein the divalent or higher organic acid is oxalic acid or citric acid.
酸である特許請求の範囲第１項記載の方法。(3) The method according to claim 1, wherein the monovalent organic acid or inorganic acid is sulfamic acid or hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20910286A JPS6366205A (en) | 1986-09-05 | 1986-09-05 | Production of water-soluble polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20910286A JPS6366205A (en) | 1986-09-05 | 1986-09-05 | Production of water-soluble polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6366205A true JPS6366205A (en) | 1988-03-24 |
Family
ID=16567319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20910286A Pending JPS6366205A (en) | 1986-09-05 | 1986-09-05 | Production of water-soluble polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6366205A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998011145A1 (en) * | 1996-09-11 | 1998-03-19 | Basf Aktiengesellschaft | Insoluble polymers which can swell only slightly with modified amino groups, processes for their preparation, and their use |
| WO1999053104A1 (en) * | 1998-04-09 | 1999-10-21 | Basf Aktiengesellschaft | Polymer tanning agents containing n-vinyl units |
-
1986
- 1986-09-05 JP JP20910286A patent/JPS6366205A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998011145A1 (en) * | 1996-09-11 | 1998-03-19 | Basf Aktiengesellschaft | Insoluble polymers which can swell only slightly with modified amino groups, processes for their preparation, and their use |
| WO1999053104A1 (en) * | 1998-04-09 | 1999-10-21 | Basf Aktiengesellschaft | Polymer tanning agents containing n-vinyl units |
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