JP5575445B2 - Styrene polymer - Google Patents
Styrene polymer Download PDFInfo
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- JP5575445B2 JP5575445B2 JP2009226377A JP2009226377A JP5575445B2 JP 5575445 B2 JP5575445 B2 JP 5575445B2 JP 2009226377 A JP2009226377 A JP 2009226377A JP 2009226377 A JP2009226377 A JP 2009226377A JP 5575445 B2 JP5575445 B2 JP 5575445B2
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- cutting oil
- emulsion
- soluble cutting
- type water
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- 229920000642 polymer Polymers 0.000 title claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 10
- 239000010730 cutting oil Substances 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- -1 cationic organic compound Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Description
本発明は、新規なスチレン系ポリマーと、それを用いた水溶性切削油の処理用として適した凝集剤に関する。 The present invention relates to a novel styrenic polymer and a flocculant suitable for treating water-soluble cutting oil using the same.
金属加工で使用する切削油として、エマルション型の水溶性切削油が汎用されているが、使用後の水溶性切削油は焼却処分されているが、固形分が５質量％程度であるため、処理効率が非常に悪い。 Emulsion-type water-soluble cutting oil is widely used as the cutting oil used in metal processing, but the water-soluble cutting oil after use is incinerated, but the solid content is about 5% by mass, The efficiency is very bad.
特許文献１には、鋳造、鍛造、切削、研削、プレス、圧延、引き抜き、研磨等の金属加工のときに発生する廃液を、カチオン系およびアニオン系高分子凝集剤の少なくとも一つを加える凝集分離工程と、凝集分離工程で分離した凝集分離物を除いた廃水を、活性汚泥を用いた微生物処理槽で処理する微生物処理工程とを備えた処理方法が記載されており、ｐＨを６．５〜ＰＨ７．５の範囲に調整することが記載されている。 In Patent Document 1, the waste liquid generated during metal processing such as casting, forging, cutting, grinding, pressing, rolling, drawing, and polishing is agglomerated and separated by adding at least one of a cationic and anionic polymer flocculant. A treatment method comprising a step and a microbial treatment step of treating waste water from which the flocculated separation separated in the flocculation separation step is treated in a microbial treatment tank using activated sludge is described, and the pH is 6.5 to 6.5. It is described to adjust to the range of PH7.5.
特許文献２には、少なくとも使用済切削油を含有する廃水に、カチオン系有機化合物を添加することにより該廃水中の少なくとも水不溶成分を凝結させて凝結粒子を形成する工程、さらにアニオン系有機高分子を添加して該凝結粒子を凝集フロックに成長させる工程、及び形成された凝集フロックを分離させる工程を含む切削油含有廃水の処理方法が記載されており、処理過程においてｐＨを７に調整することが記載されている。 Patent Document 2 discloses a step of forming agglomerated particles by adding a cationic organic compound to waste water containing at least used cutting oil to condense at least water-insoluble components in the waste water. A method for treating cutting oil-containing wastewater comprising a step of adding molecules to grow the aggregated particles into aggregated flocs and a step of separating the formed aggregated flocs is described, and the pH is adjusted to 7 in the process It is described.
特許文献３には、クーラント廃液に酸化アルミニウムを含む焼却灰およびアルミニウム塩を添加して凝集処理し、脱水するクーラント廃液の処理方法が記載されており、凝集処理時には、ｐＨ５〜８に調整することが記載されている。 Patent Document 3 describes a method for treating a coolant waste liquid in which an incinerated ash containing aluminum oxide and an aluminum salt are added to a coolant waste liquid to agglomerate and dehydrate, and the pH is adjusted to 5 to 8 during the agglomeration process. Is described.
本発明は、新規なスチレン系ポリマーと、それを用いたエマルション型の水溶性切削油の処理用として好適な凝集剤を提供することを課題とする。 An object of the present invention is to provide a novel styrenic polymer and a flocculant suitable for processing an emulsion-type water-soluble cutting oil using the same.
本発明は、課題の解決手段として、被処理液となるエマルション型の水溶性切削油にｐＨ調整剤を添加してｐＨを１〜５の範囲に調整した後、下記一般式（１）で示されるスチレン系ポリマーを含有する凝集剤を前記スチレン系ポリマー濃度が５００〜５，０００ｐｐｍになるように添加する、エマルション型の水溶性切削油の処理方法を提供する。
As a means for solving the problem, the present invention adds a pH adjuster to an emulsion-type water-soluble cutting oil to be treated to adjust the pH to a range of 1 to 5, and then represents the following general formula (1). A method for treating an emulsion-type water-soluble cutting oil is provided , wherein a flocculant containing a styrenic polymer is added so that the styrenic polymer concentration is 500 to 5,000 ppm .
本発明の一般式（１）で示されるスチレン系ポリマーを含む凝集剤は、エマルション型の水溶性切削油の処理用として適している。 The flocculant containing the styrenic polymer represented by the general formula (1) of the present invention is suitable for processing emulsion-type water-soluble cutting oil.
本発明のスチレン系ポリマーは、上記の一般式（１）で示されるものである。一般式（１）中のｍ及びｎはいずれも１以上の数であり、ｍ：ｎ＝３：１〜１：２で、固有粘度範囲が０．３〜０．５ｄＬ／ｇ（２５℃でジメチルスルホキシドを溶媒とする）のものが好ましく、ｍ：ｎ＝２．５：１〜１：１で、固有粘度範囲が０．３５〜０．４５ｄＬ／ｇ（２５℃でジメチルスルホキシドを溶媒とする）のものがより好ましい。
The styrenic polymer of the present invention is represented by the above general formula (1). In the general formula (1), m and n are each a number of 1 or more, m: n = 3: 1 to 1: 2, and an intrinsic viscosity range of 0.3 to 0.5 dL / g (25 ° C. In which dimethyl sulfoxide is used as a solvent), m: n = 2.5: 1 to 1: 1, and the intrinsic viscosity range is 0.35 to 0.45 dL / g (dimethyl sulfoxide is used as a solvent at 25 ° C.). Is more preferable.
本発明の凝集剤は、一般式（１）で示されるポリマーを含有するものである。本発明の凝集剤は、粉末状、液状等にすることができるが、保管や取り扱い性の観点から、粉末状が好ましい。 The flocculant of the present invention contains a polymer represented by the general formula (1). The flocculant of the present invention can be made into a powder form, a liquid form, etc., but from the viewpoint of storage and handling properties, a powder form is preferred.
本発明の凝集剤は、エマルション型の水溶性切削油の処理用として特に適している。以下、エマルション型の水溶性切削油の処理に適用した場合の一例を説明する。 The flocculant of the present invention is particularly suitable for the treatment of emulsion-type water-soluble cutting oil. Hereinafter, an example in the case of applying to the processing of emulsion type water-soluble cutting oil will be described.
被処理液となるエマルション型の水溶性切削油は、金属加工等で使用後の水溶性切削油であり、通常は、固形分濃度が５質量％程度のものである。不要になった未使用の水溶性切削油を処理することもできるが、その場合には、必要に応じて水で希釈して処理する。 The emulsion-type water-soluble cutting oil used as the liquid to be treated is a water-soluble cutting oil after use in metal processing or the like, and usually has a solid concentration of about 5% by mass. Although it is possible to treat unused water-soluble cutting oil that is no longer needed, in that case, it is diluted with water as necessary.
本発明の凝集剤を用いて処理するとき、被処理液のｐＨは１〜７の範囲が好ましく、２〜５の範囲がより好ましい。 When processing using the flocculant of this invention, the range of 1-7 is preferable and, as for the pH of a to-be-processed liquid, the range of 2-5 is more preferable.
本発明の凝集剤を用いて処理するとき、ｐＨを調整後に凝集剤を添加してもよいし、凝集剤を添加後にｐＨを調整してもよいし、凝集剤とｐＨ調整剤を並行して添加してもよい。また、被処理液（使用後の水溶性切削油等）に大きめの異物が混入しているときには、予め除去することが望ましいが、砂や泥程度であれば、取り除くことなく処理することができる。 When processing using the flocculant of the present invention, the flocculant may be added after adjusting the pH, the pH may be adjusted after the flocculant is added, or the flocculant and the pH adjuster are used in parallel. It may be added. Further, when a large foreign matter is mixed in the liquid to be treated (water-soluble cutting oil after use, etc.), it is desirable to remove it in advance, but if it is about sand or mud, it can be treated without removing it. .
本発明の凝集剤は、被処理液に添加したときの一般式（１）で示すポリマーの濃度が２００ｐｐｍ以上（質量基準）となる量であり、好ましくは２００〜１０，０００ｐｐｍ、より好ましくは５００〜５，０００ｐｐｍ、さらに好ましくは５００〜２，０００ｐｐｍである。 The flocculant of the present invention is an amount such that the concentration of the polymer represented by the general formula (1) when added to the liquid to be treated is 200 ppm or more (mass basis), preferably 200 to 10,000 ppm, more preferably 500. ˜5,000 ppm, more preferably 500 to 2,000 ppm.
実施例１＜一般式（１）のスチレン系ポリマーの製造＞
p-スチレンスルホン酸ナトリウム（1.03 g, 5 mmol）、スチレン(0.523 g, 5 mmol)、N’，N-アゾイソブチロニトリル（7.77mg）、溶媒としてN,N-ジメチルホルムアミド（DMF）18.5mlをそれぞれ量り取り重合管に加えた。アルゴン置換による凍結脱気法を5回行った後、ガスバーナーで封管し、振とう器を用いて60℃で24時間反応させた。反応後、白色固体とDMFの溶液が得られた。DMF中にモノマーが溶けていると判断し、固体をろ過後DMFで何度か洗浄し、アセトンで3度洗浄して室温で減圧乾燥を行い、白色固体を得た。得られた固体はDMSO-d6を溶媒として1H NMRにより目的物であることを確認した。
Example 1 <Production of Styrene Polymer of General Formula (1)>
Sodium p-styrenesulfonate (1.03 g, 5 mmol), styrene (0.523 g, 5 mmol), N ′, N-azoisobutyronitrile (7.77 mg), N, N-dimethylformamide (DMF) 18.5 as a solvent Each ml was weighed and added to the polymerization tube. The freeze deaeration method by argon substitution was performed 5 times, and then the tube was sealed with a gas burner and reacted at 60 ° C. for 24 hours using a shaker. After the reaction, a white solid and DMF solution was obtained. It was judged that the monomer was dissolved in DMF, and the solid was filtered, washed several times with DMF, washed three times with acetone, and dried under reduced pressure at room temperature to obtain a white solid. The obtained solid was confirmed to be the target product by 1 H NMR using DMSO-d 6 as a solvent.
実施例２
凝集剤として、一般式（１）のスチレン系ポリマー（ｍとｎの比率が、１３：８で、固有粘度が０.４ｄＬ／ｇ（２５℃でジメチルスルホキシドを溶媒とする））を用いた。被処理液として、市販のエマルション型の標準的水溶性切削油（出光社製）を水道水で２０倍に希釈したものを用いた。
Example 2
As the aggregating agent, a styrene polymer of the general formula (1) (m: n ratio is 13: 8, intrinsic viscosity is 0.4 dL / g (dimethylsulfoxide as a solvent at 25 ° C.)) was used. . As the liquid to be treated, a commercially available emulsion-type standard water-soluble cutting oil (manufactured by Idemitsu Co., Ltd.) diluted 20-fold with tap water was used.
被処理液５００ｍｌをビーカーに入れた後、塩酸を添加して、ｐＨ３に調整した。 After 500 ml of the liquid to be treated was placed in a beaker, hydrochloric acid was added to adjust the pH to 3.
次に、ビーカー内を攪拌しながら、凝集剤を１０００ｐｐｍになるように添加し、約２００ｒ/mで、５分間攪拌した。その後、一晩放置して、ビーカー内の分離状態を観察した。なお、凝集剤は、１０％水溶液（wt／vol）として添加した。 Next, the flocculant was added to 1000 ppm while stirring the inside of the beaker, and the mixture was stirred at about 200 r / m for 5 minutes. Then, it left to stand overnight and observed the separation state in a beaker. The flocculant was added as a 10% aqueous solution (wt / vol).
次に、４００メッシュの篩いで濾過して、上層部分を取り除き、下層（濾過液）を分取した。濾過液は、肉眼による観察によるとほぼ透明であった。 Next, it filtered with the sieve of 400 mesh, the upper layer part was removed, and the lower layer (filtrate) was fractionated. The filtrate was almost transparent as observed by the naked eye.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009226377A JP5575445B2 (en) | 2009-09-30 | 2009-09-30 | Styrene polymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009226377A JP5575445B2 (en) | 2009-09-30 | 2009-09-30 | Styrene polymer |
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| JP2011074185A JP2011074185A (en) | 2011-04-14 |
| JP5575445B2 true JP5575445B2 (en) | 2014-08-20 |
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| JP2009226377A Expired - Fee Related JP5575445B2 (en) | 2009-09-30 | 2009-09-30 | Styrene polymer |
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| CN105217895A (en) * | 2015-10-30 | 2016-01-06 | 无锡市嘉邦电力管道厂 | Heavy crude sewage water treating method |
| CN109999678A (en) * | 2019-04-25 | 2019-07-12 | 山东师范大学 | A kind of ion exchange membrane material and the preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS60202109A (en) * | 1984-03-26 | 1985-10-12 | Toyobo Co Ltd | Styrene copolymer |
| JPH09188707A (en) * | 1996-01-11 | 1997-07-22 | Lion Corp | Dispersant for emulsion polymerization |
| JP3460469B2 (en) * | 1996-09-27 | 2003-10-27 | ソニー株式会社 | Polymer dehydrating agent and wastewater treatment method |
| JPH10314570A (en) * | 1997-05-14 | 1998-12-02 | Tosoh Corp | Dispersant |
| JPH10324866A (en) * | 1997-05-23 | 1998-12-08 | Tosoh Corp | Antistatic agent and styrene resin composition using the same |
| JP3924068B2 (en) * | 1998-06-11 | 2007-06-06 | ソニー株式会社 | Waste water treatment agent and waste water treatment method using the same |
| JP4142598B2 (en) * | 2004-03-01 | 2008-09-03 | 日本アルシー株式会社 | Waste liquid treatment method |
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