CN1025560C - 丙烯酸及丙烯酸酯类的阻聚方法 - Google Patents
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 15
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- 150000002148 esters Chemical class 0.000 claims description 10
- 150000003254 radicals Chemical class 0.000 claims description 7
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 abstract description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 235000019253 formic acid Nutrition 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract 2
- 230000008901 benefit Effects 0.000 abstract 2
- UBONKQIVJMCFNM-UHFFFAOYSA-L copper;n,n-dibutylcarbamothioate Chemical compound [Cu+2].CCCCN(C([O-])=S)CCCC.CCCCN(C([O-])=S)CCCC UBONKQIVJMCFNM-UHFFFAOYSA-L 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 125000003368 amide group Chemical group 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 5
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
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- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940065472 octyl acrylate Drugs 0.000 description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
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- HRXNUGQWQXSUOD-UHFFFAOYSA-N 1-(1-hydroxyindol-3-yl)-N,N-dimethylmethanamine Chemical compound CN(C)Cc1cn(O)c2ccccc12 HRXNUGQWQXSUOD-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
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- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 231100000989 no adverse effect Toxicity 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229940099204 ritalin Drugs 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明为一种丙烯酸及丙烯酸酯类的阻聚方法,该方法是在丙烯酸及丙烯酸酯类的生产过程中加入哌啶氮氧自由基型高效阻聚剂,其化学名称为2,2,6,6-四甲基-4-羟基氮氧自由基。该阻聚剂具有无毒、无害、易于溶解、使用量小,阻聚性能高等优点,完全取代了通常使用的阻聚剂二丁基氨基硫代甲酸铜,解决了无机铜带来的三废问题和甲酸对设备的腐蚀问题,实现了阻聚剂完全国产化,同时还减少了阻聚剂对苯二酚的使用量,经济效益显著。
Description
本发明涉及一种丙烯酸(CH2CHCOOH)及丙烯酸酯类(CH2CHCOOCnH2n+1)产生产过程中的阻聚方法。
在丙烯酸及丙烯酸酯类的生产过程中,由于这两类物质均含有不饱和键而极易聚合,所以在生产过程中特别是精制过程中需加入一定量的阻聚剂。通过所用的阻聚剂是对苯二酚和二丁基氨基硫代甲酸铜。前者使用量较大,生产成本高,后者所含的无机铜给三废治理带来困难,所含的甲酸对设备有一定腐蚀性。此外二丁基氨基硫代甲酸铜不易溶解,易结晶,经常堵塞过滤器及管道。
本发明的目的是使用一种新型的高效的阻聚剂来取代二丁基氨基硫代甲酸铜。同时减少对苯二酚的用量。
本发明所采用的阻聚剂为哌啶氮氧自由基型阻聚剂。分子式为C9H18NO2,化学名称为2,2,6,6-四甲基-4-羟基氮氧自由基。结构式为:
将这种阻聚剂按一定量与丙烯酸或丙烯酸酯类的溶液均匀混合后,按已知的方法进行生产,实现其阻聚目的。
在丙烯酸及丙烯酸酯类的生产过程中,哌啶氮氧自由基型阻聚剂的用量分别为:
表2见文后:
下面提供几个实施例,以便证明本发明所获得的效果。
实施例1:取丙烯酸溶液2000毫升,其中含丙烯酸23%,醋酸0.76%,水8.98%,醋酸异丙酯67.26%,投入三(2,2,6,6-四甲基哌啶氮氧自由基)亚磷酸酯(C27H51O6N3P.)阻聚剂30ppm和对苯二酚650ppm。在常压、恒温100℃下,采用内回流装置,经过65小时以上的静态试验,未发现有聚合现象。
实施例2:取丙烯酸甲酯溶液500毫升,内含丙烯酸甲酯96.15%甲醇0.12%,水2.66%,醋酸甲酯0.5%,加入阻聚剂三(2,2,6,6-四甲基哌啶氮氧自由基)亚磷酸酯(C27H51O6N3P.)0.4克和对苯二酚2克。在常压、恒温30℃的条件下,采用内回流装置,经过30小时的静态试验,未发现有聚合现象。
实施例3:取丙烯酸丁酯溶液2000毫升,内含内烯酸丁酯81.29%丁醇12.85%,水2.3%,丁氧基丙酸丁酯2.16%,其它1.4%,加入阻聚剂2,2,6,6-四甲基-4-羟基氮氧自由基0.3克,在内填O型高效填料1250毫米(理论塔板20~23块/每米填料)的填料塔内连续精馏72小时,控制绝压300mmHg,釜温121℃。分析釜出:丙烯酸丁酯95.74%,丁氧基丙酸丁酯2.76%,其它1.5%,没有聚合现象产生。
实施例4:在丙烯酸精制过程中,在溶剂分离塔中,用表计量加入15m3/hr的萃取液,其中含丙烯酸23.5%。从塔顶加入阻聚剂与回流液汇合进塔,其中2,2,6,6-四甲基-4-羟基氮氧自由基的浓度为0.2%,对苯二酚的浓度为2.3%,用醋酸异丙酯做溶剂,控制塔内压力150mmHg(绝压),温度塔顶为39℃,塔釜为101℃。在此条件下连续运转131天未见聚合。
采用现有技术的阻聚方法与本发明进行比较,在实施例4中其它条件不变的情况下,加入浓度为
0.36%的二丁基氨基硫代甲酸铜和4.5%的对苯二酚,连续运转100天,未见聚合。
本发明提供的阻聚剂经实践证明对丙烯酸及丙烯酸酯类产品的产量、质量和消耗定额均无不利影响,且无毒无害,没有三废问题和对设备的腐蚀问题。该阻聚剂易于溶解,使用量小,阻聚性能高,完全取代了二丁基氨基硫代甲酸铜,减少对苯二酚使用量约50%,带来了较显著的经济效益,并实现了阻聚剂完全国产化。
表1:
阻聚剂 哌啶氮氧自由基型阻聚剂用量
产物 (Wtppm)
丙烯酸 20-100
丙烯酸甲酯 50-150
丙烯酸乙酯 15-150
丙烯酸丁酯 10-150°
丙烯酸异丁酯 10-150
丙烯酸辛酯 20-150
表2:
阻聚剂 哌啶氮氧自由基型阻聚剂用量
产物 (Wtppm)
丙烯酸 20~100
丙烯酸甲酯 50~150
丙烯酸乙酯 15~150
丙烯酸丁酯 10~150
丙烯酸异丁酯 10~150
丙烯酸辛酯 20~150
Claims (3)
1、一种丙烯酸(CH2CHCOOH)及丙烯酸酯类(CH2CH-COOCaH2a+1)的阻聚方法,通过加入阻聚剂来防止丙烯酸及丙烯酸酯类在生产过程中聚合,其特征在于加入了阻聚剂三(2,2,6,6-4甲基-4-羟基-哌啶氮氧自由基)亚磷酸酯-(C27H51O6N3P),将该阻聚剂按一定量与丙烯酸或丙烯酸酯类的溶液混合均匀后,用已知的方法加入到生产装置中。
2、根据权利要求1所述的丙烯酸及丙烯酸酯类的阻聚方法,其特征在于丙烯酸或丙烯酸酯类的溶液中加入的三(2,2,6,6,-4甲基-4-羟基-哌啶氮氧自由基)亚磷酸酯阻聚剂量分别为:
表1见文后
3、根据权利要求1所述的丙烯酸及丙烯酸酯类的阻聚方法,其特征在于与哌啶氮氧自由基三亚磷酸酯阻聚剂配合使用的还有对苯二酚。
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US5322960A (en) * | 1993-04-15 | 1994-06-21 | Nippon Shokubai Co., Ltd. | Method for inhibiting polymerization of (meth) acrylic acid and esters thereof |
TW294658B (zh) | 1994-06-02 | 1997-01-01 | Nippon Catalytic Chem Ind | |
US5728872A (en) * | 1994-06-27 | 1998-03-17 | Lutz Riemenschneider | Stabilized acrylic acid compositions |
DE19727505A1 (de) | 1997-06-27 | 1999-01-07 | Basf Ag | Verfahren der radikalisch initiierten wäßrigen Emulsionspolymerisation zur Herstellung einer wäßrigen Polymerisatdispersion |
DE19727502A1 (de) | 1997-06-27 | 1999-01-07 | Basf Ag | Verfahren der radikalisch initiierten wäßrigen Emulsionspolymerisation zur Herstellung einer wäßrigen Polymerisatdispersion |
WO1999007664A1 (de) | 1997-08-07 | 1999-02-18 | Basf Aktiengesellschaft | Verfahren zur stabilisierung von (meth)acrylsäureestern gegen unerwünschte radikalische polymerisation |
KR100417098B1 (ko) | 1998-07-27 | 2004-02-05 | 니폰 쇼쿠바이 컴파니 리미티드 | 비닐 화합물의 중합 억제 방법 |
DE19856565A1 (de) | 1998-12-08 | 2000-06-15 | Basf Ag | Verfahren zur Stabilisierung von wenigstens eine ethylenisch ungesättigte Bindung aufweisenden chemischen Verbindungen gegen unerwünschte radikalische Polymerisation |
JP2008137948A (ja) * | 2006-12-01 | 2008-06-19 | Showa Denko Kk | 重合性単量体組成物および重合防止方法 |
WO2016202883A1 (de) | 2015-06-17 | 2016-12-22 | Basf Se | Zusammensetzung zur sofortbeendigung einer radikalischen polymerisation |
CN113429947B (zh) * | 2021-07-01 | 2022-03-04 | 本时智能技术发展(上海)有限公司 | 一种阻聚功能化导热粒子及其应用 |
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Free format text: CORRECT: PATENTEE; FROM: DONGFANG CHEMICAL PLANT, BEIJING, THE EAST CHEMICAL PLANT,BEIJING TO: DONGFANG CHEMICAL FACTORY, BEIJING CHEMICAL INDUSTRY GROUP CO., LTD. |
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CP01 | Change in the name or title of a patent holder |
Patentee after: Dongfang Chemical Plant, Beijing Chemical Industry Group Co., Ltd. Patentee before: Dongfang Chemical Plant, Beijing |
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C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
OR01 | Other related matters | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |