CN1384095A - 不饱和季铵盐水溶液的制造方法 - Google Patents
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- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 19
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- 238000000034 method Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 10
- 229960003330 pentetic acid Drugs 0.000 claims description 5
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
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- 239000002738 chelating agent Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
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- 238000003756 stirring Methods 0.000 claims description 3
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- 239000000203 mixture Substances 0.000 claims description 2
- -1 quinhydrones Chemical compound 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 abstract description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 abstract 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
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- 229940050176 methyl chloride Drugs 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000539 dimer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
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- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- VVEPKWSPMLXNKZ-UHFFFAOYSA-M trimethyl(prop-2-enoyloxy)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)OC(=O)C=C VVEPKWSPMLXNKZ-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
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Abstract
此相当于通式(I)的不饱和季铵盐水溶液的制备方法是在水存在下通过丙烯酸N,N-二甲基氨基乙酯(ADAME)与通式(II)的季铵化试剂反应,此方法的特征在于,在一个以旋转盘搅拌的塔中连续地进行所述反应,在塔底加入季铵化试剂,在塔顶加入ADAME和水,所述反应在35~60℃的温度下和在10~20bar的压力下进行。R=甲基或苄基。
Description
技术领域
本发明涉及通过下面的反应制造如下通式(I)不饱和季铵盐(在下面称为季铵盐)水溶液的制造方法:其中,R表示甲基或苄基,此反应是在水存在下,使丙烯酸N,N-二甲基氨基乙酯(ADAME)和通式(II)季铵化试剂反应:
R-Cl (II)其中,R如上面所定义。
使用季铵盐(I)的水溶液,用于制备当作水处理阳离子絮凝剂的聚合物。
背景技术
欧洲专利EP-B-250,325叙述了通式(I)季铵盐水溶液的制备方法,按照此方法,在至少一种阻聚剂存在下:
—在第一步(a),使在ADAME与5~20wt%的反应必需重量的季铵化试剂反应,或者在一个实施方案(a’)中,与占ADAME重量520wt%的季铵盐水溶液反应,此水溶液含有50~85wt%季铵盐;以及
—在第二步(b),连续加入水和季铵化试剂,直至在水中得到希望的季铵盐浓度。
在步骤(a)和(b)当中,保持温度在30~60℃。再有,在步骤(a)和(b)中,特别在接近反应结束时,在反应介质中要保持氧气流,使得在反应器出口处气体总量与加入到同一反应器入口处氧气的体积(或体积流量)比低于100。
在国际专利申请WO 89/07588中,提供了一种方法,用于减少在季铵化反应中杂质的形成。按照这个方法,在10~80℃的温度下进行如下的反应:
—在第一步,在反应器中加入全部或部分反应所必需的季铵化试剂,此试剂在反应条件下是液态;
—然后加入ADAME,以及
—一旦在反应器中加入了化学当量0~30%的ADAME,就连续地同时加入其余季铵化试剂,其余的ADAME和水,直至得到希望浓度的季铵盐;
—以及,当在反应条件下以气态形式加入季铵化试剂的情况下,此反应在氧存在下进行,提供的压力使得在反应温度下此季铵化试剂是液态,而且在反应结束时,逐渐降低压力,直至降到大气压,同时保证在反应器出口处全部气体的体积流量与加入到反应器中氧的体积流量之比小于100。
按照WO 89/07588的上述方法对按照EP-B-250325的方法做了明显的改善。但是,显示出所得到的季铵盐的纯度还不够。因此,在ADAME和CH3Cl于水性介质中反应的过程中会产生在下文中用缩写词ADAMQUAT MC表示的盐,它是作为丙烯酸(AA)以外的杂质,由ADAME水解而形成的,ADAMQUAT MC的二聚体由下面的通式(I)表示:
由一系列聚合活性的测试,可以证明,这些杂质会影响到由ADAMQUAT得到的阳离子聚合物的质量。
发明内容
因此,本申请公司研究了制备通式(I)盐的水溶液的操作条件,能够尽量减少上述的杂质,提供很高分析质量的盐(I)水溶液。
因此作为本发明目的的此新方法具有很大附加优点,就是提供质量稳定的产物,此方法的特征在于,在一个以旋转盘搅拌的塔中连续地进行所述反应,在塔底加入季铵化试剂,在塔顶加入ADAME和水,所述反应在35~60℃,优选在40~50℃的温度下和在10~20bar,优选在12~16bar的压力下进行。
另外,进行此反应的CH3Cl与ADAME摩尔比一般为1~1.5,特别为1.02~1.15,停留时间为2~6小时,特别为2.5~3.5小时。至于加入的水/季铵化试剂的流量比,一般为0.3~1.2,特别为0.5~0.9。
此外,本发明的方法最好在至少一种稳定剂存在下进行,此稳定剂选自3,5-二叔丁基-4-羟基甲苯、氢醌甲基醚、氢醌、儿茶酚、叔丁基儿茶酚和这些稳定剂的混合物,相对于季铵盐(I)水溶液,此稳定剂的含量特别为20~2000ppm,优选100~1200ppm。
本发明最好还在一种金属螯合剂存在下进行,它们特别选自二亚乙基三胺五乙酸、二亚乙基三胺五乙酸五钠盐、N-羟乙基乙二胺三乙酸和N-羟乙基乙二胺三乙酸的三钠盐,相对于季铵盐(I)的水溶液,此螯合剂的含量特别为1~100ppm,优选为5~30ppm。
一般说来,螯合剂以水溶液的形式加入,因为它们一般以此形式获得。比如,二亚乙基三胺五乙酸的五钠盐,其商品名为VERSENEX80,是大约40wt%水溶液的形式。
按照本发明的方法特别能够制备浓度为50~85wt%的季铵盐(I)的水溶液,其中含有如下面表1所述的很少量杂质。
附图说明
附图1表示按照本发明实施例,连续制备丙烯酰氧基三甲基氯化铵水溶液时使用的装置。在实施例1中对此装置进行了叙述。
具体实施方式
下面的实施例说明本发明并不特别限制其范围。在这些实施例当中,如无特别指出,百分比都是重量百分比。
实施例1:连续制备ADAMQUAT MC水溶液
使用以旋转盘搅拌的塔(1),该塔由容量0.5L的不锈钢管构成,它包括反应物预混区(2)(总体积的1/10),并装有7个取样口(3)、5个测温仪(4)、一个压力计(5)、一个配衡(tarée)17bar的角阀(6)、一个配衡25bar的防爆膜(7)和能够引入反应物的孔。
三个加料罐(8、9、10)分别装有ADAME、水和氯甲烷,通过加料管(8a、9a、10a)与搅拌塔(1)相连,中间插有送料泵(8b、9b、10b)和压力计(分别为8c、9c、10c)。送入氯甲烷的加料管(10a)通到塔底,两根送入ADAME和水的加料管(分别是8a、9a)通到塔顶。
在操作时,密度高于ADAME和氯甲烷的ADAMQUAT MC水溶液从塔(1)的底部经过流出管道(11)注入到两个容器(12、13)中的一个,此容器各装有压力调节器(12a、13a)、压力计(12b、13b)、在压力下操作的特殊搅拌器(12c、13c)、配衡25bar的角阀(12d、13d)、脱气器(12e、13e)、空气引入管(12f、13f)、液面计(14)和测温点(12g、13g)。在其中送入ADAMQUAT MC的容器用作脱气器。一旦装满,就将其断开,将其内容的物料脱气,然后放出,此时将由塔(1)出来的ADAMQUAT MC水溶液送往另一个容器,在那里再进行脱气,然后放出。换句话说,塔是连续操作,而对于脱气,装置则是半连续操作的。
操作模式如下:
在塔(1)中加入550g精ADAMQUAT MC(80%的水溶液)。借助于200bar的贫化空气钢瓶将此装置加压(11bar)。一旦塔(I)达到希望的45℃的温度,就启动三个加料泵(8b、9b、10b),按照平均停留时间2.93小时(hr)和使CH3Cl/ADAME的摩尔比为1.18来调节其流量。为此,加入ADAME的流量是120mL/hr,水的流量是30mL/hr,氯甲烷的流量是49~53mL/hr。在此条件下,CH3Cl/ADAME的摩尔比是1.14~1.23(平均摩尔比1.18),水/CH3Cl的加料流量比为0.71~0.78,停留时间为2.93hr。
在下面的表1中给出结果。ADAME的转化率仍为100%,在操作7.5hr后达到平衡状态。
分析技术如下:
—用电位计测定ADAMQUAT MC的百分比,此电位计借助于硝酸银可以给氯离子计量。
—用高性能液相色谱(HPLC)分析杂质AA和ADAMQUAT MC二聚体含量。
实施例2
如实施例1的操作,只是降低CH3Cl/ADAME的摩尔比。操作条件和结果也报道在表1中。对于操作时间为6小时,ADAME的转化率仍为100%。
表1
实施例 | 温度(℃) | 压力bar | 反应物流量(mL/hr) | 停留时间(hr) | CH3Cl/ADAME平均摩尔比 | 加入水/CH3Cl流量比 | 结果 | ||||||
ADAME | 水 | CH3Cl | 时间min | ADAMQUATMC(%) | 水(%) | AA*ppm | ADAMQUATMC二聚体**ppm | ||||||
1 | 45 | 11 | 120 | 35 | 49~53 | 2.93 | 1.18 | 0.71~0.78 | 加料 | 78.4 | 20.4 | 2001 | 1456 |
105 | 81 | 27.1 | 1552 | 1515 | |||||||||
195 | 72.8 | 27.1 | 820 | 328 | |||||||||
315 | 76.3 | 22.5 | 531 | 141 | |||||||||
450 | 80.5 | 18.2 | 329 | - | |||||||||
585 | 82.9 | 17.6 | 237 | - | |||||||||
635 | 82.8 | 20.4 | 288 | - | |||||||||
2 | 45 | 11 | 120 | 35 | 44~47 | 3 | 1.05 | 0.81~0.86 | 加料 | 81.3 | 19.7 | 1221 | 1309 |
120 | 74.2 | 26.2 | 1100 | 1181 | |||||||||
180 | 77 | 23.9 | 669 | 408 | |||||||||
370 | 80.4 | 20.3 | 360 | 149 | |||||||||
555 | 80.4 | 19.8 | 214 | - |
AA=丙烯酸;*ADAMQUAT MC=丙烯酰氧基三甲基氯化铵
Claims (10)
2.如权利要求1的方法,其特征在于,该反应在40~50℃的温度下进行。
3.如权利要求1和2中之一的方法,其特征在于,该反应在12~16bar的压力下进行。
4.如权利要求1~3中之一的方法,其特征在于,进行该反应时CH3Cl/ADAME的摩尔比为1~1.5。
5.如权利要求4的方法,其特征在于,进行该反应时季铵化试剂/ADAME的摩尔比为1.02~1.15。
6.如权利要求1~5中之一的方法,其特征在于,在进行此反应时,加入水/季铵化试剂的流量比为0.3~1.2,特别为0.5~0.9。
7.如权利要求1~6中之一的方法,其特征在于,进行此反应时的停留时间为2~6小时。
8.如权利要求7的方法,其特征在于,进行此反应的停留时间为2.5~3.5小时。
9.如权利要求1~8中之一的方法,其特征在于,在至少一种稳定剂存在下进行该方法,这些稳定剂选自3,5-二叔丁基-4-羟基甲苯、氢醌甲基醚、氢醌、儿茶酚、叔丁基儿茶酚和这些稳定剂的混合物,相对于季铵盐(I)水溶液,此稳定剂的含量特别为2 0~2000ppm,优选100~1200ppm。
10.如权利要求9的方法,其特征在于,还在至少一种金属螯合剂存在下进行此方法,该金属螯合剂选自二亚乙基三胺五乙酸、二亚乙基三胺五乙酸五钠盐、N-羟乙基乙二胺三乙酸和N-羟乙基乙二胺三乙酸的三钠盐,相对于季铵盐(I)的水溶液,此螯合剂的含量特别为1~100ppm,优选为5~30ppm。
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FR0105701A FR2824062B1 (fr) | 2001-04-27 | 2001-04-27 | Procede de fabrication de solutions aqueuses de sels insatures d'ammonium quaternaire |
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KR (1) | KR20020083444A (zh) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101717340A (zh) * | 2009-12-10 | 2010-06-02 | 淮海工学院 | 高纯度(甲基)丙烯酰氧乙基苄基二甲基氯化铵的清洁生产方法 |
CN102712573A (zh) * | 2010-01-21 | 2012-10-03 | 纳尔科公司 | Dmaea季盐的连续制备 |
CN104744275A (zh) * | 2015-03-23 | 2015-07-01 | 浙江友联化学工业有限公司 | 一种季铵盐型阳离子单体水溶液的制备方法 |
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-
2001
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2002
- 2002-04-11 EP EP02290903A patent/EP1253136A1/fr not_active Withdrawn
- 2002-04-17 TW TW091107815A patent/TWI258461B/zh not_active IP Right Cessation
- 2002-04-24 KR KR1020020022451A patent/KR20020083444A/ko not_active IP Right Cessation
- 2002-04-25 JP JP2002123951A patent/JP2002363144A/ja active Pending
- 2002-04-26 US US10/132,690 patent/US6683203B2/en not_active Expired - Fee Related
- 2002-04-27 CN CN02118479A patent/CN1384095A/zh active Pending
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CN101717340B (zh) * | 2009-12-10 | 2012-10-31 | 淮海工学院 | 高纯度(甲基)丙烯酰氧乙基苄基二甲基氯化铵的清洁生产方法 |
CN102712573A (zh) * | 2010-01-21 | 2012-10-03 | 纳尔科公司 | Dmaea季盐的连续制备 |
CN105646241A (zh) * | 2010-01-21 | 2016-06-08 | 纳尔科公司 | Dmaea季盐的连续制备 |
CN104744275A (zh) * | 2015-03-23 | 2015-07-01 | 浙江友联化学工业有限公司 | 一种季铵盐型阳离子单体水溶液的制备方法 |
CN115745813A (zh) * | 2022-10-26 | 2023-03-07 | 浙江海联新材料科技有限公司 | 一种甲基丙烯酰氧乙基二甲基苄基氯化铵溶液的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US6683203B2 (en) | 2004-01-27 |
FR2824062A1 (fr) | 2002-10-31 |
FR2824062B1 (fr) | 2004-10-15 |
JP2002363144A (ja) | 2002-12-18 |
KR20020083444A (ko) | 2002-11-02 |
US20030023113A1 (en) | 2003-01-30 |
TWI258461B (en) | 2006-07-21 |
EP1253136A1 (fr) | 2002-10-30 |
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