WO2020107197A1 - 一种n-乙烯基吡咯烷酮单体的阻聚剂及其应用 - Google Patents

一种n-乙烯基吡咯烷酮单体的阻聚剂及其应用 Download PDF

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WO2020107197A1
WO2020107197A1 PCT/CN2018/117618 CN2018117618W WO2020107197A1 WO 2020107197 A1 WO2020107197 A1 WO 2020107197A1 CN 2018117618 W CN2018117618 W CN 2018117618W WO 2020107197 A1 WO2020107197 A1 WO 2020107197A1
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polymerization inhibitor
polymerization
vinylpyrrolidone
self
potassium
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PCT/CN2018/117618
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English (en)
French (fr)
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孙旭东
牛磊
张森林
李海朋
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博爱新开源医疗科技集团股份有限公司
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Priority to ES18941896T priority Critical patent/ES2933348T3/es
Priority to US16/964,940 priority patent/US20210040125A1/en
Priority to CN201880016117.5A priority patent/CN113166052B/zh
Priority to EP18941896.5A priority patent/EP3738951B1/en
Priority to PCT/CN2018/117618 priority patent/WO2020107197A1/zh
Publication of WO2020107197A1 publication Critical patent/WO2020107197A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives

Definitions

  • the invention belongs to the technical field of chemical reagents, and particularly relates to an N-vinylpyrrolidone monomer inhibitor and its application.
  • NVP N-vinylpyrrolidone
  • Ether and other organic solvents melting point 13.5 °C, the structural formula is as follows:
  • N-vinylpyrrolidone is affected by the five-membered ring carbonyl group, N-vinylpyrrolidone is lively, polymerizes under weak acidic conditions or initiators, and accelerates N-ethylene under heat, vibration, air/oxygen contact, etc. Pyrrolidone self-polymerizes. According to reports in the literature, N-vinylpyrrolidone is sealed and stored at 17 to 23°C. When stored for a long time, self-polymers are also formed. Therefore, in order to avoid the generation of self-polymers and extend the shelf life in the commercialization process, 0.1% sodium hydroxide or ammonia water, low molecular organic amines, etc. are usually added as polymerization inhibitors.
  • the object of the present invention is to provide a polymerization inhibitor for N-vinylpyrrolidone monomer and its application.
  • a class of weak acid potassium salt was developed and directly added in proportion to inhibit the self-polymerization of N-vinylpyrrolidone monomer, prolong the shelf life, and to a great extent The reduction of monomer color and toxicity.
  • the first aspect of the present invention provides an N-vinylpyrrolidone monomer polymerization inhibitor selected from the group consisting of inorganic weak acid potassium salts and/or organic acid potassium salts.
  • the polymerization inhibitor may be a conventional inorganic weak acid potassium salt or an organic acid potassium salt, or a mixture of the two.
  • the polymerization inhibitor is selected from one or more of potassium carbonate, potassium acetate, potassium propionate, potassium oxalate, potassium citrate and potassium tartrate.
  • the second aspect of the present invention provides the application of the above polymerization inhibitor in the storage or transportation of N-vinylpyrrolidone monomer.
  • the polymerization inhibitor is added to the N-vinylpyrrolidone monomer, which is sealed and stored under the protection of inert gas. That is, the polymerization inhibitor is directly added to the storage or transportation container of N-vinylpyrrolidone monomer for storage or transportation, to achieve the purpose of preventing self-polymerization and prolong the shelf life.
  • the addition amount of the polymerization inhibitor may be 0.005-0.2% of the mass of the N-vinylpyrrolidone monomer.
  • the added amount of the polymerization inhibitor is 0.01-0.15% of the mass of the N-vinylpyrrolidone monomer.
  • the addition amount of the polymerization inhibitor is 0.02-0.12% of the mass of the N-vinylpyrrolidone monomer.
  • the polymerization inhibitor of the invention can be used in a wide temperature range, and all have obvious polymerization inhibition effects.
  • the storage temperature of the N-vinylpyrrolidone monomer added with the polymerization inhibitor is below 120°C.
  • the storage temperature of the N-vinylpyrrolidone monomer added with the polymerization inhibitor is 15-40°C.
  • the present invention has the following advantages:
  • the polymerization inhibitor of the present invention does not affect the normal use of N-vinylpyrrolidone monomer, affects a small change in chromaticity, the color of the monomer is basically unchanged, and is colorless to pale yellow, mainly used for N-ethylene
  • the storage and transportation of pyrrolidone monomers prevent the occurrence of self-polymerization during the storage and transportation of N-vinylpyrrolidone monomers, extend the shelf life, and reduce the risk of severe discoloration of N-vinylpyrrolidone.
  • the shelf life of the N-vinylpyrrolidone monomer can be extended by more than 2 times.
  • the N-vinylpyrrolidone used after the polymerization inhibitor can be directly solution polymerized without removing the polymerization inhibitor, without affecting the color of the N-vinylpyrrolidone monomer and the polymerization rate and solution color during solution polymerization.
  • the dosage of the polymerization inhibitor is small, the temperature range with the polymerization inhibition effect is wide, and the polymerization inhibitor itself is extremely toxic, it is a white solid, and does not carry or produce other colors.
  • Examples 1-7 are used to illustrate the polymerization inhibitor of N-vinylpyrrolidone monomer of the present invention and its application.
  • Example 1 The experimental conditions were the same as in Example 1. A group of brown reagent bottles were filled with pure N-vinylpyrrolidone, nitrogen was evacuated and sealed, and the detection was used as a blank control. For the blank control sample, the self-polymerization time is 50 minutes, and the sample detected by the self-polymer is a colorless transparent liquid. The specific results are shown in Table 1.
  • Example 2 The experimental conditions were the same as in Example 3. A group of brown reagent bottles were filled with pure N-vinylpyrrolidone, evacuated and sealed with nitrogen. On the 10th day of heating test, self-polymerization had occurred, but the viscosity was small and the sample was a colorless liquid. The specific results are shown in Table 2.
  • Example 5 N-vinylpyrrolidone monomer was added to 0.025% potassium acetate and stored at room temperature for 10 months. Using purified water as the solvent, PVP was synthesized according to the current PVP K30 polymerization process. After polymerization, the K value was 31.5. The polymerization solution is a colorless and transparent solution.
  • Example 4 Potassium propionate 0.1% 150 days ⁇ 50Haze Comparative Example 2 - - 10 days ⁇ 50Haze Comparative Example 3 Sodium hydroxide 0.1% 50 days 400Haze
  • the polymerization inhibitor of the present invention can effectively inhibit the polymerization of N-vinylpyrrolidone monomer, the dosage is small, it has high efficiency, and has a wide temperature range with polymerization inhibitory effect , Within the range of preferred conditions, the effect is better.
  • the use of the polymerization inhibitor basically does not affect the color of the N-vinylpyrrolidone monomer, the polymerization rate and the color of the polymerization solution during solution polymerization.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Pyrrole Compounds (AREA)

Abstract

N-乙烯基吡咯烷酮单体的阻聚剂及其应用。该阻聚剂选自无机弱酸钾盐和/或有机酸钾盐；将阻聚剂加入N-乙烯基吡咯烷酮单体中，在惰性气体保护下密封保存，所述阻聚剂的添加量为N-乙烯基吡咯烷酮单体质量的0.005-0.2％。将该阻聚剂直接按比例投加至N-乙烯基吡咯烷酮单体中，可抑制N-乙烯基吡咯烷酮单体的自聚，延长保质期，且极大程度的降低单体色度和毒性，在溶液聚合时可直接使用，不需除去阻聚剂，且阻聚剂亦不影响聚合溶液的色度。

Description

一种N-乙烯基吡咯烷酮单体的阻聚剂及其应用 技术领域
本发明属于化学试剂技术领域，具体涉及一种N-乙烯基吡咯烷酮单体的阻聚剂及其应用。
背景技术
N-乙烯吡咯烷酮(N-vinylpyrrolidone)简称NVP，其是2-吡咯烷酮的乙烯化产物，分子结构由乙烯基与五元环内酰胺基组成，是一种无色透明液体，易溶于水、醇、醚及其它有机溶剂，熔点13.5℃，结构式如下：
Figure PCTCN2018117618-appb-000001
N-乙烯基吡咯烷酮受五元环羰基的影响，N-乙烯基吡咯烷酮性质活泼，在弱酸性条件或引发剂作用下发生聚合，在受热、震荡、空气/氧气接触等条件下则加速N-乙烯基吡咯烷酮自聚。据文献报道，N-乙烯基吡咯烷酮在17～23℃下密闭保存，贮存时间较长时，亦有自聚物生成。因此在商业化过程为避免自聚物的产生，延长保质期，通常加入0.1％氢氧化钠或氨水、低分子有机胺等作为阻聚剂。
但是氢氧化钠、氨水的加入，虽抑制了自聚物的快速生成，但加速了N-乙烯基吡咯烷酮颜色的加深，逐渐由无色变成，淡黄色、黄色，乃至褐色；低分子有机氨以N,N-二仲丁基对苯二胺为主，10ppm的用量，即能达到极佳的阻聚效果，但依然不能避免颜色的加深，且由无色到粉红色、红色、棕红色发展，且N,N-二仲丁基对苯二胺本身为褐色剧毒物质；其它常用的贮存阻聚剂如2,6-二叔丁基对甲苯酚、叔丁基邻苯二酚、苯醌等抗氧 型酚/醌类阻聚剂普遍存在颜色加深和毒性大的问题；另有其它高温阻聚剂，大多都需要在使用前通过蒸馏或其它方式除去。
发明内容
针对上述情况，本发明的目的是提供一种N-乙烯基吡咯烷酮单体的阻聚剂及其应用。依据N-乙烯基吡咯烷酮在偏酸性条件下易于自聚的特点，开发出一类弱酸钾盐，直接按比例投加，抑制N-乙烯基吡咯烷酮单体的自聚，延长保质期，且极大程度的降低单体色度和毒性。
本发明的第一方面提供了一种N-乙烯基吡咯烷酮单体的阻聚剂，该阻聚剂选自无机弱酸钾盐和/或有机酸钾盐。
本发明中，所述阻聚剂可选用常规的无机弱酸钾盐或有机酸钾盐，或者两者的混合物。优选地，所述阻聚剂选自碳酸钾、乙酸钾、丙酸钾、草酸钾、柠檬酸钾和酒石酸钾中的一种或几种。
本发明的第二方面提供了上述的阻聚剂在N-乙烯基吡咯烷酮单体储存或运输中的应用。
具体地，将阻聚剂加入N-乙烯基吡咯烷酮单体中，在惰性气体保护下密封保存。即将阻聚剂直接投加至储存或运输的N-乙烯基吡咯烷酮单体的储运容器中，实现防止自聚的目的，延长保质期。
本发明中，所述阻聚剂的添加量可以为N-乙烯基吡咯烷酮单体质量的0.005-0.2％。优选地，所述阻聚剂的添加量为N-乙烯基吡咯烷酮单体质量的0.01-0.15％。进一步优选地，所述阻聚剂的添加量为N-乙烯基吡咯烷酮单体质量的0.02-0.12％。
本发明的阻聚剂可在较宽的温度范围内进行使用，均具有明显的阻聚效果。优选地，加入所述阻聚剂的N-乙烯基吡咯烷酮单体的保存温度在120℃以下。
为了保证更佳的阻聚效果，进一步优选地，加入所述阻聚剂的N-乙烯基吡咯烷酮单体的保存温度为15-40℃。
与现有技术相比，本发明具有如下有益点：
本发明的阻聚剂投加后不影响N-乙烯基吡咯烷酮单体的正常使用，影响色度变化较小，单体的颜色基本不变，为无色至淡黄色，主要用于N-乙烯基吡咯烷酮单体的储存与运输，预防N-乙烯基吡咯烷酮单体储存与运输过程中自聚的发生，延长保质期，降低N-乙烯基吡咯烷酮严重变色的风险。阻聚剂在40℃以下使用时，可将N-乙烯基吡咯烷酮单体的保质期延长2倍以上。另外，阻聚剂使用后的N-乙烯基吡咯烷酮无需除去阻聚剂，可直接溶液聚合，不影响N-乙烯基吡咯烷酮单体的颜色及溶液聚合时的聚合速率及聚合液色度。阻聚剂的投加量较少，具有阻聚功效的温度范围较宽，且阻聚剂本身毒性极小，为白色固体，本身不携带或产生其他颜色。
具体实施方式
下面将结合本发明实施例对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。
实施例1-7用于说明本发明的N-乙烯基吡咯烷酮单体的阻聚剂及其应用。
实施例1
在容量大小相同的一组棕色试剂瓶中，分别装入新产N-乙烯基吡咯烷酮单体100±0.5g，分别投加碳酸钾0.10±0.002g，通氮气鼓泡排出空气后密封。摇匀后置于120℃烘箱，每隔10分钟取一瓶，测试自聚情况。第90分钟时，有自聚物检出，样品为无色透明液体。具体结果如表1所示。
实施例2
在容量大小相同的一组棕色试剂瓶中，分别装入新产N-乙烯基吡咯烷酮单 体100±0.5g，分别投加乙酸钾0.0250±0.0005g，通氮气鼓泡排出空气后密封。摇匀后置于120℃烘箱，每隔20分钟取一瓶，测试自聚情况。第300分钟时，有自聚物检出，样品仍为无色透明液体。具体结果如表1所示。
实施例3
在容量大小相同的一组棕色试剂瓶中，分别装入新产N-乙烯基吡咯烷酮单体100±0.5g，分别投加乙酸钾0.0250±0.0005g，通氮气鼓泡排出空气后密封。摇匀后置于40℃烘箱，每隔10天取一瓶，测试自聚情况。第190天时，有自聚物检出，样品仍为淡黄色透明液体。具体结果如表2所示。
实施例4
在容量大小相同的一组棕色试剂瓶中，分别装入新产N-乙烯基吡咯烷酮单体200±0.5g，分别投加丙酸钾0.10±0.005g，通氮气鼓泡排出空气后密封。摇匀后置于40℃烘箱，每隔10天取一瓶，测试自聚情况。第150天时，有自聚物检出，样品仍为无透明液体，色度＜50Haze。具体结果如表2所示。
实施例5
在容量大小相同的一组棕色试剂瓶中，分别装入新产N-乙烯基吡咯烷酮单体100±0.5g，分别投加乙酸钾0.0250±0.0005g，通氮气鼓泡排出空气后密封。摇匀后置于25℃稳定性实验箱(模拟室温)，每隔30天(一个月)取一瓶，测试自聚情况。第10个月时有自聚物检出(第9个月未检出)，样品为轻微淡黄色透明液体，色度50Haze。具体结果如表3所示。
实施例6
在容量大小相同的一组棕色试剂瓶中，分别装入新产N-乙烯基吡咯烷酮单体100±0.5g，分别投加乙酸钾0.050±0.005g，通氮气鼓泡排出空气后密封。摇匀后置于25℃稳定性实验箱(模拟室温)，每隔30天(一个月)取一瓶，测试 自聚情况。第10个月时有自聚物检出，样品为淡黄色透明液体，色度125Haze。具体结果如表3所示。
实施例7
在容量大小相同的一组棕色试剂瓶中，分别装入新产N-乙烯基吡咯烷酮单体200±0.5g，分别同时投加乙酸钾和柠檬酸钾各0.050±0.005g，通氮气鼓泡排出空气后密封。摇匀后置于25℃稳定性实验箱(模拟室温)，每隔30天(一个月)取一瓶，测试自聚情况。第10个月时有自聚物检出，样品为淡黄色透明液体，色度100Haze。具体结果如表3所示。
对比例1
实验条件同实施例1，在一组棕色试剂瓶中装有纯N-乙烯吡咯烷酮，氮气排空、密封，检测做空白对照。空白对照样，自聚时间为50分钟，有自聚物检出的样品为无色透明液体。具体结果如表1所示。
对比例2
实验条件同实施例3，在一组棕色试剂瓶中装有纯N-乙烯吡咯烷酮，氮气排空、密封，加热测试第10天，已发生自聚，但粘度较小，样品为无色液体。具体结果如表2所示。
对比例3
在容量大小相同的一组棕色试剂瓶中，分别装入新产N-乙烯基吡咯烷酮单体100±0.5g，分别投加氢氧化钠0.10±0.01g，通氮气鼓泡排出空气后密封。摇匀后置于40℃烘箱，每隔10天取一瓶，测试自聚情况。第50天时，有自聚物检出，样品为黄色透明液体，色度400Haze。具体结果如表2所示。
对比例4
在容量大小相同的一组棕色试剂瓶中，分别装入新产N-乙烯基吡咯烷酮单 体100±0.5g，分别投加氢氧化钠0.10±0.01g，通氮气鼓泡排出空气后密封。摇匀后置于25℃稳定性实验箱，每隔30天取一瓶，测试自聚情况。第7个月(180～210)天时有自聚物检出，样品为黄色透明液体，色度250Haze。具体结果如表3所示。
对比例5
在容量大小相同的一组棕色试剂瓶中，分别装入新产N-乙烯基吡咯烷酮单体100±0.5g，通氮气鼓泡排出空气，分别投加26.5％氨水0.38mL后密封。摇匀后置于25℃稳定性实验箱，每隔30天取一瓶，测试自聚情况。第4个月(90～120)天时有自聚物检出，样品为无色透明液体，色度＜50Haze。具体结果如表3所示。
应用实施例
将实施例5中投加过0.025％乙酸钾，室温存放10个月的N-乙烯基吡咯烷酮单体，以纯化水为溶剂，按照现行PVP K30聚合工艺合成PVP，聚合后测试K值为31.5，聚合溶液为无色透明溶液。
以下表1、表2和表3中分别记载了在120℃、40℃和25℃下的实施例和对比例的相应数据。
表1
项目 阻聚剂 投加量 发生自聚时时长 颜色
实施例1 碳酸钾 0.1％ 90分钟 无色
实施例2 乙酸钾 0.025％ 300分钟 无色
对比例1 -- -- 50分钟 无色
表2
项目 阻聚剂 投加量 发生自聚时时长 单体色度
实施例3 乙酸钾 0.025％ 190天 50Haze
实施例4 丙酸钾 0.1％ 150天 ＜50Haze
对比例2 -- -- 10天 ＜50Haze
对比例3 氢氧化钠 0.1％ 50天 400Haze
表3
项目 阻聚剂 投加量 发生自聚时时长 单体色度
实施例5 乙酸钾 0.025％ 10个月 50Haze
实施例6 乙酸钾 0.05％ 10个月 125Haze
实施例7 乙酸钾+柠檬酸钾 0.05％+0.05％ 10个月 100Haze
对比例4 氢氧化钠 0.1％ 7个月 250Haze
对比例5 氨水 0.1％ 4个月 <50Haze
由表1-表3的数据可知，本发明的阻聚剂可有效的抑制N-乙烯基吡咯烷酮单体的聚合，投加量较少，具有高效性，且具有阻聚功效的温度范围较宽，在优选条件范围内，效果更佳。另外，由应用实施例可知，该阻聚剂使用后基本不影响N-乙烯基吡咯烷酮单体的颜色及溶液聚合时的聚合速率及聚合液色度。
以上已经描述了本发明的实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的实施例。在不偏离所说明实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。

Claims (8)

  1. 一种N-乙烯基吡咯烷酮单体的阻聚剂，其特征在于，该阻聚剂选自无机弱酸钾盐和/或有机酸钾盐。
  2. 根据权利要求1所述的阻聚剂，其特征在于：所述阻聚剂选自碳酸钾、乙酸钾、丙酸钾、草酸钾、柠檬酸钾和酒石酸钾中的一种或几种。
  3. 权利要求1或2所述的阻聚剂在N-乙烯基吡咯烷酮单体储存或运输中的应用。
  4. 根据权利要求3所述的应用，其特征在于：将阻聚剂加入N-乙烯基吡咯烷酮单体中，在惰性气体保护下密封保存。
  5. 根据权利要求4所述的应用，其特征在于：所述阻聚剂的加入量为N-乙烯基吡咯烷酮单体质量的0.005-0.2％。
  6. 根据权利要求5所述的应用，其特征在于：所述阻聚剂的添加量为N-乙烯基吡咯烷酮单体质量的0.01-0.15％。
  7. 根据权利要求4所述的应用，其特征在于：所述保存的温度在120℃以下。
  8. 根据权利要求7所述的应用，其特征在于：所述保存的温度为15-40℃。
PCT/CN2018/117618 2018-11-27 2018-11-27 一种n-乙烯基吡咯烷酮单体的阻聚剂及其应用 WO2020107197A1 (zh)

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