WO2013166782A1 - Procédé de préparation d'iode n-vinyl butyl lactame homopolymérisé ayant une teneur effective en iode de 20 % - Google Patents

Procédé de préparation d'iode n-vinyl butyl lactame homopolymérisé ayant une teneur effective en iode de 20 % Download PDF

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Publication number
WO2013166782A1
WO2013166782A1 PCT/CN2012/079056 CN2012079056W WO2013166782A1 WO 2013166782 A1 WO2013166782 A1 WO 2013166782A1 CN 2012079056 W CN2012079056 W CN 2012079056W WO 2013166782 A1 WO2013166782 A1 WO 2013166782A1
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Prior art keywords
iodine
preparation
homopolymerized
particle size
vinylbutyrolactam
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PCT/CN2012/079056
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English (en)
Chinese (zh)
Inventor
王宇
刘薇
陈占
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上海宇昂生物科技有限公司
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Publication of WO2013166782A1 publication Critical patent/WO2013166782A1/fr

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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
    • C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F126/10—N-Vinyl-pyrrolidone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens

Definitions

  • the invention relates to the technical field of compound preparation, in particular to the technical field of preparation of homopolymerized N-vinyl butyrolactam iodine, and specifically relates to a method for preparing homopolymeric N-vinyl butyrolactam iodine having a 20% effective iodine content. Background technique
  • the homopolymerized N-ethylglycolyl lactam iodine is a yellow-brown to reddish-brown amorphous powder formed by the hydrogen bonding and other external forces in the complexation of N-ethylglycolyl lactam homopolymer with iodine.
  • An amorphous complex iodine is a kind of iodophor (Cui Yingde, Yi Guobin, Liao Lewen. Synthesis and application of polyvinylpyrrolidone [M]. Science Press, 2001, 2:161). It is an excellent disinfectant, and the 1990 edition of the Pharmacopoeia in China began to be included.
  • N-Ethylbutyrolactam homopolymer is a nonionic surfactant, which has no antibacterial effect itself, but can improve the solubility of iodine, and help to improve the wetting and penetrating ability of iodine solution to objects, so that effective iodine
  • the affinity for the cell membrane is enhanced, and the effective iodine can be directly introduced into the cell membrane and cytoplasm of the bacteria, and the bacteria are immediately killed within a few seconds, thereby enhancing the bactericidal ability of iodine, and the N-vinyl butyrolactam iodine also has It is easily soluble in water and has no irritation, allergies and poisoning to skin and mucous membranes.
  • the homopolymerized N-vinyl butylamide iodine can be used not only as an aqueous solution but also in a solid form in some special cases. This makes the homopolymerized N-vinyl butyrolactam iodine widely used in various fields of sterilization and disinfection, expands the use range of iodine, and is widely used in hospital disinfection at home and abroad.
  • the effective iodine content of homopoly N-vinyl butyrolactone iodine powder currently on the market and the effective iodine content specified in the Pharmacopoeia are both 9%-12%, however, the homopolymeric N-vinyl butyrolactam with higher effective iodine content Iodine shows good advantages both in terms of application and storage, especially in terms of market profit, using homogeneous N-vinyl butyrolactam iodine with an effective iodine content of 10% and 20% homopolymerized N- Vinyl butyrolactam iodine to prepare homopoly N-vinyl butyrolactam iodine disinfectant of the same specification, and the effective iodine of 20% homopolymerized N-vinyl butyrolactam iodine greatly reduces the cost of the disinfectant. It also proves its market operability.
  • the preparation method of butyl iodide iodine, the preparation method of the homopolymerized N-vinyl butyrolactone iodine with 20% effective iodine content is ingeniously designed, and the preparation of the homopolymer N-vinyl butyrolactam iodine is effective.
  • the iodine content is 20%, and it also has high stability and photo-bactericidal performance, which is suitable for large-scale popularization and application.
  • a 20% effective iodine content homopolymeric N-vinyl butyrolactam iodine preparation method of the present invention is characterized in that N-vinyl butyrolactam homopolymer and 850 ⁇ ⁇ particle size or less
  • the iodine is a raw material, wherein the mass ratio of the ⁇ -vinyl butyrolactam homopolymer to the iodine below the 850 ⁇ m particle size is 7:3 to 5:5, and 0.01 is added based on the amount of the raw material. % ⁇ 5.0% by weight of the auxiliary agent, the fractional preparation method is stirred at a temperature of 50-100 ° C for 5-20 hours.
  • the auxiliaries may be any suitable auxiliaries.
  • the auxiliaries are sodium citrate, sodium chloride or sodium acetate.
  • the N-vinyl butyrolactam homopolymer, the iodine having a particle diameter of 850 ⁇ m or less, the auxiliary agent, the temperature, and the stirring reaction time may be selected from the above range, preferably, The ⁇ -ethylglycolyl lactam homopolymer is 68 g, the iodine of the 850 ⁇ particle size is 32 g, the amount of the auxiliary agent is 0.46 g, the temperature is 60 ° C, the stirring The reaction time was 17 hours.
  • the segmented preparation method refers to first reacting an excess amount of N-ethylglycolide lactam homopolymer, a small amount of iodine and an auxiliary agent for a period of time, and then adding a certain amount of iodine and a small amount of auxiliary agent.
  • the excess homo-N-vinyl butyrolactam in the reactants is further reacted with iodine, and may of course be divided into three or more segments. More preferably, the fractional preparation method is to firstly apply 68 g of the N.
  • a vinyl butyrolactam homopolymer 22 g of the 850 ⁇ m particle size iodine and 0.35 g of the auxiliary agent were stirred at 60 ° C for 8 hours, after which 10 g of the above-mentioned 850 ⁇ m particle size were further added.
  • the auxin and the promoter of O.lg were continuously stirred at 60 ° C for 9 hours.
  • the N-vinyl butyrolactam homopolymer, the iodine having a particle diameter of 850 ⁇ m or less, the auxiliary agent, the temperature, and the stirring reaction time may be selected from the above range, preferably,
  • the ⁇ -ethylglycolyl lactam homopolymer is 62 g
  • the iodine of the 550 ⁇ particle size is 38 g
  • the amount of the auxiliary agent is 2.6 g
  • the temperature is 75 ° C
  • the stirring The reaction time was 19 hours.
  • the segmented preparation method refers to first reacting an excess amount of N-ethylglycolide lactam homopolymer, a small amount of iodine and an auxiliary agent for a period of time, and then adding a certain amount of iodine and a small amount of auxiliary agent.
  • the excess homo- N-vinyl butyrolactam in the reactants is further reacted with iodine, and may of course be divided into three or more segments.
  • the fractional preparation method is to firstly 62g the N a vinyl butyrolactam homopolymer, 20 g of the 550 ⁇ m particle size iodine and 1.4 g of the auxiliary agent were stirred at 75 ° C for 11 hours, after which 18 g of the 550 ⁇ m particle size were added. Iodine and 1.2 g of the above-mentioned auxiliary agent were further stirred at 75 ° C for 8 hours.
  • the N-vinyl butyrolactam homopolymer, the iodine having a particle diameter of 850 ⁇ m or less, the auxiliary agent, the temperature, and the stirring reaction time may be selected from the above range, preferably, The ⁇ -ethylglycolyl lactam homopolymer is 70 g, the iodine of the 750 ⁇ particle size is 30 g, the amount of the auxiliary agent is 0.2 g, the temperature is 97 ° C, the stirring The reaction time is 19 hour.
  • the segmented preparation method refers to first reacting an excess amount of N-ethylglycolide lactam homopolymer, a small amount of iodine and an auxiliary agent for a period of time, and then adding a certain amount of iodine and a small amount of auxiliary agent.
  • the excess homo-N-vinyl butyrolactam in the reactants is further reacted with iodine, and may of course be divided into three or more segments. More preferably, the fractional preparation method is to firstly apply 70 g of the N.
  • the beneficial effects of the present invention are specifically as follows:
  • the preparation method of the 20% effective iodine content homopolymer N-vinyl butyrolactam iodine of the present invention is an N-vinyl butyrolactam homopolymer and an iodine having a particle diameter of 850 ⁇ m or less
  • the fractional preparation method is stirred at a temperature of 50-100 ° C for 5-20 hours, thereby obtaining a homopolymerized N-ethylglycolyl lactam iodine effective iodine
  • the content is more than 20%, the design is ingenious, the preparation of the single, and also has high stability and optical bactericidal performance, suitable for large-scale promotion and application.
  • Figure 1 is a graph showing the effect of reaction temperature on effective iodine content.
  • Figure 2 is a graph showing the effect of additive addition on reaction time.
  • Figure 3 is a graph showing the effect of the addition of an adjuvant on the effective iodine content.
  • Figure 4 is a graph showing the effect of particle size of iodine on effective iodine content. detailed description
  • the effective iodine concentration of the sample can be determined by referring to the Chinese Pharmacopoeia (Chinese Pharmacopoeia. Part 2 [S]. 2005: 823) method.
  • the effective iodine content was measured by the United States Pharmacopoeia: Weigh the sample about lg, accurately weigh it in a beaker, add some water to stir it, dissolve it, transfer it to a 100 mL volumetric flask, and accurately measure the sample solution with a pipette.
  • the effective iodine content in the sample is expressed in mass fraction (%):
  • V 2 the volume of the sodium thiosulfate standard solution consumed in the blank test, in milliliters (mL);
  • the maximum effective iodine content of homopolymerized N-vinyl butyrolactam is limited by solubility. In order to reduce the total iodine content and reduce the cost of the product, it is necessary to find a reasonable ratio of homopolymeric N-vinyl butyrolactam to iodine.
  • the effective iodine content in the homopolymerized N-vinyl butyrolactam iodine increases with the increase of the amount of iodine in a certain range, and the value tends to be stable after reaching a certain content.
  • the reason may be that the number of terminal groups of the homopolymerized N-ethylglycolyl lactam molecular chain limits the amount of iodine complexed by it.
  • the total amount of iodine in the homo- N-vinyl butyrolactam iodine raw material having an effective iodine content of 20% is preferably 30% to 50%.
  • N-vinyl butyrolactam homopolymer and iodine can be complexed at room temperature, but the time required at different temperatures is different, and the effective iodine content of the final product is also different.
  • the general reaction temperature is controlled at 45-100 ° C. .
  • the effect of the study temperature on the effective iodine content of the product is shown in Figure 1 when the mass fraction of homopolymerized N-vinyl butyrolamide is 70%, the mass fraction of iodine is 30%, and the same auxiliaries are reacted for 6 hours.
  • 70 ° C is the optimum temperature for the preparation of homopolymerized N-vinyl butyrolactam iodine; meanwhile, under the same conditions, the effective iodine content of N-vinyl butyrolactam iodine
  • the increase in temperature first increases and then decreases. This is mainly because the increase of temperature is beneficial to increase the number of activated molecules of the reactants, thereby accelerating the frequency of intermolecular collisions and allowing the reactants to fully react; however, the reaction rate is too high, and the peak of effective iodine content during the reaction is peaked. It was greatly advanced, and as the reaction time prolonged, the complex bond between the homopolymerized N-vinyl butyrolactam and iodine gradually broke, and the effective iodine content rapidly decreased.
  • additives such as sodium citrate acts as a grinding aid, which promotes the contact between iodine and homopolymerized N-vinyl butyrolactam to exacerbate the internal friction, thereby causing an increase in the reaction rate, a sufficient complexation reaction, and further reaction.
  • the time is reduced and the effective iodine content is increased.
  • the mass fraction of N-vinyl butyrolactam was 70%, the mass fraction of iodine was 30%, and the reaction was carried out at 70 °C for 12 hours.
  • the effect of iodine with different particle sizes on the effective iodine content of the product was studied, as shown in Fig. 4.
  • the reaction of homopolymeric N-vinyl butyrolactam and iodine is essentially a solid-solid reaction and a gas-solid reaction of iodine with homopolymeric N-vinyl butyrolactam.
  • the contact surface of the iodine with the homopolymerized N-vinyl butyrolactam can be greatly improved, thereby increasing the reaction rate and the effective iodine content to reduce the reaction time and the quality influencing factors during the reaction. This is mainly because of the strong oxidizing property of iodine. If the reaction time is too long, iodine will cause some oxidation of N-vinyl butyrolactam to break the molecular chain, which will affect the progress of the complexation reaction.
  • the processing is indispensable, can be obtained from Figure 4. Real.
  • Segmented preparation firstly use an excess of homopolyvinylbutyrolactam with a small amount of iodine, complexed with sodium chloride and other auxiliaries to form a homogenous N- with a lower effective iodine content (12% - 18%). Vinyl butyrolactam iodine, and then add a certain amount of iodine and a small amount of sodium chloride and other additives, so that the excess homopolymerized N-vinyl butyrolactam in the reactants continues to react with iodine to prepare high effective iodine. Content (more than 20%) of homopolymeric N-vinyl butyrolactam iodine.
  • the method has a higher effective iodine content of homopolymerized N-ethylglycolyl lactam iodine, generally more than 20%.
  • the reasons may be: On the one hand, the complexation performance of iodine is very good, and it is easy to prepare 8%-12% effective iodine content of homopolymeric N-vinyl butyrolactam under normal conditions; however, due to homopolymerization of N-ethylene The limited number of end groups of the chitin lactam and the large steric hindrance between the groups on the molecular chain make it difficult to achieve theoretically sufficient complexation with iodine.
  • this segmented preparation process overcomes the deactivation of homopolymerized N-vinyl butyrolactam by temperature and oxidative denaturation of iodine during prolonged reaction.
  • the complexation process of homopolymerized N-vinyl butyrolactam with iodine is a typical exothermic reaction. During the reaction, more heat is released, which will increase the temperature of the reaction system in a shorter period of time, resulting in homopolymerization of N-ethylene.
  • the partial deactivation of the butyrolactam is inactivated; and by the fractional preparation, since the "reaction point" is less in the whole process, the generated heat is relatively small and can be released relatively quickly, and at the same time, the addition of additives such as sodium chloride
  • additives such as sodium chloride
  • the steric hindrance of each group of the homopolymeric N-vinyl butyrolactam molecular chain is effectively reduced, thereby greatly increasing the degree of complexation, and a homogenous N-vinyl butyrolactam iodine having a higher effective iodine content is prepared.
  • the effective iodine content of N-vinyl butyrolactam iodine is above 20%.
  • the invention will be more specifically illustrated by the following examples, but the invention is not limited by these examples. In the following, "% by weight” is only expressed as “%” unless otherwise stated.
  • Example 2 The same operation as in Example 1 was carried out except that sodium citrate was not added, and as a result, the effective iodine content was found to be 15.72%.
  • Example 2 The same operation as in Example 1 was carried out except that sodium citrate was not added, and as a result, the effective iodine content was found to be 15.72%.
  • Example 3 The same operation as in Example 2 was carried out except that iodine having an unpulverized iodine (particle diameter of more than 1500 ⁇ m) was used instead of iodine having a particle diameter of 550 ⁇ m, and as a result, an effective iodine content of 16.22% was detected.
  • iodine having an unpulverized iodine particle diameter of more than 1500 ⁇ m
  • the raw material N-vinyl butyrolactam homopolymer and the iodine mass ratio after particle size selection treatment are 7:3 ⁇ 5:5, and 0.01% ⁇ 5.0% by weight of the auxiliary agent is added based on the amount of the raw material.
  • the auxiliary agent is added based on the amount of the raw material.
  • sodium citrate, sodium chloride, sodium acetate sodium citrate
  • the fractional preparation method is stirred at 50-100 ° C for about 5-20 hours to obtain a homogenous N-vinyl butyl with high effective iodine content. Lactam iodine powder.
  • the preparation method of the 20% effective iodine content of the homopolymerized N-ethylglycolyl lactam iodine of the invention is ingeniously designed, and the prepared iodine has an effective iodine content of the homopolymerized N-vinyl butyrolactam. 20%, it also has high stability and spectral sterilization performance, suitable for large-scale promotion and application.

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Abstract

La présente invention concerne un procédé de préparation d'iode de N-vinyl butyl lactame homopolymérisé ayant une teneur effective en iode de 20 %, consistant à : utiliser un homopolymère d'iode de N-vinyl butyl lactame et de l'iode dont les particules ont une taille inférieure à 850 μm comme matières premières, le rapport de masse entre l'homopolymère d'iode de N-vinyl butyl lactame et l'iode dont les particules ont une taille inférieure à 850 μm allant de 7/3 à 5/5 ; dans le même temps, en utilisant la quantité de matières premières comme référence, ajouter un additif de 0,01 % à 5 % en poids ; agiter à une température allant de 50 à 100 °C pour que la réaction se produise pendant 5 à 20 heures, selon une manière de préparation segmentée. L'additif peut être du citrate de sodium, du chlorure de sodium ou de l'acétate de sodium.
PCT/CN2012/079056 2012-05-10 2012-07-23 Procédé de préparation d'iode n-vinyl butyl lactame homopolymérisé ayant une teneur effective en iode de 20 % WO2013166782A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1341361A (zh) * 2001-09-02 2002-03-27 广东庆发药业有限公司 聚维酮碘的制备方法
CN101838359A (zh) * 2010-05-21 2010-09-22 上海宇昂生物科技有限公司 非离子n-乙烯基丁内酰胺碘、高稳定性非离子n-乙烯基丁内酰胺碘及相关超速制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006348118A (ja) * 2005-06-14 2006-12-28 Dai Ichi Kogyo Seiyaku Co Ltd ポリビニルピロリドン−ヨウ素複合体
CN102125053B (zh) * 2011-01-07 2013-08-07 上海宇昂水性新材料科技股份有限公司 高稳定非离子n-乙烯基丁内酰胺碘溶液及相关配制方法
CN102093279B (zh) * 2011-01-07 2012-05-23 上海宇昂化工科技发展有限公司 高稳定非离子n-乙烯基丁内酰胺碘及相关制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1341361A (zh) * 2001-09-02 2002-03-27 广东庆发药业有限公司 聚维酮碘的制备方法
CN101838359A (zh) * 2010-05-21 2010-09-22 上海宇昂生物科技有限公司 非离子n-乙烯基丁内酰胺碘、高稳定性非离子n-乙烯基丁内酰胺碘及相关超速制备方法

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