WO2013166782A1 - Preparation method of homopolymerized n-vinyl butyl lactam iodine with effective iodide content of 20% - Google Patents
Preparation method of homopolymerized n-vinyl butyl lactam iodine with effective iodide content of 20% Download PDFInfo
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- 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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- homopolymerized
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- vinylbutyrolactam
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- 239000011630 iodine Substances 0.000 title claims abstract description 159
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 159
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 150000003951 lactams Chemical class 0.000 title abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 title abstract description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 title abstract 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 title abstract 2
- 229920001519 homopolymer Polymers 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 11
- 239000001509 sodium citrate Substances 0.000 claims abstract description 10
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000011780 sodium chloride Substances 0.000 claims abstract description 9
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000001632 sodium acetate Substances 0.000 claims abstract description 7
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 40
- OVUJFYLDKRZVME-UHFFFAOYSA-N [I].C=CN1CCCC1=O Chemical compound [I].C=CN1CCCC1=O OVUJFYLDKRZVME-UHFFFAOYSA-N 0.000 claims description 28
- 239000012752 auxiliary agent Substances 0.000 claims description 27
- 230000035484 reaction time Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- -1 N-vinylbutyrolactam iodine Butyrolactam Chemical compound 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000000996 additive effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 13
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 9
- 238000010668 complexation reaction Methods 0.000 description 7
- 239000000376 reactant Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 239000000645 desinfectant Substances 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- 229930192334 Auxin Natural products 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GGJYJVJFZBPEEZ-UHFFFAOYSA-N N-(1-ethenylpyrrolidin-2-ylidene)hydroxylamine Chemical compound C(=C)N1C(CCC1)=NO GGJYJVJFZBPEEZ-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- DGKMAOSPHRIZST-UHFFFAOYSA-N [I].ICCCC Chemical compound [I].ICCCC DGKMAOSPHRIZST-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002363 auxin Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000001941 photobactericidal effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
A preparation method of homopolymerized N-vinyl butyl lactam iodine with an effective iodide content of 20%, comprises: using an N-vinyl butyl lactam iodine homopolymer and iodine with the particle size being small than 850 μm as raw materials, the mass ratio of the N-vinyl butyl lactam iodine homopolymer to the iodine with the particle size being small than 850 μm being 7:3-5:5; meanwhile, with the amount of the raw materials being the reference, adding an additive of 0.01%-5% by weight; stirring at the temperature of 50-100°C for reaction for 5-20 hours in a segmented preparation manner. The additive may be sodium citrate, sodium chloride, or sodium acetate.
Description
20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法 技术领域 Method for preparing homopolymerized N-vinyl butyrolactam iodine with 20% effective iodine content
本发明涉及化合物制备技术领域, 特别涉及均聚 N-乙烯基丁内酰胺碘制备技术领域, 具 体是指一种 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法。 背景技术 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
均聚 N-乙婦基丁内酰胺碘为黄棕色至红棕色的无定形粉末 , 是由 N-乙婦基丁内酰胺均 聚物与碘以络合的形式借助氢键和其他外力作用形成的一种不定型络合碘,是碘伏的一种(崔 英德, 易国斌, 廖列文.聚乙烯吡咯烷酮的合成与应用 [M].科学出版社, 2001 , 2:161 )。 它是 一种优秀的消毒剂, 我国 1990年版药典开始收载。 可以保持较长时间的杀菌力, 为广语的强 力杀菌消毒剂 ( G & SMED ICAL LTD(US).Infection fighting composition for topical application[P].US5137718 1992:5 ), 对病毒、 细菌、 真菌及霉菌孢子都有较强的杀灭作用, 被 中国药典批准为人体可直接使用的消毒杀菌剂。 N-乙婦基丁内酰胺均聚物为非离子型表面活 性剂, 本身无抗菌作用, 但可提高碘的溶解度, 有助于提高碘溶液对物体的润湿和穿透能力, 使得有效碘对细胞膜的亲和力增强, 能将有效碘直接 I入到细菌的细胞膜、 细胞质上, 在几 秒钟内立即杀灭细菌,进而增强了碘的杀菌能力,同时 N-乙烯基丁内酰胺碘还具有易溶于水, 对皮肤、 粘膜无刺激性、 过敏和中毒现象, 因而国内外评价甚好。 而且均聚 N-乙烯基丁内酰 胺碘不仅可以作为水溶液使用, 在某些特殊的场合还可以固体的形式被应用。 这样使得均聚 N-乙烯基丁内酰胺碘被广泛应用于各个领域的杀菌、 消毒, 扩展了碘的使用范围, 在国内外 医院消毒中得到广泛的应用。 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. Can maintain a long time of bactericidal power, is a strong disinfectant (G & SMED ICAL LTD (US). Infection fighting composition for topical application [P]. US5137718 1992: 5), for viruses, bacteria, fungi and Mold spores have a strong killing effect and are approved by the Chinese Pharmacopoeia as a disinfectant for human body. 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. Moreover, 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.
目前市场上市售的均聚 N-乙烯基丁内酰胺碘粉末有效碘含量以及药典规定的有效碘含 量均在 9%-12%, 然而更高有效碘含量的均聚 N-乙烯基丁内酰胺碘无论在应用方面还是贮存 方面都显示出较好的优势,尤其是在市场利润方面一一用有效碘含量为 10%的均聚 N-乙烯基 丁内酰胺碘和 20%的均聚 N-乙烯基丁内酰胺碘去配制同一种规格的均聚 N-乙烯基丁内酰胺 碘消毒液, 有效碘为 20%的均聚 N-乙烯基丁内酰胺碘大大降低了该消毒液的成本, 同时也证 明了其市场可操作性。 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.
因此, 希望提供一种 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法。 发明内容 Therefore, it is desirable to provide a process for the preparation of homopolymeric N-vinyl butyrolactam iodine having a 20% effective iodine content. Summary of the invention
本发明的目的是克服了上述现有技术中的缺点,提供一种 20%有效碘含量的均聚 N-乙烯
基丁内酰胺碘的制备方法,该 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法设计巧 妙, 制备筒单, 制备出的均聚 N-乙烯基丁内酰胺碘有效碘含量为 20%, 同时还具备较高的稳 定性和光语杀菌性能, 适于大规模推广应用。 It is an object of the present invention to overcome the above-mentioned shortcomings of the prior art and to provide a homopolymeric N-ethylene having an effective iodine content of 20%. 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.
为了实现上述目的, 本发明的 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法, 其特点是, 以 N-乙烯基丁内酰胺均聚物和 850 μ ηι粒径以下的碘为原料, 其中所述 Ν-乙烯基 丁内酰胺均聚物和所述的 850 μ m粒径以下的碘的质量比为 7:3~5:5 , 同时以原料量为基准加 入 0.01%~5.0%重量百分含量的助剂, 釆取分段式制备法在温度为 50-100°C条件下搅拌反应 5-20小时。 In order to achieve the above object, 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 μ ηι particle size or less The iodine is a raw material, wherein the mass ratio of the Ν-vinyl butyrolactam homopolymer to the iodine below the 850 μm 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.
所述助剂可以是任何合适的助剂, 较佳地, 所述助剂为柠檬酸钠、 氯化钠或醋酸钠。 所述 N-乙烯基丁内酰胺均聚物、 所述的 850 μ ηι粒径以下的碘、 所述助剂、 所述温度、 所 述搅拌反应的时间可以选自上述范围, 较佳地, 所述 Ν-乙婦基丁内酰胺均聚物为 68g, 所述的 850 μ ηι粒径的碘为 32g, 所述助剂的量为 0.46g, 所述温度为 60°C , 所述搅拌反应的时间为 17 小时。 The auxiliaries may be any suitable auxiliaries. Preferably, the auxiliaries are sodium citrate, sodium chloride or sodium acetate. The N-vinyl butyrolactam homopolymer, the iodine having a particle diameter of 850 μm or less, the auxiliary agent, the temperature, and the stirring reaction time may be selected from the above range, preferably, The Ν-ethylglycolyl lactam homopolymer is 68 g, the iodine of the 850 μηη 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.
所述分段式制备法指的是先将过量的 N-乙婦基丁内酰胺均聚物、 少量的碘和助剂先反应 一段时间, 然后再补充加入一定量的碘和少量助剂, 使反应物中过量的均聚 N-乙烯基丁内酰 胺继续与碘反应, 当然还可以分为三段乃至更多段, 更佳地, 所述分段式制备法是首先将 68g 所述 N-乙烯基丁内酰胺均聚物、 22g所述的 850 μ m粒径的碘和 0.35g所述助剂在 60°C搅拌反应 8 小时, 之后再加入 10g所述的 850 μ m粒径的碘和 O.lg所述助剂在 60°C继续搅拌反应 9小时。 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 μm 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 μm particle size were further added. The auxin and the promoter of O.lg were continuously stirred at 60 ° C for 9 hours.
所述 N-乙烯基丁内酰胺均聚物、 所述的 850 μ ηι粒径以下的碘、 所述助剂、 所述温度、 所 述搅拌反应的时间可以选自上述范围, 较佳地, 所述 Ν-乙婦基丁内酰胺均聚物为 62g, 所述的 550 μ ηι粒径的碘为 38g, 所述助剂的量为 2.6g, 所述温度为 75 °C , 所述搅拌反应的时间为 19 小时。 The N-vinyl butyrolactam homopolymer, the iodine having a particle diameter of 850 μm or less, the auxiliary agent, the temperature, and the stirring reaction time may be selected from the above range, preferably, The Ν-ethylglycolyl lactam homopolymer is 62 g, the iodine of the 550 μηη 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.
所述分段式制备法指的是先将过量的 N-乙婦基丁内酰胺均聚物、 少量的碘和助剂先反应 一段时间, 然后再补充加入一定量的碘和少量助剂, 使反应物中过量的均聚 N-乙烯基丁内酰 胺继续与碘反应, 当然还可以分为三段乃至更多段, 更佳地, 所述分段式制备法是首先将 62g 所述 N-乙烯基丁内酰胺均聚物、 20g所述的 550 μ m粒径的碘和 1.4g所述助剂在 75 °C搅拌反应 11 小时, 之后再加入 18g所述的 550 μ m粒径的碘和 1.2g所述助剂在 75 °C继续搅拌反应 8小时。 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 62g the N a vinyl butyrolactam homopolymer, 20 g of the 550 μm 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 μm particle size were added. Iodine and 1.2 g of the above-mentioned auxiliary agent were further stirred at 75 ° C for 8 hours.
所述 N-乙烯基丁内酰胺均聚物、 所述的 850 μ ηι粒径以下的碘、 所述助剂、 所述温度、 所 述搅拌反应的时间可以选自上述范围, 较佳地, 所述 Ν-乙婦基丁内酰胺均聚物为 70g, 所述的 750 μ ηι粒径的碘为 30g, 所述助剂的量为 0.2g, 所述温度为 97°C , 所述搅拌反应的时间为 19
小时。 The N-vinyl butyrolactam homopolymer, the iodine having a particle diameter of 850 μm or less, the auxiliary agent, the temperature, and the stirring reaction time may be selected from the above range, preferably, The Ν-ethylglycolyl lactam homopolymer is 70 g, the iodine of the 750 μηη 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.
所述分段式制备法指的是先将过量的 N-乙婦基丁内酰胺均聚物、 少量的碘和助剂先反应 一段时间, 然后再补充加入一定量的碘和少量助剂, 使反应物中过量的均聚 N-乙烯基丁内酰 胺继续与碘反应, 当然还可以分为三段乃至更多段, 更佳地, 所述分段式制备法是首先将 70g 所述 N-乙烯基丁内酰胺均聚物、 30g所述的 750 μ m粒径的碘和 0.15g所述助剂在 97°C搅拌 反应 13小时, 之后再加入 5g所述的 750 μ ηι粒径的碘和 0.5g所述助剂在 97°C继续搅拌反应 6小时。 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. - vinyl butyrolactam homopolymer, 30 g of the 750 μm particle size iodine and 0.15 g of the auxiliary agent were stirred at 97 ° C for 13 hours, after which 5 g of the above-mentioned 750 μηη particle size were added. Iodine and 0.5 g of the auxiliary were further stirred at 97 ° C for 6 hours.
本发明的有益效果具体在于: 本发明的 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制 备方法以 N-乙烯基丁内酰胺均聚物和 850 μ ηι粒径以下的碘为原料,其中所述 Ν-乙烯基丁内 酰胺均聚物和所述的 850 μ ηι粒径以下的碘的质量比为 7:3~5:5 , 同时以原料量为基准加入 0.01%~5.0%重量百分含量的助剂,釆取分段式制备法在温度为 50-100°C条件下搅拌反应 5-20 小时, 从而得到的均聚 N-乙婦基丁内酰胺碘有效碘含量为 20%以上, 设计巧妙, 制备筒单, 同时还具备较高的稳定性和光语杀菌性能, 适于大规模推广应用。 附图说明 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 μm or less The raw material, wherein the mass ratio of the Ν-vinyl butyrolactam homopolymer to the iodine below the 850 μηη 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, 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. DRAWINGS
图 1是反应温度对有效碘含量的影响曲线图。 Figure 1 is a graph showing the effect of reaction temperature on effective iodine content.
图 2是助剂加入对反应时间的影响曲线图。 Figure 2 is a graph showing the effect of additive addition on reaction time.
图 3是助剂的加入对有效碘含量的影响曲线图。 Figure 3 is a graph showing the effect of the addition of an adjuvant on the effective iodine content.
图 4是碘的粒径对有效碘含量的影响曲线图。 具体实施方式 Figure 4 is a graph showing the effect of particle size of iodine on effective iodine content. detailed description
为了能够更清楚地理解本发明的技术内容, 特举以下实施例详细说明 , In order to more clearly understand the technical content of the present invention, the following embodiments are specifically described.
1.1 实验原料 1.1 Experimental materials
表 1 主要原料 Table 1 Main raw materials
名称 规格 生产厂家 Name Specifications Manufacturer
均聚 N-乙烯基丁内酰胺 医药级 上海宇昂化工科技发展有限公司 柠檬酸钠 分析纯 国药集团化学试剂有限公司 Homopolymerization N-vinyl butyrolactam Pharmaceutical grade Shanghai Yuang Chemical Technology Development Co., Ltd. Sodium citrate Analytical pure Sinopharm Chemical Reagent Co., Ltd.
蒸馏水 自制 Distilled water
石克代石克酸钠 分析纯 国药集团化学试剂有限公司 Shike Dai Shike Sodium Acid Analysis Pure Sinopharm Chemical Reagent Co., Ltd.
淀粉指示液 自制
1.2 实验仪器设备 Starch indicator liquid homemade 1.2 Experimental equipment
250ml三口烧瓶、 HH-WO恒温油浴锅、 S312电动搅拌器、 FA2004分析天平、 锥形瓶、 lO mLl移液管、 碱式滴定管。 250 ml three-necked flask, HH-WO thermostatic oil bath, S312 electric mixer, FA2004 analytical balance, conical flask, lO mLl pipette, basic burette.
1.3 有效碘含量的测定 1.3 Determination of effective iodine content
样品的有效碘浓度可参照中国药典(中国药典.二部 [S].2005:823 )方法测定浓度。 本实验 釆用美国药典测其有效碘含量: 称取样品约 lg, 精密称定置于烧杯中, 加水适量搅拌使其全 部溶解后转入 100 mL容量瓶中, 用移液管精密量取样品溶液 20 mL 2份至碘量瓶中, 用硫代 硫酸钠标准滴定液(O. lmol/L ) 滴定, 近淡黄色时滴加适量淀粉指示剂继续用硫代硫酸钠滴 至蓝色消失, 记录所用硫代硫酸钠的体积并计算样品的有效碘含量。 The effective iodine concentration of the sample can be determined by referring to the Chinese Pharmacopoeia (Chinese Pharmacopoeia. Part 2 [S]. 2005: 823) method. In this experiment, 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. 20 mL 2 parts into the iodine measuring flask, titrated with sodium thiosulfate standard titration solution (0.1 mol/L), add appropriate amount of starch indicator when it is light yellow, continue to drop with sodium thiosulfate until the blue disappears, record The volume of sodium thiosulfate used was used and the effective iodine content of the sample was calculated.
样品中有效碘含量 w以质量分数 ( % )表示: The effective iodine content in the sample is expressed in mass fraction (%):
(「 2 )x l2.69 ÷ 1000 (" 2 ) x l2.69 ÷ 1000
w =— ― x lOO w =— ― x lOO
m 式中: m where:
Vi——样品消耗硫代硫酸钠标准溶液的体积, 单位为毫升 ( mL ); Vi - volume of sample consumption sodium thiosulfate standard solution in milliliters (mL);
V2——空白试验消耗的硫代硫酸钠标准溶液的体积, 单位为毫升 (mL ); V 2 - the volume of the sodium thiosulfate standard solution consumed in the blank test, in milliliters (mL);
m __所取样品的质量, 单位为克 (g )。 m __ The mass of the sample taken, in grams (g).
2 结果与讨论 2 Results and discussion
2.1总用碘量对有效碘的影响 2.1 The effect of total iodine on effective iodine
均聚 N-乙烯基丁内酰胺碘的最大有效碘含量受溶解度的制约, 为了降低总用碘量降低产 品成本, 需要找出均聚 N-乙烯基丁内酰胺与碘的合理配比。 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.
表 2: 总用碘量对有效碘的影响 Table 2: Effect of total iodine on effective iodine
项目 总用碘量 有效捵含量 Item Total Iodine Effective Effective Content
1 20% 15.35% 1 20% 15.35%
2 24% 17.32% 2 24% 17.32%
3 26% 18.91% 3 26% 18.91%
4 30% 20.82% 4 30% 20.82%
5 35% 21.05% 5 35% 21.05%
6 50% 20.88%
从表 2数据可知, 均聚 N-乙烯基丁内酰胺碘中有效碘含量在一定范围内随用碘量的增加 而增加, 达到一定含量后数值趋于稳定。 原因可能是均聚 N-乙婦基丁内酰胺分子链的端基数 量限制了它所络合碘的量。 有效碘含量为 20%的均聚 N-乙烯基丁内酰胺碘原料中总用碘量 30%~50%为最佳。 6 50% 20.88% It can be seen from the data in Table 2 that 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%.
2.2温度对有效碘含量的影响 2.2 Effect of temperature on effective iodine content
N-乙烯基丁内酰胺均聚物和碘在常温下既可以发生络合, 但是不同温度下所需的时间不 同、 最终产品的有效碘含量亦不同, 一般反应温度控制在 45-100°C。 在均聚 N-乙烯基丁内酰 胺质量分数为 70%, 碘的质量分数为 30%, 相同助剂, 反应 6小时, 研究温度对产品有效碘 含量的影响, 见图 1。 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.
从图 1 中数据可以看出, 70°C为制备均聚 N-乙烯基丁内酰胺碘的最佳温度; 同时, 在 相同条件下, N-乙烯基丁内酰胺碘的有效碘含量随着温度的升高先升高后降低。 这主要是因 为温度的升高有利于提高反应物的活化分子数, 从而加快分子间碰撞频率, 使反应物充分反 应; 但是温度过高反应速率加快, 该反应过程中有效碘含量最高峰出现时间被大幅提前, 而 随着反应时间的延长, 均聚 N-乙烯基丁内酰胺和碘之间的络合键逐渐断裂, 有效碘含量迅速 下降。 As can be seen from the data in Figure 1, 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.
2.3加入助剂对有效碘含量的影响 2.3 Effect of adding additives on effective iodine content
取均聚 N-乙烯基丁内酰胺的质量分数 70%, 碘的质量分数 30%, 70°C条件下反应, 通过 加入柠檬酸钠等助剂考察助剂的加入对反应时间 (图 2 ) 以及有效碘含量(图 3 ) 的影响: 从图 2和图 3可以看出, 柠檬酸钠等助剂的加入可以大大缩短反应时间, 同时也可以有 效的提高反应中最大有效碘含量, 其最佳加入量为原料的 1.0%。 柠檬酸钠等助剂的加入起到 助磨剂作用, 促进了碘与均聚 N-乙烯基丁内酰胺之间的接触使得内摩擦加剧, 从而造成反应 速率加快、 络合反应充分, 进而反应时间降低、 有效碘含量升高。 Take the mass fraction of homopolymerized N-vinyl butyrolactam 70%, the mass fraction of iodine is 30%, and react at 70 °C. Add the auxiliaries to the reaction time by adding additives such as sodium citrate (Fig. 2) And the effect of effective iodine content (Figure 3): As can be seen from Figure 2 and Figure 3, the addition of citrate and other additives can greatly shorten the reaction time, and can also effectively increase the maximum effective iodine content in the reaction, which is the most The amount added is 1.0% of the raw material. The addition of 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.
2.4原料的处理对有效碘含量的影响 2.4 The effect of raw material treatment on effective iodine content
取 N-乙烯基丁内酰胺的质量分数为 70%, 碘的质量分数为 30%, 70°C条件下反应 12小 时, 研究不同粒径的碘对产品有效碘含量的影响, 见图 4。 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.
均聚 N-乙烯基丁内酰胺和碘的反应实质是碘与均聚 N-乙烯基丁内酰胺的固-固反应和气- 固反应。 对原料碘进行粒径处理后, 可以大大提高碘与均聚 N-乙烯基丁内酰胺的接触面, 从 而提高反应速率和有效碘含量降低反应时间以及反应过程中的质量影响因素。 这主要是因为 碘的强氧化性, 如果反应时间过长碘会对 N-乙烯基丁内酰胺造成一定的氧化使其分子链断 裂, 影响络合反应的进行; 由此可见对原料碘粒径的处理是必不可少的, 从图 4可以得到证
实。 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. After the particle size treatment of the raw material iodine, 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.
2.5分段式制备工艺对有效碘含量的影响 Effect of 2.5-stage preparation process on effective iodine content
分段式制备: 先用过量的均聚乙烯基丁内酰胺与少量的碘, 在氯化钠等助剂作用下络合 生成较低有效碘含量 ( 12%- 18% )的均聚 N-乙烯基丁内酰胺碘, 然后再补充加入一定量的碘 和少量氯化钠等助剂, 使反应物中过量的均聚 N-乙烯基丁内酰胺继续与碘反应, 从而制备出 高有效碘含量 ( 20%以上) 的均聚 N-乙烯基丁内酰胺碘。 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.
该法与传统一次投料制备工艺相比, 其制备出的均聚 N-乙婦基丁内酰胺碘的有效碘含量 较高, 一般在 20%以上。 原因可能为: 一方面, 碘的络合性能很好, 一般条件下很容易制备 出 8%-12%有效碘含量的均聚 N-乙烯基丁内酰胺碘; 但是, 由于均聚 N-乙烯基丁内酰胺自身 端基数量有限加上分子链上各基团之间位阻较大, 使其很难与碘达到理论上的充分络合。 这 就是传统工艺无法做出高含量均聚 N-乙婦基丁内酰胺碘的原因。 另一方面, 该分段式制备工 艺克服了均聚 N-乙烯基丁内酰胺在长时间的反应过程中受温度以及碘强氧化性变性失活。 均 聚 N-乙烯基丁内酰胺与碘的络合过程属于典型的放热反应, 反应过程中会放出较多热量, 会 在较短时间使反应体系温度升高, 从而造成均聚 N-乙烯基丁内酰胺部分变性失活; 而通过分 段式制备由于整个过程中 "反应点" 较少, 产生的热量相对较少亦可以较快散出, 同时, 由 于氯化钠等助剂的加入有效地降低了均聚 N-乙烯基丁内酰胺分子链各基团的位阻, 从而大大 提高络合度 , 制备出较高有效碘含量的均聚 N-乙烯基丁内酰胺碘。 Compared with the traditional one-time preparation process, 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 is why traditional processes cannot produce high levels of homopolymerized N-ethylglycolyl lactam iodine. On the other hand, 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 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.
3结 论 3 Conclusion
以均聚 N-乙烯基丁内酰胺与碘的投料比例为 7:3~5:5 ,通过对反应温度、助剂以及碘的粒 径进行调节控制, 研发出一套实际生产性高、 操作条件温和、 成本低, 以固相加热方法制备 20%有效碘含量均聚 N-乙烯基丁内酰胺碘的生产工艺:均聚 N-乙烯基丁内酰胺的质量分数为 50%~70%, 850μηι粒径以下的碘质量分数为 50%~30%,助剂加入量为原料量的 0.01%~5.0%, 在 50°C~100°C条件下通过分段法搅拌反应制备出的均聚 N-乙烯基丁内酰胺碘的有效碘含量 在 20%以上。 下面列举几个实施例更具体地说明本发明, 但本发明不受这些实施例的限制。 在下面的 内容中, 除非特殊说明, 将 "重量%" 仅表示为 "%"。 With a ratio of homopolymerized N-vinyl butyrolactam to iodine of 7:3 to 5:5, a set of practical high productivity and operation was developed by adjusting the reaction temperature, additives and iodine particle size. Mild conditions, low cost, the production process of 20% effective iodine content homopolymerization of N-vinyl butyrolactam by solid phase heating method: the mass fraction of homopolymerized N-vinyl butyrolactam is 50%~70%, The mass fraction of iodine below 850μηι particle size is 50%~30%, the amount of auxiliary agent is 0.01%~5.0% of the amount of raw materials, and the homopolymerization is prepared by the stirring method of segmentation method at 50°C~100°C. 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.
实施例 1 Example 1
称取 60g上海宇昂化工科技发展有限公司生产的均聚 N-乙烯基丁内酰胺 K30 ,粒径为 850 μ ηι的碘 22g, 0.35g柠檬酸钠加入到 500ml三口烧瓶中, 插入搅拌桨低速搅拌使原料混合均
匀, 然后放入 50°C油浴中搅拌加热反应 8小时, 之后再加入粒径为 850 μ m的碘 18g和 O.lg 柠檬酸钠,继续加热搅拌反应 9小时后冷却过筛即得有效碘含量为 21.11%的均聚 N-乙烯基丁 内酰胺捵。 Weighed 60g of homo-N-vinyl butyrolactam K30 produced by Shanghai Yuang Chemical Technology Development Co., Ltd., 22g of iodine with a particle size of 850μηηι, 0.35g of sodium citrate was added to a 500ml three-necked flask, and the stirring paddle was inserted at a low speed. Stirring to mix the raw materials Stir well, then put in a 50 ° C oil bath and stir to heat the reaction for 8 hours, then add 18g of iodine with a particle size of 850 μm and O.lg sodium citrate, continue to heat and stir the reaction for 9 hours, then cool and sieve to be effective Homogeneous N-vinyl butyrolactam oxime having an iodine content of 21.11%.
对比例 1 : Comparative example 1 :
除了不加柠檬酸钠以外, 进行和实施例 1同样的操作, 结果检测有效碘含量为 15.72%。 实施例 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:
称取 50g上海宇昂化工科技发展有限公司生产的均聚 N-乙烯基丁内酰胺 K30 ,粒径为 550 μ m的碘 25g, 2.6g醋酸钠加入到 500ml三口烧瓶中, 插入搅拌桨低速搅拌使原料混合均匀, 然后放入 75 °C油浴中搅拌加热反应 11小时, 之后再加入粒径为 550 μ ηι的碘 25g和 2.4g醋 酸钠,继续加热搅拌反应 9小时后冷却过筛即得有效碘含量为 21.63%的均聚 N-乙烯基丁内酰 胺碘。 Weigh 50g of homopolymerized N-vinyl butyrolactam K30 produced by Shanghai Yuang Chemical Technology Development Co., Ltd., 25g of iodine with a particle size of 550 μm, add 2.6g of sodium acetate to a 500ml three-necked flask, and insert a stirring paddle for low-speed stirring. The raw materials were uniformly mixed, and then heated in a 75 ° C oil bath for 11 hours with stirring. Then, 25 g of iodine having a particle diameter of 550 μm and 2.4 g of sodium acetate were added, and the mixture was further heated and stirred for 9 hours, and then cooled and sieved. The effective iodine content is 21.63% of homopoly N-vinyl butyrolactam iodine.
对比例 2: Comparative example 2:
除了用未经粉碎的碘(粒径大于 1500 μ ηι )代替粒径为 550 μ m的碘以外, 进行和实施 例 2同样的操作, 结果检测有效碘含量 16.22%。 实施例 3 The same operation as in Example 2 was carried out except that iodine having an unpulverized iodine (particle diameter of more than 1500 μm) was used instead of iodine having a particle diameter of 550 μm, and as a result, an effective iodine content of 16.22% was detected. Example 3
称取 70g上海宇昂化工科技发展有限公司生产的均聚 N-乙烯基丁内酰胺 K30 ,粒径为 750 μ m的碘 25g, 0.005g氯化钠加入到 500ml三口烧瓶中, 插入搅拌桨低速搅拌使原料混合均 匀,然后放入 100'C油浴中搅拌加热反应 3小时,之后再加入粒径为 750 μ m的碘 5g和 0.005g 氯化钠,继续加热搅拌反应 2小时后冷却过筛即得有效碘含量为 20.05%的均聚 N-乙烯基丁内 酰胺捵。 Weighed 70g of homopolymerized N-vinyl butyrolactam K30 produced by Shanghai Yuang Chemical Technology Development Co., Ltd., 25g of iodine with a particle size of 750 μm, 0.005g of sodium chloride was added to a 500ml three-necked flask, and inserted into the stirring paddle at low speed. Stir the raw materials evenly, then put them in a 100'C oil bath and heat them for 3 hours. Then add 5 g of iodine with a particle size of 750 μm and 0.005 g of sodium chloride. Continue to stir the reaction for 2 hours, then cool and sieve. That is, a homopolymeric N-vinyl butyrolactam having an effective iodine content of 20.05% is obtained.
对比例 3: Comparative example 3:
称取 70g上海宇昂化工科技发展有限公司生产的均聚 N-乙烯基丁内酰胺 K30 ,粒径为 750 μ m的碘 30g, O.lg醋酸钠加入到 500ml三口烧瓶中, 插入搅拌桨低速搅拌使原料混合均匀, 然后放入 100°C油浴中搅拌加热反应 5小时,冷却过筛得有效碘含量为 17.83%均聚 N-乙烯基 丁内酰胺捵。 本发明以原料 N-乙烯基丁内酰胺均聚物和经过粒径选择处理后的碘质量比为 7:3~5:5 ,同 时以原料量为基准加入 0.01%~5.0%重量的助剂 (柠檬酸钠、 氯化钠、 醋酸钠), 釆取分段式 制备法在 50-100°C条件下搅拌反应 5-20小时左右, 即得到高有效碘含量的均聚 N-乙烯基丁
内酰胺碘粉末。 Weighed 70g of homopolymerized N-vinyl butyrolactam K30 produced by Shanghai Yuang Chemical Technology Development Co., Ltd., 30g of iodine with a particle size of 750μm, and added O.lg sodium acetate to a 500ml three-necked flask. The raw materials were uniformly mixed by stirring, and then stirred and heated in a 100 ° C oil bath for 5 hours, and cooled to obtain an effective iodine content of 17.83% of homopolymer N-vinyl butyrolactam. In the invention, 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. (sodium citrate, sodium chloride, sodium acetate), 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.
综上, 本发明的 20%有效碘含量的均聚 N-乙婦基丁内酰胺碘的制备方法设计巧妙, 制备 筒单, 制备出的均聚 N-乙烯基丁内酰胺碘有效碘含量为 20%, 同时还具备较高的稳定性和光 谱杀菌性能, 适于大规模推广应用。 In summary, 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.
在此说明书中, 本发明已参照其特定的实施例作了描述。 但是, 很显然仍可以作出各种 修改和变换而不背离本发明的精神和范围。 因此, 说明书和附图应被认为是说明性的而非限 制性的。
In this specification, the invention has been described with reference to specific embodiments thereof. However, it will be apparent that various modifications and changes can be made without departing from the spirit and scope of the invention. Accordingly, the specification and figures are to be regarded as illustrative and not limiting.
Claims
1、 一种 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法, 其特征在于, 以 N-乙婦 基丁内酰胺均聚物和 850 μ m粒径以下的碘为原料, 其中所述 N-乙烯基丁内酰胺均聚物和所述 的 850 μ m粒径以下的碘的质量比为 7:3~5:5 ,同时以原料量为基准加入 0.01%~5.0%重量百分含 量的助剂, 釆取分段式制备法在温度为 50-100°C条件下搅拌反应 5-20小时。 1. A method for preparing homopolymerized N-vinylbutyrolactam iodine with 20% effective iodine content, which is characterized in that N-vinylbutyrolactam homopolymer and iodine with a particle size of less than 850 μm are used as the preparation method. Raw materials, wherein the mass ratio of the N-vinyl butyrolactam homopolymer and the iodine with a particle size below 850 μm is 7:3~5:5, and at the same time, 0.01%~5.0 is added based on the amount of raw materials. % weight percentage of additives, adopt a staged preparation method, stir and react for 5-20 hours at a temperature of 50-100°C.
2、 根据权利要求 1所述的 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法, 其特 征在于, 所述助剂为柠檬酸钠、 氯化钠或醋酸钠。 2. The preparation method of homopolymerized N-vinylbutyrolactam iodine with 20% available iodine content according to claim 1, wherein the auxiliary agent is sodium citrate, sodium chloride or sodium acetate.
3、 根据权利要求 1所述的 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法, 其特 征在于, 所述 N-乙婦基丁内酰胺均聚物为 68g, 所述的 850 μ ηι粒径的碘为 32g, 所述助剂的量 为 0.46g, 所述温度为 60°C , 所述搅拌反应的时间为 17小时。 3. The preparation method of homopolymerized N-vinylbutyrolactam iodine with 20% available iodine content according to claim 1, characterized in that the N-vinylbutyrolactam homopolymer is 68g, so The iodine with a particle size of 850 μm is 32g, the amount of the auxiliary agent is 0.46g, the temperature is 60°C, and the stirring reaction time is 17 hours.
4、 根据权利要求 3所述的 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法, 其特 征在于, 所述分段式制备法是首先将 68g所述 N-乙烯基丁内酰胺均聚物、 22g所述的 850 μ ηι粒 径的碘和 0.35g所述助剂在 60°C搅拌反应 8小时, 之后再加入 10g所述的 850 μ m粒径的碘和 O.lg 所述助剂在 60 C继续搅拌反应 9小时。 4. The preparation method of homopolymerized N-vinylbutyrolactam iodine with 20% available iodine content according to claim 3, characterized in that, the segmented preparation method is to first prepare 68g of the N-vinylbutyrolactam iodine Butyrolactam homopolymer, 22g of the iodine with a particle size of 850 μm and 0.35g of the auxiliary were stirred and reacted at 60°C for 8 hours, and then 10g of the iodine with a particle size of 850 μm and O were added. .lg of the auxiliary agent was stirred and reacted at 60 C for 9 hours.
5、 根据权利要求 1所述的 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法, 其特 征在于, 所述 N-乙婦基丁内酰胺均聚物为 62g, 所述的 550 μ ηι粒径的碘为 38g, 所述助剂的量 为 2.6g, 所述温度为 75 °C , 所述搅拌反应的时间为 19小时。 5. The preparation method of homopolymerized N-vinylbutyrolactam iodine with 20% available iodine content according to claim 1, wherein the N-vinylbutyrolactam homopolymer is 62g, so The iodine with a particle size of 550 μm is 38g, the amount of the auxiliary agent is 2.6g, the temperature is 75°C, and the stirring reaction time is 19 hours.
6、 根据权利要求 5所述的 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法, 其特 征在于, 所述分段式制备法是首先将 62g所述 N-乙烯基丁内酰胺均聚物、 20g所述的 550 μ m粒 径的碘和 1.4g所述助剂在 75 °C搅拌反应 11小时, 之后再加入 18g所述的 550 μ m粒径的碘和 1.2g 所述助剂在 75 C继续搅拌反应 8小时。 6. The preparation method of homopolymerized N-vinylbutyrolactam iodine with 20% available iodine content according to claim 5, characterized in that, the segmented preparation method is to first prepare 62g of the N-vinylbutyrolactam iodine Butyrolactam homopolymer, 20g of the iodine with a particle size of 550 μm and 1.4g of the auxiliary were stirred and reacted at 75°C for 11 hours, and then 18g of the iodine with a particle size of 550 μm and 1.2 g were added. g The auxiliary agent was continued to stir and react at 75 C for 8 hours.
7、 根据权利要求 1所述的 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法, 其特 征在于, 所述 N-乙婦基丁内酰胺均聚物为 70g, 所述的 750 μ ηι粒径的碘为 30g, 所述助剂的量 为 0.2g, 所述温度为 97°C , 所述搅拌反应的时间为 19小时。 7. The preparation method of homopolymerized N-vinylbutyrolactam iodine with 20% available iodine content according to claim 1, wherein the N-vinylbutyrolactam homopolymer is 70g, so The iodine with a particle size of 750 μm is 30g, the amount of the auxiliary agent is 0.2g, the temperature is 97°C, and the stirring reaction time is 19 hours.
8、 根据权利要求 7所述的 20%有效碘含量的均聚 N-乙烯基丁内酰胺碘的制备方法, 其特 征在于, 所述分段式制备法是首先将 70g所述 N-乙烯基丁内酰胺均聚物、 30g所述的 750 μ ηι粒 径的碘和 0.15g所述助剂在 97°C搅拌反应 13小时, 之后再加入 5g所述的 750 μ m粒径的碘和 0.5g 所述助剂在 97 °C继续搅拌反应 6小时。
8. The preparation method of homopolymerized N-vinylbutyrolactam iodine with 20% available iodine content according to claim 7, characterized in that, the segmented preparation method is to first prepare 70g of the N-vinylbutyrolactam iodine Butyrolactam homopolymer, 30g of the iodine with a particle size of 750 μm and 0.15g of the auxiliary were stirred and reacted at 97°C for 13 hours, and then 5g of the iodine with a particle size of 750 μm and 0.5 g were added. g The auxiliary agent was continued to stir for 6 hours at 97°C.
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