CN101838359A - Non-ionic N-vinyl butyrate lactam iodine, high-stability non-ionic N-vinyl butyrate lactam iodine and relevant overspeed preparation method - Google Patents
Non-ionic N-vinyl butyrate lactam iodine, high-stability non-ionic N-vinyl butyrate lactam iodine and relevant overspeed preparation method Download PDFInfo
- Publication number
- CN101838359A CN101838359A CN 201010181336 CN201010181336A CN101838359A CN 101838359 A CN101838359 A CN 101838359A CN 201010181336 CN201010181336 CN 201010181336 CN 201010181336 A CN201010181336 A CN 201010181336A CN 101838359 A CN101838359 A CN 101838359A
- Authority
- CN
- China
- Prior art keywords
- iodine
- vinyl butyrate
- ionic
- butyrate lactam
- stability
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention provides a preparation method of non-ionic N-vinyl butyrate lactam iodine. The non-ionic N-vinyl butyrate lactam iodine is prepared by stirring homopolymerized N-vinyl butyrate lactam and iodine for 20 to 25 minutes at the temperature of 60 to 70 DEG C and the speed of 200 to 250r/min, wherein the viscosity-average molecular weight of the homopolymerized N-vinyl butyrate lactam is 40000 to 45000, and the PD value is smaller than 5.5; and the water content is 2.0 to 3.0 percent. The invention also provides non-ionic N-vinyl butyrate lactam iodine prepared in such a way, a method for preparing high-stability non-ionic N-vinyl butyrate lactam iodine in such a way and the relevant high-stability non-ionic N-vinyl butyrate lactam iodine. The non-ionic N-vinyl butyrate lactam iodine has high iodine content, simple, convenient and quick preparation and low cost, and the high-stability non-ionic N-vinyl butyrate lactam iodine has high stability and convenient use, meets the highest requirements of the relevant dispensatories of USP, ISP, BP, EP, CP and the like completely and is suitable for large-scale popularization and application.
Description
Technical field
The present invention relates to compound technical, more specifically, relate to the non-ionic N-vinyl butyrate lactam iodine technical field, be meant a kind of non-ionic N-vinyl butyrate lactam iodine, high-stability non-ionic N-vinyl butyrate lactam iodine and relevant overspeed preparation method especially.
Background technology
Non-ionic N-vinyl butyrate lactam iodine, be called for short PVPI, Povidone-Iodine Solution, be the complex compound of non-ionic type homopolymerization N-vinyl butyrate lactam and elemental iodine, its solid be yellowish brown to the reddish-brown amorphous powder, in water or ethanol, dissolve, solution is reddish-brown, acidity, insoluble in ether or chloroform, available iodine often is 9.0%～12.0%.
PVPI solution has the effect of wide spectrum antibacterium, fungi and virus, and sterilization is quick, stable, lasting, reliable, and nontoxic, harmless to human body, nonirritant is efficient, safety, and fast disinfection sanitizer has become world today's sterilizing agent choice drug.Its mechanism of action is that the avidity to mycoderm by tensio-active agent PVP combines the active iodine that it was loaded with cytolemma and tenuigenin, makes iodate and oxidation rapidly such as sulfhydryl compound, peptide, protein, enzyme, lipid, thereby reaches germ-resistant purpose.Be mainly used in each field sterilization such as pharmaceutical sector, catering trade, family hotel, livestock industry, water industry.Compare with tincture of iodine phase solvent, it has, and effect is lasting, nonirritant and side effect, easy to use, water-soluble fully, no iodine is smelly and advantage such as dirty clothing not.Promptly promote the use of the external sixties, and the present well afoot of domestic-developed is the ideal substitute with the sterilizing agent that contains reactive chlorine, estimates that in the near future it will become domestic most popular high-end sterilizing agent, and market outlook are inestimable.
But the shortcoming of PVPI liquid is that the available iodine degraded is too fast, and stability is very bad, and its solution is all multifactor all extremely responsive to pH value, temperature, outer packaging, sight etc., and under general case, the available iodine content of PVPI can descend 15～25% rapidly in two weeks.Available iodine content changes by zeroth order reaction under constant temperature in the PVPI solution, presents the linear pattern downtrending, and this large-scale promotion to it has caused many restrictions.How to keep its stability also to become global problem.Its reason one is because PVP and iodine are intermolecular complexing, each other linkage force a little less than, PVP-HI
3Molecule very easily is subjected to the attack of external cause and ruptures; In addition, free-iodine itself has the characteristic of distillation, its volatilization can promote positive reaction continue carry out, this two aspect makes that all the solution of PVPI is extremely unstable.
At present, the method for producing PVPI both at home and abroad roughly has three kinds:
1, solvent method; Make PVPK30 and I
2In specific organic solvent, reaction at a certain temperature, underpressure distillation obtains solid PVP-I after removing and desolvating then.And then obtain finished product behind the crushing screening.Advantage is that iodine and the complexing in solution of PVP molecule are complete rapidly, the available iodine content height.Its shortcoming is to need to use organic solvent, the aftertreatment trouble; Solvent utilizes after need purifying and reclaiming again; Drying process has the distillation of elemental iodine, the content of corresponding reduction available iodine; In addition, big small particle size was inhomogeneous when solid was pulverized, and need sieve, thereby cause cost to rise.This method is mainly BASF, and ISP company and domestic minority enterprise use.
2, solid abrasive method; Make PVPK30 and I
2In the ball milling device, fully grind,, add specific adjuvant, thereby obtain the PVPI powder in order to improve available iodine content.Its advantage is that production unit is simple, does not need solvent, does not also need aftertreatment.Get product after the discharging.Shortcoming is that available iodine content is lower than solvent method, and stability is very poor, and the rate of loss of available iodine is more than 25% under the identical accelerated tests situation.So be usually used in middle and low-end market.And the client needs matching while using in order to obtain stable available iodine solution, must add relevant various auxiliary agents simultaneously again to keep stability; This causes sizable trouble to the client, and use cost is too high.
3, microwave is consolidated complexometry; This is a kind of method of rising in recent years.Elemental iodine and K30 be positioned over carry out microwave heating in the particular encapsulated container.Utilize iodine steam and K30 to carry out complexing, thereby obtain final finished.Its advantage is to use thick iodine, and less demanding to the source of iodine, complexing is rapid.Shortcoming is: iodine steam is poisonous, its complexing power, and seepage force is extremely strong again, and a spot of iodine steam promptly can damage operative employee's health.Simultaneously, it is corrosion-resistant that special container requires, good seal, and non-standard equipments such as magnetron that must customized costliness, thus cause the disposable input of equipment too high, be not suitable for conventional production.It is a spot of synthetic that this method is suitable for the laboratory, but still be not suitable for large-scale industrial production at present.The available iodine content of this method is higher, but its less stable.
At present, domestic and international pharmacy corporation mainly concentrates on two fields to the Study on Stability of PVPI:
1, takes all factors into consideration the factor such as purity, temperature of reaction, pH value scope, reaction times, rotating speed of agitator, grinding aid of raw material iodine and select the suitable parameters condition, thereby produce high-load raw material and keep its stability as far as possible; Its shortcoming is that the PVPI solid keeps relative stability, but solution less stable still, at 54 degree, in 14 days the accelerated tests, the rate of loss of available iodine content is usually more than 5%, although can satisfy the basic demand less than 15%, but for high-end customer, its stability still still has gap.In addition, in order to obtain high stability to greatest extent, general technology requires the complexing time of PVPI to want 3 hours at least (being generally about 6～10 hours); Though long content and the stability thereof that reaction can corresponding raising available iodine, but shortcoming is that the content and the stability of reaction times and available iodine is not linear relationship, too high energy consumption can not promote the quality of product significantly, PVP is through phenomenons such as long break-in meeting generation chain ruptures on the contrary, thereby makes product quality reduce;
2, not that direct wiring solution-forming uses after producing the PVPI powder, but matching while using, and when dosing, add the pH value conditioning agent simultaneously; buffered soln; the iodide ion stablizer, relevant auxiliary agent such as Derma-Guard, thus make the stability of PVPI can reach the officinal requirement.This also is the technology of the most normal application at present both at home and abroad.But its interpolation process is very loaded down with trivial details, uses extremely inconveniently, needs matching while using, and the use of various auxiliary agents usually pins down mutually and interferes with adding during preparation.This has caused the stability of PVPI to strengthen, but the production circulation ratio is bad, and impurity is too much, and heavy metal content exceeds standard, nitrogen content reduces, extra shortcoming such as ash content increase, thus increased corresponding artificial greatly, use and storage cost, be not suitable for scale operation, sell and use.
Along with the progress and the expanding economy of society, the above-mentioned weakness of PVPI is more and more obvious, the also more and more incompatible present application requiring of above-mentioned stability maintenance method.Many PVPI client's strong requests manufacturer can provide a kind of high steady PVPI dry powder that can directly use, and no longer needs during obtain solution to add various auxiliary agents, thereby the client is really freed temporarily.Therefore, press for and can produce a kind of non-ionic N-vinyl butyrate lactam iodine, its iodine content height, preparation are fast, cost is low, stability is high, and easy to use.
Summary of the invention
Main purpose of the present invention is exactly the problems and shortcomings at above existence, a kind of non-ionic N-vinyl butyrate lactam iodine, high-stability non-ionic N-vinyl butyrate lactam iodine and relevant overspeed preparation method are provided, this non-ionic N-vinyl butyrate lactam iodine iodine content height, preparation is easy fast, cost is low, this high-stability non-ionic N-vinyl butyrate lactam iodine stability is high, easy to use, satisfy relevant officinal peak demands such as USP, ISP, BP, EP, CP fully, be suitable for large-scale promotion application.
In order to solve above-mentioned purpose, in a first aspect of the present invention, a kind of preparation method of non-ionic N-vinyl butyrate lactam iodine is provided, be characterized in, by homopolymerization N-vinyl butyrate lactam and iodine were prepared from described non-ionic N-vinyl butyrate lactam iodine in 20～25 minutes with 200～250r/min stirring under 60 ℃～70 ℃ temperature, the viscosity-average molecular weight of wherein said homopolymerization N-vinyl butyrate lactam is 40000-45000, and the PD value is less than 5.5; Moisture is 2.0-3.0%.
Preferably, described homopolymerization N-vinyl butyrate lactam is the YK001 powder, and described iodine adopts the crystalline flake of iodine.
Preferably, described homopolymerization N-vinyl butyrate lactam and described iodine stir under the grinding aid existence condition.
More preferably, described grinding aid is a sodium-chlor.
Further, described homopolymerization N-vinyl butyrate lactam is 46～47g, and described iodine is 7g, and described grinding aid is 0.19～0.27g.
In a second aspect of the present invention, a kind of non-ionic N-vinyl butyrate lactam iodine is provided, be characterized in that the preparation method by above-mentioned non-ionic N-vinyl butyrate lactam iodine prepares.
In a third aspect of the present invention, a kind of preparation method of high-stability non-ionic N-vinyl butyrate lactam iodine is provided, be characterized in, by non-ionic N-vinyl butyrate lactam iodine according to claim 6 and pH buffer reagent, iodide ion stablizer, iodide ion conditioning agent and pH value conditioning agent are prepared from described high-stability non-ionic N-vinyl butyrate lactam iodine through the 20000-30000r/min high speed pulverization after 50～60 seconds, the available iodine content of wherein said non-ionic N-vinyl butyrate lactam iodine is higher than 10.5%.
Preferably, described pH buffer reagent is a Trisodium Citrate, and described iodide ion stablizer is a Potassium Iodate, and described iodide ion conditioning agent is a potassiumiodide, and described pH value conditioning agent is a sodium hydroxide.
More preferably, described non-ionic N-vinyl butyrate lactam iodine is 5g, and described Trisodium Citrate is 0.30～0.50g, and described Potassium Iodate is 0.25～0.30g, and described potassiumiodide is 0.45～0.50g, and described sodium hydroxide is 0.0035～0.0045g.
In a fourth aspect of the present invention, a kind of high-stability non-ionic N-vinyl butyrate lactam iodine is provided, be characterized in that the preparation method by above-mentioned high-stability non-ionic N-vinyl butyrate lactam iodine prepares.
Beneficial effect of the present invention is:
1, the present invention is by 20～25 minute being prepared from described non-ionic N-vinyl butyrate lactam iodine with 200～250r/min stirring with homopolymerization N-vinyl butyrate lactam and iodine under 60 ℃～70 ℃ temperature, the available iodine content of the non-ionic N-vinyl butyrate lactam iodine of making is higher than 10.5%, the iodine content height, preparation is easy fast, cost is low, is suitable for large-scale promotion application.
2, the present invention does not use conventional PVPK30, and the viscosity-average molecular weight of the homopolymerization N-vinyl butyrate lactam of employing is 40000-45000, and the PD value is less than 5.5; Moisture is 2.0-3.0%, the YK001 product produced of Shanghai Yu'ang Chemical Technology Development Co., Ltd. for example, and its viscosity-average molecular weight is 40000, the PD value is less than 5.5, and the water content solid is 2.5%, compares conventional PVPK30, the YK001 molecular weight is bigger, and molecular weight distribution is narrower.And the molecular weight of conventional K30 is less, the molecular weight distribution broad, and the PD value is often greater than 8, and water content is wide in range, generally 3～5%; Former because bigger molecular weight has longer molecular chain, thus hapto is more; Then effectively hapto is concentrated for the little then molecular chain of PD value narrowly distributing, and complexing is even rapidly, and suitable water content (2.5% for best) can guarantee the carrying out of complex reaction to greatest extent.Moisture is low, then iodine can't with the better complexing of PVP, then the PVP flowability is bad for the moisture height, stirs easily unevenly, the reaction times is long.
3, iodine of the present invention can directly use the SQM company sheet iodine (it is cheap that sheet iodine is compared spherical iodine) of purchase, and does not need earlier it to be ground to form iodine powder (generally need grind to form more than 50 orders) earlier; This has saved a procedure, greatly reduce production cost, ordinary method will be produced the iodine powder earlier, thereby the specific surface area that improves the iodine grain is with the ratio of increase with the PVP complexing, but because the present invention adopts highly active YK001 raw material, avoided the infull problem of complexing from the source, thus do not need to produce in advance again the iodine powder, prepare easy fast, cost is low.
4, the preparation time of non-ionic N-vinyl butyrate lactam iodine of the present invention only needs 20～25 minutes, not 3～9 hours of ordinary method, reason is that ordinary method is in order to improve the content of available iodine, have to sacrifice the reaction times, but the height of reaction times and available iodine is not a linear relationship, the lifting of overlong time available iodine content is not obvious, in addition, long complexing meeting causes PVP chain break, degraded, its basic reason is that general PVPK30 raw material activity is not strong, and relevant operational parameter is incomplete yet; Along with development of science and technology and progress, the PVP raw material of preparation PVPI is also changed, and K30 not necessarily, the inventor find the homopolymerization N-vinyl butyrate lactam of optimum PVPI complexing, for example the YK001 raw material finally through secular research and development.
5, the present invention is by being prepared from described high-stability non-ionic N-vinyl butyrate lactam iodine with above-mentioned non-ionic N-vinyl butyrate lactam iodine and pH buffer reagent, iodide ion stablizer, iodide ion conditioning agent and pH value conditioning agent through the 20000-30000r/min high speed pulverization after 50～60 seconds, excellent in stability, be controlled in 1.5% at available iodine content degradation rate in the accelerated tests, stability is high, easy to use, satisfies requirement of client fully.
6, the present invention selects for use Trisodium Citrate as buffer reagent, this is different from conventional Sodium phosphate dibasic/SODIUM PHOSPHATE, MONOBASIC system, advantage is that Trisodium Citrate is a kind of weak acid strong alkali salt, can form stronger pH buffer reagent with the citric acid compatibility, therefore in some occasion that is not suitable for the pH wide variation its important usefulness is arranged, have good pH regulator and shock-absorbing capacity.And Sodium phosphate dibasic/SODIUM PHOSPHATE, MONOBASIC very easily absorbs water and becomes tide, is not suitable for directly adding PVPI dry powder.
7, high-stability non-ionic N-vinyl butyrate lactam iodine of the present invention can directly use with the pure water wiring solution-forming, and is simple and convenient; Get final product matching while using, also can join the back prolonged preservation, make things convenient for client's use and storage greatly, and conventional PVPI dry powder is because the defective of self has to add various auxiliary agents when obtain solution, but its interpolation process is very loaded down with trivial details, use extremely inconveniently, need matching while using, and the use of various auxiliary agents usually pins down mutually and interferes with adding during preparation, though this has caused the stability of PVPI to strengthen, but the production circulation ratio is bad, and impurity is too much, and heavy metal content exceeds standard, nitrogen content reduces, extra shortcoming such as ash content increase, thus increased greatly accordingly manually, use and storage cost, be not suitable for scale operation, sell and use.
Description of drawings
Fig. 1 is the influence figure of mixing speed to available iodine content.
Fig. 2 is the influence figure of raw material YK001 water content to available iodine content.
Fig. 3 is the Potassium Iodate consumption to the figure that influences of the stability of high stability PVPI.
Fig. 4 is the potassiumiodide consumption to the figure that influences of the stability of high stability PVPI.
Fig. 5 is the Trisodium Citrate consumption to the figure that influences of the stability of high stability PVPI.
Fig. 6 is the pH value to the figure that influences of the stability of high stability PVPI.
Embodiment
In order more to be expressly understood technology contents of the present invention, describe in detail especially exemplified by following examples.The preparation of embodiment 1 non-ionic N-vinyl butyrate lactam iodine
1, the reaction times is to the influence of available iodine content
The accurate weighing 7g crystalline flake of iodine, 46.84gYK001 powder and 0.27g sodium-chlor, disposable joining in the 250ml there-necked flask, 60 ℃ of heating in water bath, the 200r/min mechanical stirring, sampling at set intervals, the test available iodine content, it is as shown in table 1 with the variation in reaction times to get available iodine content.
Table 1 reaction times is to the influence of available iodine content
| Sample time | Available iodine content | Reaction times |
| ??11:13 | ??6.37％ | ??3min |
| ??11:17 | ??10.26％ | ??7min |
| ??11:20 | ??10.51％ | ??10min |
| ??11:25 | ??10.52％ | ??15min |
| ??11:30 | ??10.57％ | ??20min |
| ??11:35 | ??10.56％ | ??25min |
As shown in Table 1, iodine and YK001 to be reflected at the initial stage very fast, react 7 minutes available iodine contents and can reach 10.26%, this is because initial reaction stage YK001 has a lot of active haptoes to react with elemental iodine, prolongation along with the reaction times, available iodine content is more and more higher, available iodine content reaches 10.57% when reacting 20 minutes, prolonging the reaction times available iodine content again reduces on the contrary, this is because the moisture in the reaction system constantly leaves YK001 with the prolongation in reaction times, originally rupture, make available iodine content reduce by water molecules complexing iodine oxygen complex bonds together.So general normal getting 20～25 minutes.
2, temperature is to the influence of available iodine content
The accurate weighing 7g crystalline flake of iodine, 46.84gYK001 powder and 0.27g sodium-chlor, disposable joining in the 250ml there-necked flask, respectively at 30 ℃, 40 ℃, 50 ℃, 60 ℃, heat in 70 ℃ of water-baths, the 200r/min mechanical stirring, sampling at set intervals, test available iodine content maximum and required time are listed in table 2.
Table 2 temperature is to the influence of available iodine content
| ??NO. | Temperature of reaction | Reaction times | Available iodine content |
| ??1 | ??30 | ??80 | ??7.8 |
[0048]
| ??2 | ??40 | ??60 | ??9.5 |
| ??3 | ??50 | ??40 | ??10.7 |
| ??4 | ??60 | ??20 | ??11.4 |
| ??5 | ??70 | ??20 | ??11.3 |
As shown in Table 2, temperature of reaction raises, reaching the highest available iodine content required time is shortening, 30 ℃ reach the highest available iodine content required time is 4 times of 60 ℃ of required times, and available iodine content is with the non-linear relation of the variation of temperature of reaction, this mainly is because the moisture in the reaction system has material impact to available iodine content in reaction process, only just can obtain the higher effective iodine content under suitable moisture content and suitable reaction times double influence.Event is general normal gets 60～70 ℃.
3, mixing speed is to the influence of available iodine content
The accurate weighing 7g crystalline flake of iodine, 46.84gYK001 powder and 0.27g sodium-chlor, disposable joining in the 250ml there-necked flask, in 60 ℃ of water-baths, heat respectively, respectively in 50r/min, 100r/min, 150r/min, 200r/min, 250r/min mechanical stirring, the 80min sampling, the test available iodine content is seen Fig. 1.
As shown in Figure 1, available iodine content improves with the raising of mixing speed, this is because under the higher rotation speed condition, elemental iodine mixes more abundant with YK001, the effective contact that reacts is more, available iodine content is 11.4% when 200r/min, continues to increase the mixing speed available iodine content again and does not continue to increase, in case this is because elemental iodine can just depend on the character of material itself with YK001 thorough mixing level of response.So general normal 200～250r/min that gets.
4, raw material YK001 water content is to the influence of available iodine content
Accurately the weighing 7g crystalline flake of iodine, water content are respectively 1.5%, 2.0%, 2.3%, 2.8%, 3.3%, 46.84gYK001 powder and 0.27g sodium-chlor, disposable joining in the 250ml there-necked flask, respectively at 60 ℃ of heating in water bath, the 200r/min mechanical stirring, the 80min sampling, the test available iodine content is seen Fig. 2.
As shown in Figure 2, the product available iodine content is also lower when raw material YK001 water content is relatively low, and this YK001 raw material is better mobile, can be as the unrestricted flow of exsiccant sand in the reaction process.Increase along with YK001 raw material water content, the product available iodine content increases, occurring maximum available iodine content when water content is 2.5% is 11.4%, and sharply descend when YK001 raw material water content continues to increase the product available iodine content, this is because of the increase along with water content, raw material is mobile to descend, when water content is 3.4%, raw material loses flowability, promptly using agitator to stir can not make it flow, therefore elemental iodine can not with the YK001 thorough mixing, so the product available iodine content is very low.
5, raw material iodine shape is to the influence of available iodine content
The accurate weighing 7g sheet iodine of difference and spherical iodine, 46.84gYK001 powder and 0.27g sodium-chlor, disposable joining in the 250ml there-necked flask heated in 60 ℃ of water-baths, the 200r/min mechanical stirring, the 80min sampling, the test available iodine content sees Table 3.
Table 3 raw material iodine shape is to the influence of available iodine content
| Shape | Available iodine content/% |
| Spherical | ??10.5 |
| Sheet | ??11.4 |
As shown in Table 3, under the same test conditions, sheet iodine products therefrom available iodine content is higher, and this is because spherical iodine is difficult to be pulverized by mutual frictional impact in whipping process, even reaction 80min can see still when surveying available iodine content again that unreacted black iodine particle exists.Sheet iodine is pulverized by mutual frictional impact easily, so elemental iodine can better contact with the YK001 powder, it is more thorough that reaction is carried out, product available iodine content height.
6, grinding aid is to the influence of available iodine content
Accurately weighing 7g sheet iodine, 46.84gYK001 powder and 0.27g sodium-chlor or do not add sodium-chlor respectively, disposable joining in the 250ml there-necked flask heated in 60 ℃ of water-baths, the 200r/min mechanical stirring, the 80min sampling, the test available iodine content sees Table 4.
Table 4 grinding aid is to the influence of available iodine content
| Whether add sodium-chlor | Available iodine content/% |
| Not | ??10.5 |
| Be | ??11.4 |
Adding by the visible grinding aid sodium-chlor of table 4 has tangible effect for improving the product available iodine content, and 5 ‰ grinding aid consumption can make available iodine content improve 0.9%.
The preparation of embodiment 2 high-stability non-ionic N-vinyl butyrate lactam iodines
1, the Potassium Iodate consumption is to the influence of PVPI stability
The accurate homemade PVPI5g in weighing laboratory, Trisodium Citrate 0.48g takes by weighing Potassium Iodate 0.15g, 0.20g, 0.25g, 0.30g, 0.35g respectively, potassiumiodide 0.45g, sodium hydroxide 0.0040g pulverized 60 seconds in high speed disintegrator, promptly got composite PVPI.Get and be made into 1% aqueous solution in right amount, put into 54 ℃ of air dry ovens, test available iodine content behind the fortnight, data as shown in Figure 3.
With the stable increase of the increase PVPI of Potassium Iodate consumption, this is because PVPI solution in storage process, decomposites iodide ion, generates iodine after adding Potassium Iodate under acidic conditions, and available iodine content is kept relative stability as shown in Figure 3.Yet along with the further increase of Potassium Iodate consumption, the stability of PVPI solution increases slowly, again because the Potassium Iodate price is higher, is optimum amount so get 0.25～0.30.
2, the potassiumiodide consumption is to the influence of PVPI stability
The accurate homemade PVPI5g in weighing laboratory, Trisodium Citrate 0.48g, Potassium Iodate 0.25g takes by weighing potassiumiodide 0.20g, 0.30g, 0.40g, 0.45g, 0.50g respectively, and sodium hydroxide 0.0040g pulverized 60 seconds in high speed disintegrator, promptly got composite PVPI.Get and be made into 1% aqueous solution in right amount, put into 54 ℃ of air dry ovens, test available iodine content behind the fortnight, data as shown in Figure 4.
As shown in Figure 4 with the stable increase of the increase PVPI of potassiumiodide consumption, this is because PVPI solution in storage process, decomposites iodide ion, after adding potassiumiodide because common-ion effcet, make the generation of iodide ion become difficult, make available iodine content keep relative stability.Yet along with the further increase of Potassium Iodate consumption, the stability of PVPI solution does not change, and is optimum amount so get 0.45～0.50.
3, the acid-base buffer agent consumption is to the influence of PVPI stability
The accurate homemade PVPI5g in weighing laboratory, Trisodium Citrate 0.48g, Potassium Iodate 0.25g, potassiumiodide 0.45g, sodium hydroxide 0.0040g pulverized 60 seconds in high speed disintegrator, promptly got composite PVPI.Get and be made into 1% aqueous solution in right amount, put into 54 ℃ of air dry ovens, test available iodine content behind the fortnight, data as shown in Figure 5.
As shown in Figure 5, increase Trisodium Citrate and can improve the PVPI stability of solution, this be because PVPI solution in storage process, thereby decompositing iodide ion and iodate ion reduces the available iodine content of solution, acidic conditions can quicken above-mentioned decomposition reaction, an amount of Trisodium Citrate can make solution system be stabilized within the suitable scope, solution system pH value is too high when Trisodium Citrate is excessive, it is faster to make that available iodine content reduces, and therefore selects the optimum amount of 0.30～0.50g as Trisodium Citrate.
4, the pH value is to the influence of PVPI stability
The accurate homemade PVPI5g in weighing laboratory, Trisodium Citrate 0.48g, Potassium Iodate 0.25g, potassiumiodide 0.45g, 1% pH value of water solution that makes by the adjusting sodium hydroxide concentration is respectively 3.0,4.0,5.0,6.0,7.0, pulverizes 60 seconds in high speed disintegrator, promptly gets composite PVPI.Get and be made into 1% aqueous solution in right amount, put into 54 ℃ of air dry ovens, test available iodine content behind the fortnight, data as shown in Figure 6.
Can verify further that by Fig. 6 PVPI has an optimum pH scope in storage process, from the table we as can be seen this scope between 4.5～5.5, this is because elemental iodine and water reaction generation iodate ion and being reflected under peracid or the parlkaline condition of iodide ion all can be accelerated, so need keep the pH value of solution between 4.5～5.5 when storing PVPI solution.
The preparation of embodiment 3 non-ionic N-vinyl butyrate lactam iodines
Accurately the weighing 7g crystalline flake of iodine, (require viscosity-average molecular weight is 40000 to the 46.15gYK001 powder, the PD value is less than 5.5, water content 2.5%) and 0.21g sodium-chlor, disposable joining in the 250ml there-necked flask, 60 ℃ of heating in water bath, the 200r/min mechanical stirring, 20 minutes reaction times promptly stopped, obtain non-ionic N-vinyl butyrate lactam iodine A, available iodine content is higher than 10.5%.Available iodine content can be every sampling in five minutes once, and the test available iodine content gets final product stopped reaction when effective iodine content is higher than 10.5%.
Accurately the weighing 7.005g crystalline flake of iodine, (require viscosity-average molecular weight is 45000 to the 46.15gYK001 powder, the PD value is less than 5.5, water content 3.0%) and 0.19g sodium-chlor, disposable joining in the 250ml there-necked flask, 65 ℃ of heating in water bath, the 220r/min mechanical stirring, 20 minutes reaction times promptly stopped, obtain non-ionic N-vinyl butyrate lactam iodine B, available iodine content is higher than 10.5%.Available iodine content can be every sampling in five minutes once, and the test available iodine content gets final product stopped reaction when effective iodine content is higher than 10.5%.
Accurately the weighing 7.001g crystalline flake of iodine, (require viscosity-average molecular weight is 42000 to the 46.84gYK001 powder, the PD value is less than 5.5, water content 2.0%) and 0.27g sodium-chlor, disposable joining in the 250ml there-necked flask, 70 ℃ of heating in water bath, the 250r/min mechanical stirring, 25 minutes reaction times promptly stopped, obtain non-ionic N-vinyl butyrate lactam iodine C, available iodine content is higher than 10.5%.Available iodine content can be every sampling in five minutes once, and the test available iodine content gets final product stopped reaction when effective iodine content is higher than 10.5%.
The preparation of embodiment 4 high-stability non-ionic N-vinyl butyrate lactam iodines
The non-ionic N-vinyl butyrate lactam iodine A 5g of accurate weighing embodiment 3 preparations, Trisodium Citrate (buffer reagent) 0.30g, Potassium Iodate (iodide ion conditioning agent) 0.25g, potassiumiodide (iodide ion conditioning agent) 0.45g, sodium hydroxide (pH value conditioning agent) 0.0045g, in high speed disintegrator (20000r/min), pulverized 50 seconds, promptly get high stability PVPI-1.
The non-ionic N-vinyl butyrate lactam iodine B 5g of accurate weighing embodiment 3 preparations, Trisodium Citrate (buffer reagent) 0.40g, Potassium Iodate (iodide ion conditioning agent) 0.28g, potassiumiodide (iodide ion conditioning agent) 0.48g, sodium hydroxide (pH value conditioning agent) 0.0040g, in high speed disintegrator (25000r/min), pulverized 55 seconds, promptly get high stability PVPI-2.
The non-ionic N-vinyl butyrate lactam iodine C 5g of accurate weighing embodiment 3 preparations, Trisodium Citrate (buffer reagent) 0.50g, Potassium Iodate (iodide ion conditioning agent) 0.30g, potassiumiodide (iodide ion conditioning agent) 0.50g, sodium hydroxide (pH value conditioning agent) 0.0035g, in high speed disintegrator (30000r/min), pulverized 60 seconds, promptly get high stability PVPI-3.
The mensuration of available iodine: accurately non-ionic N-vinyl butyrate lactam iodine A, non-ionic N-vinyl butyrate lactam iodine B and the non-ionic N-vinyl butyrate lactam iodine C dry product of weighing 5g embodiment 3 preparations place the 400ml beaker respectively, add water 200ml, cover beaker, stirring and dissolving under room temperature, after the dissolving, use the titration of 0.05mol/L sodium thiosulfate standard solution immediately fully, add 3ml starch reagent during near terminal point and make indicator, do blank test simultaneously, calculate available iodine content.Every 1ml Sulfothiorine (0.05mol/L) solution is equivalent to the iodine of 12.69mg.
Three revision tests of priority, data statistics is in following table:
| Material | Reaction times | Available iodine content for the first time | Available iodine content for the second time | Available iodine content for the third time |
| Non-ionic N-vinyl butyrate lactam iodine A | ??20min | ??11.52％ | ??11.51％ | ??11.52％ |
| Non-ionic N-vinyl butyrate lactam iodine B | ??20min | ??11.49％ | ??11.48％ | ??11.49％ |
| Non-ionic N-vinyl butyrate lactam iodine C | ??20min | ??11.66％ | ??11.65％ | ??11.65％ |
As seen from the above table, for high stability PVPI-1, high stability PVPI-2 and high stability PVPI-3, available iodine content has reached 〉=10.5% test objective in three revision tests, and three testing datas, difference≤± 1.5% each other, also reached test objective preferably, shown that test has better repeatability.
Accelerated stability test test: get high stability PVPI-1, high stability PVPI-2 and high stability PVPI-3, decide 5g with the accurate title of electronic balance respectively, put in the beaker, add an amount of purified water, stirring makes dissolving, changes constant volume in the 500ml volumetric flask over to after the dissolving fully, makes 1% solution as sample, sample places airtight brown reagent bottle, places 54 ± 2 ℃ of constant temperature ovens.Timing sampling is accurately measured the 25ml sample with transfer pipet, cools off termination reaction rapidly, measures available iodine content in the solution.
For high stability PVPI-1 solution:
| Reaction times | Available iodine content/% | The available iodine reduced rate |
| ??20min | ??10.75 | ??0 |
| ??2Day | ??10.73 | ??-0.19％ |
| ??4Day | ??10.71 | ??-0.37％ |
| ??6Day | ??10.72 | ??-0.28％ |
| ??8Day | ??10.70 | ??-0.47％ |
[0094]
| ??10Day | ??10.68 | ??-0.65％ |
| ??12Day | ??10.67 | ??-0.74％ |
| ??14Day | ??10.63 | ??-1.12％ |
For high stability PVPI-2 solution:
| Reaction times | Available iodine content/% | The available iodine reduced rate |
| ??20min | ??10.70 | ??0 |
| ??2Day | ??10.68 | ??-0.19％ |
| ??4Day | ??10.67 | ??-0.28％ |
| ??6Day | ??10.66 | ??-0.37％ |
| ??8Day | ??10.64 | ??-0.56％ |
| ??10Day | ??10.62 | ??-0.75％ |
| ??12Day | ??10.61 | ??-0.84％ |
| ??14Day | ??10.58 | ??-1.12％ |
For high stability PVPI-3 solution:
| Reaction times | Available iodine content/% | The available iodine reduced rate |
| ??20min | ??10.88 | ??0 |
| ??2Day | ??10.86 | ??-0.18％ |
| ??4Day | ??10.85 | ??-0.28％ |
| ??6Day | ??10.83 | ??-0.46％ |
| ??8Day | ??10.82 | ??-0.55％ |
| ??10Day | ??10.80 | ??-0.74％ |
| ??12Day | ??10.79 | ??-0.83％ |
| ??14Day | ??10.75 | ??-1.19％ |
Analyze: through 54 ℃, 14 days accelerated tests, the stability of high stability PVPI of the present invention reaches design requirements, and its available iodine reduced rate is less than 1.5%; Its index far surpasses like product.Former because: with BASF, the solvent method product good stability when solid headed by the ISP, but the dissolving back is because self weakness of PVP, stability is still not so good, the available iodine reduced rate is about 5%; Its commercially available PVPI stability of solution is better, but certain taste is arranged, and should also add corresponding additive.This has also increased the weight of client's cost and burden.And the substantially directly dosing use of the PVPI dry powder of domestic other producer; Thereby the client in use, all has to add corresponding adjuvants.This can't solve still that the client is concerned about no longer adds other complicated auxiliary agent, directly uses the difficult problem of high performance PVPI dry powder.And the new disinfectant of my department is easy to use convenient, and direct available pure water is made into high steady solution.No longer need when dissolving, add other auxiliary agent, thereby really the client be freed.
Therefore, the present invention is by using prescription: the 7g crystalline flake of iodine (need not to pulverize), and (viscosity-average molecular weight PD value is less than 5.5 for 46～47gYK001 powder; Moisture 2.5%) and 0.19～0.27g sodium-chlor (grinding aid), disposable joining in the 250ml there-necked flask, 60～70 ℃ of heating in water bath, 200～250r/min mechanical stirring can obtain available iodine content and be higher than 10.5% PVPI.After reaction finishes directly according to prescription: PVPI5g (the first step self-control gained), Trisodium Citrate (buffer reagent) 0.30～0.50g, Potassium Iodate (iodide ion stablizer) 0.25～0.30g, potassiumiodide (iodide ion conditioning agent) 0.45～0.50g, sodium hydroxide (pH value conditioning agent) 0.0035～0.0045g, whole auxiliary agents are joined in the there-necked flask successively, after 50～60 seconds, can obtain the PVPI power-product of high stability through high speed pulverization.This product is 54 ℃ of two weeks of accelerated test, and available iodine content reduction value is less than 1.5%.Also can think this product under normal temperature condition the value of available iodine content reduction in two years less than 1.5%.Its optimum reacting time is 20～25 minutes only, is far smaller than 6～9 hours of ordinary method; Its 1% solution pH value remains on 4.5～5.5; Compare the market like product, its advantage shows:
1, the raw material elemental iodine need not be ground into the iodine powder, directly adopts sheet iodine; This can minus pulverizes and the technology of sieving, and has also avoided because of the corrosion to pulverizer of the strong oxidizing property of elemental iodine; It can significantly save cost.
2, the PVPI complexing time only needs 20 minutes, only needs for conventional 1/10th production times that reach still less; Can expand production capacity rapidly on the one hand, also significantly cut down the consumption of energy on the other hand; Its major cause is that raw material YK001 molecular weight is compared conventional PVPK30 height, and the PD value is little, narrow molecular weight distribution, and corresponding active high, active site is many and concentrated during with the iodine complexing, so be swift in response fully.
3, through composite PVPI dry powder good stability, accelerated tests shows that available iodine stability decreases rate is less than 1.5%; Quality guaranteed period is more than 3 years; Obtain solution no longer needs to add relevant auxiliary agent, and is easy to use, gets final product instant joining, and also can prepare the long-term placement in back.
4, by regulating processing parameter and formula rate, the PVPI available iodine content can be regulated arbitrarily from 9～12%.Thereby satisfy the segmentation requirement of different customers.
5, pH value keeps stable, is fixed on 4.5～5.5; On the one hand relative tart condition can increase the stability of available iodine, and high relatively on the other hand pH value more near the neutral pH value of human body, can significantly reduce the pungency of solution to human body; Compare BASF, the pH value of the product about 2.5 of ISP has more hommization, and using no longer needs to regulate pH value.
The inventor makes great efforts tackling key problem through the several years, independently develops high iodine content, high stability finally, produces PVPI pressed powder rapidly, and its solution does not need to add in addition relevant auxiliary agent and promptly keeps high stable, can satisfy USP, ISP, BP, EP, relevant officinal peak demand such as CP.Simultaneously, because of the reaction times only be other technology 1/10th or still less, improved production efficiency and product price ratio greatly, have great cost advantage and vast market prospect.Its key index is: available iodine content 10.5～12%, and the fluctuation ratio of available iodine stability (accelerating ability experiment) is less than 1.5%, and pH value maintains 4.5～5.5.
In sum, non-ionic N-vinyl butyrate lactam iodine iodine content height of the present invention, preparation is easy fast, cost is low, high-stability non-ionic N-vinyl butyrate lactam iodine stability is high, easy to use, satisfy relevant officinal peak demands such as USP, ISP, BP, EP, CP fully, be suitable for large-scale promotion application.
In this specification sheets, the present invention is described with reference to its certain embodiments.But, still can make various modifications and conversion obviously and not deviate from the spirit and scope of the present invention.Therefore, specification sheets is regarded in an illustrative, rather than a restrictive.
Claims (10)
1. the preparation method of a non-ionic N-vinyl butyrate lactam iodine, it is characterized in that, by homopolymerization N-vinyl butyrate lactam and iodine were prepared from described non-ionic N-vinyl butyrate lactam iodine in 20～25 minutes with 200～250r/min stirring under 60 ℃～70 ℃ temperature, the viscosity-average molecular weight of wherein said homopolymerization N-vinyl butyrate lactam is 40000-45000, and the PD value is less than 5.5; Moisture is 2.0-3.0%.
2. the preparation method of non-ionic N-vinyl butyrate lactam iodine according to claim 1 is characterized in that, described homopolymerization N-vinyl butyrate lactam is the YK001 powder, and described iodine adopts the crystalline flake of iodine.
3. the preparation method of non-ionic N-vinyl butyrate lactam iodine according to claim 1 is characterized in that, described homopolymerization N-vinyl butyrate lactam and described iodine stir under the grinding aid existence condition.
4. the preparation method of non-ionic N-vinyl butyrate lactam iodine according to claim 3 is characterized in that, described grinding aid is a sodium-chlor.
5. the preparation method of non-ionic N-vinyl butyrate lactam iodine according to claim 4 is characterized in that, described homopolymerization N-vinyl butyrate lactam is 46～47g, and described iodine is 7g, and described grinding aid is 0.19～0.27g.
6. a non-ionic N-vinyl butyrate lactam iodine is characterized in that, prepares by the preparation method according to arbitrary described non-ionic N-vinyl butyrate lactam iodine in the claim 1～6.
7. the preparation method of a high-stability non-ionic N-vinyl butyrate lactam iodine, it is characterized in that, by non-ionic N-vinyl butyrate lactam iodine according to claim 6 and pH buffer reagent, iodide ion stablizer, iodide ion conditioning agent and pH value conditioning agent are prepared from described high-stability non-ionic N-vinyl butyrate lactam iodine through the 20000-30000r/min high speed pulverization after 50～60 seconds, the available iodine content of wherein said non-ionic N-vinyl butyrate lactam iodine is higher than 10.5%.
8. the preparation method of high-stability non-ionic N-vinyl butyrate lactam iodine according to claim 7, it is characterized in that described pH buffer reagent is a Trisodium Citrate, described iodide ion stablizer is a Potassium Iodate, described iodide ion conditioning agent is a potassiumiodide, and described pH value conditioning agent is a sodium hydroxide.
9. the preparation method of high-stability non-ionic N-vinyl butyrate lactam iodine according to claim 8, it is characterized in that, described non-ionic N-vinyl butyrate lactam iodine is 5g, described Trisodium Citrate is 0.30～0.50g, described Potassium Iodate is 0.25～0.30g, described potassiumiodide is 0.45～0.50g, and described sodium hydroxide is 0.0035～0.0045g.
10. a high-stability non-ionic N-vinyl butyrate lactam iodine is characterized in that, prepares by the preparation method according to the arbitrary described high-stability non-ionic N-vinyl butyrate lactam iodine of claim 7～9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101813364A CN101838359B (en) | 2010-05-21 | 2010-05-21 | Non-ionic N-vinyl butyrate lactam iodine, high-stability non-ionic N-vinyl butyrate lactam iodine and relevant overspeed preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101813364A CN101838359B (en) | 2010-05-21 | 2010-05-21 | Non-ionic N-vinyl butyrate lactam iodine, high-stability non-ionic N-vinyl butyrate lactam iodine and relevant overspeed preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101838359A true CN101838359A (en) | 2010-09-22 |
| CN101838359B CN101838359B (en) | 2012-06-27 |
Family
ID=42742056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101813364A Active CN101838359B (en) | 2010-05-21 | 2010-05-21 | Non-ionic N-vinyl butyrate lactam iodine, high-stability non-ionic N-vinyl butyrate lactam iodine and relevant overspeed preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101838359B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125053A (en) * | 2011-01-07 | 2011-07-20 | 上海宇昂化工科技发展有限公司 | High-stability non-ionic N-vinyl butyrate lactam iodine solution and related preparation method |
| WO2012092775A1 (en) * | 2011-01-07 | 2012-07-12 | 上海宇昂化工科技发展有限公司 | High-stability non-ionic n-vinylbutyrolactam iodide and related preparation method therefor |
| CN102643377A (en) * | 2012-05-10 | 2012-08-22 | 上海宇昂生物科技有限公司 | Preparation method of homopolymerized N-vinyl butyl lactam iodine with 20% of effective iodine content |
| CN107748196A (en) * | 2017-09-26 | 2018-03-02 | 天津水泥工业设计研究院有限公司 | A kind of Grinding aid dosage adjusting indicating device for dry method grinding process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4402937A (en) * | 1979-10-18 | 1983-09-06 | Basf Aktiengesellschaft | Preparation of PVP-iodine |
| CN1341361A (en) * | 2001-09-02 | 2002-03-27 | 广东庆发药业有限公司 | Preparation method of povidone-iodine |
| CN1374835A (en) * | 1999-09-16 | 2002-10-16 | 巴斯福股份公司 | Method for the production of polyvinylpyrrolidone-iodine in an aqueous solution |
-
2010
- 2010-05-21 CN CN2010101813364A patent/CN101838359B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4402937A (en) * | 1979-10-18 | 1983-09-06 | Basf Aktiengesellschaft | Preparation of PVP-iodine |
| CN1374835A (en) * | 1999-09-16 | 2002-10-16 | 巴斯福股份公司 | Method for the production of polyvinylpyrrolidone-iodine in an aqueous solution |
| CN1341361A (en) * | 2001-09-02 | 2002-03-27 | 广东庆发药业有限公司 | Preparation method of povidone-iodine |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125053A (en) * | 2011-01-07 | 2011-07-20 | 上海宇昂化工科技发展有限公司 | High-stability non-ionic N-vinyl butyrate lactam iodine solution and related preparation method |
| WO2012092775A1 (en) * | 2011-01-07 | 2012-07-12 | 上海宇昂化工科技发展有限公司 | High-stability non-ionic n-vinylbutyrolactam iodide and related preparation method therefor |
| WO2012092776A1 (en) * | 2011-01-07 | 2012-07-12 | 上海宇昂化工科技发展有限公司 | High-stability non-ionic n-vinylbutyrolactam iodide solution and related formulation method therefor |
| CN102125053B (en) * | 2011-01-07 | 2013-08-07 | 上海宇昂水性新材料科技股份有限公司 | High-stability non-ionic N-vinyl butyrate lactam iodine solution and related preparation method |
| DE112011104683B4 (en) * | 2011-01-07 | 2021-02-25 | Shanghai Yuking Water Soluble Material Tech Co., Ltd. | Nonionic N-vinylbutyrolactam-iodine solution with high stability and its manufacturing process |
| CN102643377A (en) * | 2012-05-10 | 2012-08-22 | 上海宇昂生物科技有限公司 | Preparation method of homopolymerized N-vinyl butyl lactam iodine with 20% of effective iodine content |
| WO2013166782A1 (en) * | 2012-05-10 | 2013-11-14 | 上海宇昂生物科技有限公司 | Preparation method of homopolymerized n-vinyl butyl lactam iodine with effective iodide content of 20% |
| CN107748196A (en) * | 2017-09-26 | 2018-03-02 | 天津水泥工业设计研究院有限公司 | A kind of Grinding aid dosage adjusting indicating device for dry method grinding process |
| CN107748196B (en) * | 2017-09-26 | 2024-01-12 | 天津水泥工业设计研究院有限公司 | Grinding aid dosage adjusting and indicating device for dry grinding process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101838359B (en) | 2012-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101838359B (en) | Non-ionic N-vinyl butyrate lactam iodine, high-stability non-ionic N-vinyl butyrate lactam iodine and relevant overspeed preparation method | |
| CN102276757B (en) | Method for preparing chitin quaternary ammonium salt | |
| CN101147480B (en) | Modified lignosulfonate pesticide dispersing agent and its preparation method | |
| CN101248839A (en) | Composite aminoacid chelating microelement pre-mix material and preparation method thereof | |
| CN101870991A (en) | Method for preparing novel anti-peptic dextrin | |
| CN101589718B (en) | High-content tricyclazole suspending agent and preparation method thereof | |
| CN106187798B (en) | A kind of chelated calcium preparation method of amino acid nanometer | |
| CN103288980A (en) | Preparation method of carboxymethyl chitin | |
| CN107793262A (en) | A kind of water soluble fertilizer and preparation method thereof | |
| CN102125053B (en) | High-stability non-ionic N-vinyl butyrate lactam iodine solution and related preparation method | |
| CN103435710B (en) | A kind of preparation method being oxidized pregelatinated composite modified starch | |
| CN104311682A (en) | Preparation method of medicinal carboxymethyl starch | |
| CN102806357A (en) | Preparation method of high-stability nano-gold particles | |
| CN102432383B (en) | Humic acid organic boron fertilizer and production method thereof | |
| CN107488418A (en) | Preparation method for the adhesive of paper tube | |
| CN107098732A (en) | A kind of plant residue liquid activation method and its application | |
| CN102552065B (en) | Carboxymethyl yeast dextran eye cream, preparation method and application thereof | |
| CN101200747B (en) | Physical fields aided metal-coordination chitosan positioning enzymolysis method | |
| CN1073803C (en) | Aqueous agent of ethephon and paraquat | |
| CN207269294U (en) | A kind of external hanging type soil block reducing mechanism | |
| CN208194315U (en) | A kind of agrochemical rotating cylinder stirred type mixing arrangement | |
| CN110037050B (en) | High-efficiency compound iodine solution and preparation method thereof | |
| CN102775213B (en) | Method for preparing organic compound fertilizer | |
| CN1278608C (en) | Plant growth regulator | |
| CN101708010B (en) | Weeding water agent prepared by compounding gramoxone, 2-methyl-4-chloro-phonexyacetic and ammonium hydrogen carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210401 Address after: 441000 No.101, Guanyu Road, high tech Zone, Xiangyang City, Hubei Province Patentee after: Yuang Technology Co.,Ltd. Address before: Room 309, building 1, 88 Darwin Road, Zhangjiang hi tech park, Shanghai 201203 Patentee before: SHANGHAI YUKING BIOTECHNOLOGY Co.,Ltd. |