CN102633926B - Preparation method of low-residual-monomer N-vinyl butyl lactam homopolymer K90 aqueous solution - Google Patents
Preparation method of low-residual-monomer N-vinyl butyl lactam homopolymer K90 aqueous solution Download PDFInfo
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Abstract
The invention relates to a preparation method of low-residual-monomer N-vinyl butyl lactam homopolymer K90 aqueous solution. The preparation method comprises the following steps that: in the existence of inert gas and at a polymerization temperature ranging from 55 DEG C to 90 DEG C, a raw material, namely 10-35wt% N-vinyl butyl lactam monomer aqueous solution is stirred and reacted for 2.5 hours to 4.5 hours; during the period, an initiator is added in the raw material in batches, wherein the initiator is a mixture of azodiisobutyronitrile and azo-bis-iso-heptonitrile, and the total quantity of the initiator equals to 0.01% to 3% of the mass of N-vinyl butyl lactam monomers; and when a system K value reaches 90 to 102, the raw material with the initiator is kept at a temperature of 95 DEG C overnight to eliminate residual monomers, and in the process, mixed acid is added into the raw material with the initiator in batches to adjust the pH value to 2.0 to 7.0, thus obtaining the colorless transparent product, wherein the mixed acid is formed by mixing at least two acid selected from malonic acid, sulfuric acid and hydrochloric acid, and 10-35wt% product having the residual monomers below 10ppm and the stable K value being from 90 to 102. According to the invention, the design is ingenious, the preparation is simple, the residual monomers of the prepared N-vinyl butyl lactam homopolymer K90 aqueous solution are below 10ppm, the product is colorless, the K value of the product is stable, and thus the product is applicable to large-scale promotion and application.
Description
Technical field
The present invention relates to the compound preparing technical field, particularly N-vinyl butyrate lactam homopolymer preparing technical field, specifically refer to a kind of preparation method of the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution.
Background technology
Homopolymerization N-vinyl butyrate lactam is a kind of non-ionic water-soluble macromolecular compound, homopolymerization N-vinyl butyrate lactam is soluble in water, alcohol, amine and halohydrocarbon, and almost can be composite with other all positively charged ions, negatively charged ion and nonionic cosmetic product polymkeric substance.There is good solvability, Bc, physiology inertia, film-forming properties, film body protective capability.Homopolymerization N-vinyl butyrate lactam K90 is most characteristic in N-vinylamide homopolymer, and therefore most widely used fine chemicals kind has purposes widely.The application of homopolymerization N-vinyl butyrate lactam K90 in daily chemical industry: in daily cosmetics, good dispersion and the film-forming properties of homopolymerization N-vinyl butyrate lactam K90, can be used as dispersion agent and affinity agent in suds-stabilizing agent, wave setting agent and the hair dye of opalizer, shampoo of setting agent, the conditioner of style keeping liquid, hair spray and mousse.Add homopolymerization N-vinyl butyrate lactam in vanishing cream, sunscreen, trichogen, can strengthen moistening and lubricant effect.The application of homopolymerization N-vinyl butyrate lactam in industry and high-tech sector: homopolymerization N-vinyl butyrate lactam can be used as surperficial coating, dispersion agent, thickening material, tackiness agent in pigment, printing ink, weaving, printing and dyeing, colour picture tube.Homopolymerization N-vinyl butyrate lactam can improve the adhesive property of binding agent to metal, glass, plastic or other material, in addition, homopolymerization N-vinyl butyrate lactam is also increasingly extensive in the application of the emerging high-tech areas such as separatory membrane, paint and coating, photoconductive fiber, videodisc.The application of pharmaceutical grade homopolymerization N-vinyl butyrate lactam: one of three large medicinal new accessories that homopolymerization N-vinyl butyrate lactam is advocated in the ，Wei world that pharmaceutically is widely used.Most widely used is tablet, the tackiness agent of granule.Homopolymerization N-vinyl butyrate lactam also can be used as the glidant of capsule, the detoxicant of medicament for the eyes and lubricant, the solubility promoter of injection, the dispersion agent of liquid preparation, the stablizer of enzyme and temperature-sensitive medicine.The medicine that adopts the PVP product to make auxiliary material has hundreds of.
Because other low-molecular-weight homopolymerization N-vinyl butyrate lactam viscosity of homopolymerization N-vinyl butyrate lactam K90 viscosity ratio are all large, react residual raw material higher, the elimination of residual raw material is for being at present a bottleneck, and K value is easy to degrade.Therefore, if can produce the residual raw material of reaction below 10ppm, the homopolymerization N-vinyl butyrate lactam K90 of colourless and K value stabilization, for the pharmaceutical industries auxiliary material, will be with historically new significance.
Summary of the invention
The objective of the invention is to have overcome above-mentioned shortcoming of the prior art, a kind of preparation method of the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution is provided, the preparation method of this low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution designs ingenious, preparation is simple, the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution of preparing residual singly below 10ppm, colourless and K value stabilization, be suitable for large-scale promotion application.
To achieve these goals, the preparation method of the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution of the present invention, be characterized in, under the rare gas element existence condition, the N-vinyl butyrate lactam monomer solution of 10 ~ 35% weight of take is raw material, under 55 ℃ ~ 90 ℃ conditions of polymerization temperature, add in batches initiator during stirring reaction 2.5h-4.5h, the mixture that initiator is Diisopropyl azodicarboxylate and 2,2'-Azobis(2,4-dimethylvaleronitrile), the amount that altogether adds initiator is 0.01% ~ 3% of N-vinyl butyrate lactam monomer mass, treat that system K value reaches 90 ~ 102, adding in batches mixing acid tune pH in the residual single process of incubated overnight elimination under 95 ℃ of temperature condition is 2.0 ~ 7.0, wherein mixing acid is by being selected from propanedioic acid, two kinds of acid in sulfuric acid and hydrochloric acid mix, thereby what obtain 10 ~ 35% weight is residual singly below 10ppm and the K value stabilization water white low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution that is 90 ~ 102.
The described initiator that adds in batches can adopt any suitable step, preferably, the described initiator that adds in batches specifically adopts the following step: first add 40 ~ 60% of initiator gross weight, start polymerization, after 1h, add 20 ~ 30% of initiator gross weight, after continuing reaction 0.5h, add 10 ~ 20% of initiator gross weight, after 0.5h, add 10 ~ 30% of initiator gross weight, continue reaction 0.5-2.0h.
Described in described initiator, the ratio of Diisopropyl azodicarboxylate and described 2,2'-Azobis(2,4-dimethylvaleronitrile) can be any, and preferably, the ratio of Diisopropyl azodicarboxylate and described 2,2'-Azobis(2,4-dimethylvaleronitrile) described in described initiator is 3:7 ~ 7:3.
Describedly add in batches mixing acid to adjust pH be that the timed interval that in 2.0 ~ 7.0, mixing acid adds can be any, preferably, describedly add in batches mixing acid to adjust pH be that the timed interval that in 2.0 ~ 7.0, mixing acid adds is 1 ~ 5h.
Describedly add in batches mixing acid to adjust pH be that in 2.0 ~ 7.0, each added mixing acid can be identical, also can be different, preferably, describedly add in batches mixing acid to adjust pH be each added mixing acid difference in 2.0 ~ 7.0.
Describedly add in batches mixing acid to adjust pH be that pH each adjusted in 2.0 ~ 7.0 can be identical, also can be different, preferably, describedly add in batches mixing acid to adjust pH be pH difference each adjusted in 2.0 ~ 7.0.
Described mixing acid can be that in propanedioic acid, sulfuric acid and hydrochloric acid, any two kinds of acid mix with arbitrary proportion, preferably, and the mixing acid that described mixing acid is propanedioic acid and citric acid, or be the mixing acid of citric acid and hydrochloric acid, or be the mixing acid of propanedioic acid and hydrochloric acid.
Beneficial effect of the present invention specifically is: the preparation method of the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution of the present invention is under the rare gas element existence condition, the N-vinyl butyrate lactam monomer solution of 10 ~ 35% weight of take is raw material, under 55 ℃ ~ 90 ℃ conditions of polymerization temperature, add in batches initiator during stirring reaction 2.5h-4.5h, the mixture that initiator is Diisopropyl azodicarboxylate and 2,2'-Azobis(2,4-dimethylvaleronitrile), the amount that altogether adds initiator is 0.01% ~ 3% of N-vinyl butyrate lactam monomer mass, treat that system K value reaches 90 ~ 102, adding in batches mixing acid tune pH in the residual single process of incubated overnight elimination under 95 ℃ of temperature condition is 2.0 ~ 7.0, wherein mixing acid is by being selected from propanedioic acid, two kinds of acid in sulfuric acid and hydrochloric acid mix, thereby what obtain 10 ~ 35% weight is residual singly below 10ppm and the K value stabilization water white low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution that is 90 ~ 102, design ingenious, preparation is simple, the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution of preparing residual singly below 10ppm, colourless and K value stabilization, be suitable for large-scale promotion application.
The accompanying drawing explanation
The different polymerization time residual monomer of Fig. 1 N-vinyl butyrate lactam content figure.
Embodiment
In order more clearly to understand technology contents of the present invention, especially exemplified by following examples, describe in detail.
(1) raw material and reagent:
Table 1 raw material and reagent
(2) instrument and equipment:
Table 2 instrument and equipment
(3) polymkeric substance homopolymerization N-vinyl butyrate lactam K90 preparation
Logical rare gas element is N for example
2by air emptying in reaction system, this experiment reaction is carried out, use 10 ~ 35% N-vinyl butyrate lactam monomer solution, first distilled water and N-vinyl butyrate lactam monomer are joined in there-necked flask, be placed in the thermostatical oil bath, be warming up to 55 ℃ ~ 90 ℃, pass into nitrogen when stirring, altogether add initiator 0.01% ~ 3%(with respect to monomer N-vinyl butyrolactam mass ratio), initiator is Diisopropyl azodicarboxylate and 2,2'-Azobis(2,4-dimethylvaleronitrile) mixture, first add 40 ~ 60% of initiator gross weight, start polymerization, after 1h, add 20 ~ 30% of initiator gross weight, after continuing reaction 0.5h, add 10 ~ 20% of initiator gross weight, 0.5h after, add 10 ~ 30% of initiator gross weight, continue reaction 0.5-2.0h, treat that system K value reaches 90 ~ 102, add mixing acid (by being selected from propanedioic acid, two kinds of acid in sulfuric acid and hydrochloric acid mix) to adjust pH be 2.0 ~ 7.0, termination reaction, be warmed up to 95 ℃ of temperature, incubated overnight is eliminated residual raw material, mixing acid adds in batches during this time.By this experiment, thereby obtain the water white PVPK90 polymer water liquid that concentration is 10 ~ 35%, below residual N-vinyl butyrate lactam content 10ppm, the K value of resulting polymers solution (determination of aqueous solution that the weight concentration of take is 1%) is 90 ~ 102.
(4) Exploration of Mechanism
Fikentscher develops the aqueous solution polymerization method of NVP at first, and while adopting azo-initiator to cause, polymerization mechanism is as follows:
The initiation of chain:
The transmission of chain:
End stopping of chain:
Wherein RN ≡ NR represents azo-initiator, and R represents organic group, and N is nitrogen-atoms.
(5) results and discussions
5.1 eliminate in residual raw material process
5.1.1 the result of residual raw material is eliminated in different acid
The different acid of table 3 really affects residual unijunction
When selecting separately acetic acid and citric acid to eliminate residual raw material, the problem that the degraded of K value not only occurs, and, in the process of eliminating residual raw material, the solution jaundice occurs, and the content of residual raw material is all more than 0.01%, and select propanedioic acid/sulfuric acid/hydrochloric acid composite when acid, first use wherein two kinds of acid, eliminate residual raw material 3h, then select other the two kinds of acid in above-mentioned three kinds, eliminate residual raw material 5h, above-mentioned several problems can be solved.According to table 3, the content of residual raw material is down to below 10ppm.
5.1.2 add acid to eliminate in residual raw material process, pH affects the K value
Table 4pH affects the K value
As seen from Table 4, if pH lower than 2.0, acidity is too strong, K90 is unstable for homopolymerization N-vinyl butyrate lactam, easily decomposes, and causes the reduction of K value; If pH is higher than 7.0, under the condition that constantly stirs and heat, then polymerization of reaction, cause the viscosity of product to increase, the rising of K value; PH between 2.0 ~ 7.0 in, product is more stable, even spend the night, the K value is not degraded yet.In sum, in the process of eliminating residual raw material, best pH is 2.0 ~ 7.0.
5.1.3 add acid to eliminate in residual raw material process, the impact of pH on solution colour
The impact of table 5pH on solution colour
As can be seen from Table 5, solution is when pH is following, unstable, the solution flavescence.According to table 3, table 4 and table 5, we are when regulating pH, and preferably selecting pH is between 2.0 ~ 7.0, and the homopolymerization N-vinyl butyrate lactam K90 solution of preparation is colourless like this, and residual raw material is below 10ppm, and the K value stabilization is good.
5.2 azo-initiator
The different initiator for reaction situations of table 6
As can be seen from Table 6, only use 2,2'-Azobis(2,4-dimethylvaleronitrile), because its activation energy is low, low with respect to the Diisopropyl azodicarboxylate kick off temperature, in the time of 54 ℃, thermolysis generation free radical and nitrogen will occur in 2,2'-Azobis(2,4-dimethylvaleronitrile), but because its velocity of initiation is fast, than comparatively fast becoming sticky with Diisopropyl azodicarboxylate, but velocity of initiation is fast, causes residual raw material very high, this is its fatal shortcoming, and the product residue raw material of only making with it is very high; But use Diisopropyl azodicarboxylate, speed is slower, but it is higher to cause the beginning temperature, and advantage is that residual digital ratio is only low by 2,2'-Azobis(2,4-dimethylvaleronitrile); By the two mixing, adopt and add in batches, can prepare colourless, as almost there is no raw material taste, the product of residual raw material below 10ppm.
5.3 polymerization time affects residual raw material
During preparation homopolymerization N-vinyl butyrate lactam K90, in the situation that other condition is constant, investigate the impact of polymerization time on residual monomer content.
Table 7 polymerization time affects residual raw material
According to table 7, make the variation diagram of the content of corresponding residual monomer N-vinyl butyrolactam along with polymerization time, see Fig. 1.From table 7 and Fig. 1, along with the carrying out of polymerization time, the content of residual monomer N-vinyl butyrolactam reduces gradually, but the speed reduced is slowing down gradually, while reacting to the 3h left and right, the content of residual monomer N-vinyl butyrolactam will tend towards stability, and no longer reduce.So, when carrying out the experiment of homopolymerization N-vinyl butyrate lactam K90, it is proper that the time should be chosen in 2.5h ~ 4.5h.
(6) characterize
6.1K the mensuration of value
Usually we characterize the molecular weight of homopolymerization N-vinyl butyrate lactam by the K value of Fikentscher formula, and the K value is only relevant with molecular weight, the parameter do not changed with the concentration of homopolymerization N-vinyl butyrate lactam.Measuring K value method commonly used is viscosimetry, and dark type viscometer, under 25 ± 0.2 ℃ of bath temperatures, is measured the relative viscosity η r of this solution to water.
According to Fikentscher formula calculating K value following (Li Xinming. a kind of method [P] .CN 1712432 that eliminates residual monomer N-vinyl-pyrrolidone in polymer, 2005-12-28):
In formula:
K is the Fikentscher constant;
C dissolves the grams of homopolymerization N-vinyl butyrate lactam in 0.1L solution
η r is solution solvent viscosity ratio (the ratio T/T of solution elution time and neat solvent elution time
0)
6.2 the content of residual monomer
In homopolymerization N-vinyl butyrate lactam, the mensuration of residual monomer content is the method with reference to the 26th edition regulation of American Pharmacopeia.Get 10g homopolymerization N-vinyl butyrate lactam (accurately to 0.002g, in anhydride), be dissolved in 80ml distilled water, add the 1g sodium-acetate, be titrated to solution with the 0.1mol/L iodine solution and no longer fade, separately add again the iodine solution of 3ml 0.l mol/L, place 10 minutes, then use the iodine of the Sulfothiorine overtitration of 0.l mol/L, add the Starch Indicator of 3ml when approaching terminal, continue to be titrated to solution colour and disappear, contrast with blank assay simultaneously.
Result is calculated:
In formula:
V
1the hypo solution that-titration blank sample consumes (mL);
V
2the hypo solution that-titration sample consumes (mL);
The concentration of N-hypo solution (mol/L);
0.106 the quality (g) of-l mmol/L NVP;
The quality of m-sample (g).
Below enumerate several embodiment and be described more specifically the present invention, but the present invention is not subject to the restriction of these embodiment.In content below, unless specified otherwise only is expressed as " part " by " weight part ", " % by weight " only is expressed as to " % ".
Embodiment 1
The N-vinyl butyrate lactam monomer solution that this experiment reaction density is 18% weight, interpolation initiator gross weight is: 0.32%(is with respect to monomer N-vinyl butyrolactam mass ratio).Import nitrogen when adding 287 parts of water as reaction solvent, stirring in the reaction vessel of being furnished with gas feed, prolong, thermometer, by the air emptying in reaction vessel, form nitrogen atmosphere.Then, using oil bath to heat the internal temperature that makes reaction vessel reaches after 70 ℃, add 63 parts of N-vinyl butyrate lactams and 0.08 part of initiator that Shanghai Yu'ang Chemical Technology Development Co., Ltd. produces, this initiator is comprised of Diisopropyl azodicarboxylate/2,2'-Azobis(2,4-dimethylvaleronitrile)=5/5.After 1h, add again 0.06 part of initiator, after continuing reaction 0.5h, continue to add 0.04 part of initiator, 0.5h after, add 0.02 part of initiator, after continuing reaction 1.5h, add propanedioic acid/hydrochloric acid equal proportion mixing acid in container, the pH value is adjusted to 5.5, temperature rises to 95 ℃, after eliminating residual raw material 3h, add again sulfuric acid/hydrochloric acid equal proportion mixed solution, pH is adjusted to 4.0, after being eliminated residual raw material 5h, in reaction solution, N-vinyl butyrate lactam concentration is 8ppm, thereby obtain concentration and be 18% water white PVPK90 polymer water liquid, the K value of resulting polymers solution (determination of aqueous solution that the weight concentration of take is 1%) is 98.01.
Comparative Examples 1:
When eliminating residual raw material after reacting, in embodiment 1, mixing acid changes into only with outside sulfuric acid, remaining experimentation all with embodiment 1 in full accord, the aqueous solution that PVPK90 concentration is 18% is prepared in polymerization, residual N-vinyl butyrate lactam concentration is 51ppm, and the K value of resulting polymers solution (determination of aqueous solution that the weight concentration of take is 1%) is 97.84.
Comparative Examples 2
Initiator in embodiment 1 is changed to outside 2,2'-Azobis(2,4-dimethylvaleronitrile), in full accord in remaining experimentation and embodiment 1, preparing N-vinyl butyrate lactam concentration in the reaction solution of PVPK90 polymkeric substance is 102ppm, the water white PVPK90 polymer water liquid that concentration is 18%, the K value of resulting polymers solution (determination of aqueous solution that the weight concentration of take is 1%) is 110.11.
Embodiment 2:
As different from Example 1, adding the initiator gross weight is: 0.01%(is with respect to monomer NVP mass ratio); Use oil bath to heat the internal temperature that makes reaction vessel and reach 90 ℃; Initiator is comprised of Diisopropyl azodicarboxylate/2,2'-Azobis(2,4-dimethylvaleronitrile)=7/3; Add for the first time 0.003 part of initiator, after 1h, then add 0.0012 part of initiator, after continuing reaction 0.5h, continue to add 0.0006 part of initiator, after 0.5h, add 0.0012 part of initiator, continue polyreaction 0.5h after adding initiator; Mixing acid is propanedioic acid/hydrochloric acid equal proportion mixing acid for the first time, and regulating pH is 7, the mixing acid that mixing acid is sulfuric acid/hydrochloric acid=8/2 for the second time, and regulating pH is 5, twice acid adding 1h interval time.Preparing N-vinyl butyrate lactam concentration in the reaction solution of PVPK90 polymkeric substance is 5ppm, the water white PVPK90 polymer water liquid that concentration is 18%, and the K value of resulting polymers solution (determination of aqueous solution that the weight concentration of take is 1%) is 95.01.
Embodiment 3
As different from Example 1, adding the initiator gross weight is: 3%(is with respect to monomer NVP mass ratio); Use oil bath to heat the internal temperature that makes reaction vessel and reach 55 ℃; Initiator is comprised of Diisopropyl azodicarboxylate/2,2'-Azobis(2,4-dimethylvaleronitrile)=3/7; Add for the first time 1.134 parts of initiators, after 1h, then add 0.378 part of initiator, after continuing reaction 0.5h, continue to add 0.189 part of initiator, after 0.5h, add 0.378 part of initiator, continue polyreaction 2h after adding initiator; The mixing acid that mixing acid is sulfuric acid/hydrochloric acid=3/7 for the first time, regulating pH is 5, the mixing acid that mixing acid is propanedioic acid/sulfuric acid=1/9 for the second time, regulating pH is 2, twice acid adding 5h interval time.Prepare the aqueous solution that PVPK90 concentration is 18%, residual N-vinyl butyrate lactam concentration is 7.95ppm, and the K value of resulting polymers solution (determination of aqueous solution that the weight concentration of take is 1%) is 99.01.
This experiment reaction density is 10%, adds the initiator gross weight to be: 0.32%(is with respect to monomer N-vinyl butyrolactam mass ratio).Import nitrogen when adding 567 parts of water as reaction solvent, stirring in the reaction vessel of being furnished with gas feed, prolong, thermometer, by the air emptying in reaction vessel, form nitrogen atmosphere.Then, using oil bath to heat the internal temperature that makes reaction vessel reaches after 55 ℃, add 63 parts of N-vinyl butyrate lactams and 0.08 part of initiator that Shanghai Yu'ang Chemical Technology Development Co., Ltd. produces, this initiator is comprised of Diisopropyl azodicarboxylate/2,2'-Azobis(2,4-dimethylvaleronitrile)=5/5.After 1h, add again 0.04 part of initiator, after continuing reaction 0.5h, continue to add 0.02 part of initiator, 0.5h after, add 0.06 part of initiator, after continuing reaction 1.5h, add propanedioic acid/sulfuric acid equal proportion mixing acid in container, the pH value is adjusted to 5.5, temperature rises to 95 ℃, after eliminating residual raw material 3h, add again propanedioic acid/hydrochloric acid equal proportion mixed solution, pH is adjusted to 4.0, after being eliminated residual raw material 5h, in reaction solution, N-vinyl butyrate lactam concentration is 1ppm, thereby obtain concentration and be 10% water white PVPK90 polymer water liquid, the K value of resulting polymers solution (determination of aqueous solution that the weight concentration of take is 1%) is 93.35.
Embodiment 5
This experiment reaction density is 35%, adds the initiator gross weight to be: 0.32%(is with respect to monomer N-vinyl butyrolactam mass ratio).Import nitrogen when adding 117 parts of water as reaction solvent, stirring in the reaction vessel of being furnished with gas feed, prolong, thermometer, by the air emptying in reaction vessel, form nitrogen atmosphere.Then, using oil bath to heat the internal temperature that makes reaction vessel reaches after 95 ℃, add 63 parts of N-vinyl butyrate lactams and 0.08 part of initiator that Shanghai Yu'ang Chemical Technology Development Co., Ltd. produces, this initiator is comprised of Diisopropyl azodicarboxylate/2,2'-Azobis(2,4-dimethylvaleronitrile)=5/5.After 1h, add again 0.04 part of initiator, after continuing reaction 0.5h, continue to add 0.04 part of initiator, 0.5h after, add 0.04 part of initiator, after continuing reaction 1.5h, add hydrochloric acid/sulfuric acid equal proportion mixing acid in container, the pH value is adjusted to 5.5, temperature rises to 95 ℃, after eliminating residual raw material 3h, add again propanedioic acid/sulfuric acid equal proportion mixed solution, pH is adjusted to 4.0, after being eliminated residual raw material 5h, in reaction solution, N-vinyl butyrate lactam concentration is 2ppm, thereby obtain concentration and be 35% water white PVPK90 polymer water liquid, the K value of resulting polymers solution (determination of aqueous solution that the weight concentration of take is 1%) is 95.5.
The purpose that passes into nitrogen in system of the present invention is the oxygen of removing in reaction system, and reaction is carried out under rare gas element, and oxygen has inhibition, accelerates chain termination reaction, reduces polymericular weight.By attempting different acid, find in triturating, select the composite acid of propanedioic acid/sulfuric acid/hydrochloric acid to eliminate residual raw material, and add in batches, can not only drop to 10ppm to residual raw material with in interior, as to eliminate residual raw material process, and the color of solution does not change.Found through experiments, no matter pH is of great impact to solution colour or product stability, and pH is too high or too low, can cause the degraded of K value or raise, and when eliminating residual raw material, selects pH proper between 2.0 ~ 7.0.On the selection initiator, should select Diisopropyl azodicarboxylate and 2,2'-Azobis(2,4-dimethylvaleronitrile) mixed initiating system, and add in batches.
Therefore, the present invention has studied the various influence factors to product from aspects such as acid, initiator, pH, polymerization times, adopt special mixing acid, the composite initiation system of the present invention, and adjust initiator, sour addition sequence, prepare residual singly at 10ppm with the high stable product interior, that the K value is non-degradable, its product meets the product homopolymerization N-vinyl butyrate lactam K90 that the up-to-date state-promulgated pharmacopoeia of the American-European countries such as USP32, BP2006, EP6 requires.
To sum up, the preparation method of the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution of the present invention designs ingenious, preparation is simple, the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution of preparing residual singly below 10ppm, colourless and K value stabilization, be suitable for large-scale promotion application.
In this specification sheets, the present invention is described with reference to its specific embodiment.But, still can make various modifications and conversion obviously and not deviate from the spirit and scope of the present invention.Therefore, specification sheets and accompanying drawing are regarded in an illustrative, rather than a restrictive.
Claims (7)
1. the preparation method of a low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution, it is characterized in that, under the rare gas element existence condition, the N-vinyl butyrate lactam monomer solution of 10～35% weight of take is raw material, under 55 ℃～90 ℃ conditions of polymerization temperature, add in batches initiator during stirring reaction 2.5h-4.5h, the mixture that initiator is Diisopropyl azodicarboxylate and 2,2'-Azobis(2,4-dimethylvaleronitrile), the amount that altogether adds initiator is 0.01%～3% of N-vinyl butyrate lactam monomer mass, treat that system K value reaches 90～102, adding in batches mixing acid tune pH in the residual single process of incubated overnight elimination under 95 ℃ of temperature condition is 2.5～7.0, wherein mixing acid is by being selected from propanedioic acid, two kinds of acid in sulfuric acid and hydrochloric acid mix, thereby what obtain 10～35% weight is residual singly below 10ppm and the K value stabilization water white low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution that is 90～102.
2. the preparation method of the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution according to claim 1, it is characterized in that, the described initiator that adds in batches specifically adopts the following step: first add 40～60% of initiator gross weight, start polymerization, after 1h, add 20～30% of initiator gross weight, after continuing reaction 0.5h, add 10～20% of initiator gross weight, after 0.5h, add 10～30% of initiator gross weight, continue reaction 0.5-2.0h.
3. the preparation method of the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution according to claim 1, is characterized in that, the ratio of Diisopropyl azodicarboxylate and described 2,2'-Azobis(2,4-dimethylvaleronitrile) described in described initiator is 3:7～7:3.
4. the preparation method of the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution according to claim 1, is characterized in that, describedly adds in batches mixing acid to adjust pH be that the timed interval that in 2.5～7.0, mixing acid adds is 1～5h.
5. the preparation method of the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution according to claim 1, is characterized in that, describedly adds in batches mixing acid to adjust pH be each added mixing acid difference in 2.5～7.0.
6. the preparation method of the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution according to claim 1, is characterized in that, describedly adds in batches mixing acid to adjust pH be pH difference each adjusted in 2.5～7.0.
7. the preparation method of the low-residue single N-vinyl butyrate lactam homopolymer K90 aqueous solution according to claim 1, is characterized in that the mixing acid that described mixing acid is propanedioic acid and hydrochloric acid.
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| CN2012101549303A CN102633926B (en) | 2012-05-16 | 2012-05-16 | Preparation method of low-residual-monomer N-vinyl butyl lactam homopolymer K90 aqueous solution |
| GB1420099.2A GB2517604B (en) | 2012-05-16 | 2012-07-23 | Preparation method of an aqueous solution of the N-vinyl butyrolactam homopolymer K90 with low residual monomer content |
| PCT/CN2012/079061 WO2013170534A1 (en) | 2012-05-16 | 2012-07-23 | Method for preparing homopolymer k90 aqueous solution of n-vinyl butyrolactam with low residual monomer |
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| CN115093498B (en) * | 2022-06-17 | 2023-05-26 | 中盐安徽红四方股份有限公司 | Preparation method of PVP (polyvinyl pyrrolidone) with low residual monomer and low chromaticity |
| CN115073639A (en) * | 2022-06-17 | 2022-09-20 | 中盐安徽红四方股份有限公司 | Preparation method of polyvinylpyrrolidone K90 aqueous solution with thermal yellowing resistance |
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| CN1365367A (en) * | 2000-06-15 | 2002-08-21 | 第一工业制药株式会社 | Process for producing high-purity vinylpyrolidone polymer |
| US6465592B1 (en) * | 2000-06-15 | 2002-10-15 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for preparing vinylpyrrolidone polymer |
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| US6617420B2 (en) * | 2000-08-11 | 2003-09-09 | Nippon Shokubai Co., Ltd. | Process for reducing monomer content in N-vinyl compound polymers |
| JP3899278B2 (en) * | 2002-03-28 | 2007-03-28 | 株式会社日本触媒 | Method for producing vinyl lactam polymer |
| JP3999022B2 (en) * | 2002-04-04 | 2007-10-31 | 株式会社日本触媒 | Vinyl pyrrolidone polymer |
| JP4205731B2 (en) * | 2006-04-05 | 2009-01-07 | 株式会社日本触媒 | Polyvinylpyrrolidone powder composition and production method thereof |
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| CN1365367A (en) * | 2000-06-15 | 2002-08-21 | 第一工业制药株式会社 | Process for producing high-purity vinylpyrolidone polymer |
| US6465592B1 (en) * | 2000-06-15 | 2002-10-15 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Process for preparing vinylpyrrolidone polymer |
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| Title |
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| 低含量残留单体的中高分子量PVP K60合成研究;曾阳等;《精细与专用化学品》;20120131;第20卷(第1期);40-44 * |
| 曾阳等.低含量残留单体的中高分子量PVP K60合成研究.《精细与专用化学品》.2012,第20卷(第1期),40-44. |
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| WO2013170534A1 (en) | 2013-11-21 |
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