CN112225835A - high-K low-residue monomer polymer powder and preparation method thereof - Google Patents
high-K low-residue monomer polymer powder and preparation method thereof Download PDFInfo
- Publication number
- CN112225835A CN112225835A CN202011185195.3A CN202011185195A CN112225835A CN 112225835 A CN112225835 A CN 112225835A CN 202011185195 A CN202011185195 A CN 202011185195A CN 112225835 A CN112225835 A CN 112225835A
- Authority
- CN
- China
- Prior art keywords
- powder
- polymer powder
- polymer
- value
- residual monomer
- 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.)
- Pending
Links
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
- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
- C08F6/005—Removal of residual monomers by physical means from solid polymers
Abstract
The invention belongs to the technical field of preparation of polymer powder, and discloses high-K-value low-residue monomer polymer powder and a preparation method thereof. The residual monomer content of the high-K polymer powder prepared by the preparation method is lower than 10ppm, and the appearance of the polymer powder is light yellow to milky powder.
Description
Technical Field
The invention belongs to the technical field of preparation of polymer powder, and particularly relates to a preparation method of high-K-value low-residue monomer polymer powder and the high-K-value low-residue monomer polymer powder prepared by the preparation method.
Background
Polyvinylpyrrolidone (PVP) is a water-soluble polymer material polymerized from monomer vinyl pyrrolidone (NVP), and is mainly used in various fields such as medicine, food, personal care, industry, and the like. The vinyl pyrrolidone/vinyl caprolactam copolymer (NVP/NVCL) is a binary copolymer based on the improvement of PVP performance, and besides most of the properties of PVP, the copolymer also has unique performance, such as temperature sensitivity of an aqueous solution and certain cloud point. And the proportion of the two components is different, so that the composition is obviously different and can be used for different occasions and industries.
The PVP and the NVP/NVCL are water-soluble polymer materials, and are distinguished by adopting the K value of the Fikentscher method according to the size of the molecular weight, for example, the PVP is divided into the following components according to the K value: k12, K17, K25, K30, K60, K90, K120, and the like. The greater the difference in K value (or molecular weight) of the polymer, the more distinct the difference in solution viscosity, the greater the K value the greater the viscosity.
With the development of society, the quality requirements of people on fine chemicals are higher and higher, and various industrial standards, pharmacopoeia specifications and the like execute strict quality standards. Such as the united states pharmacopeia, european pharmacopeia, chinese pharmacopeia, etc., it is required that the residual monomer NVP of polyvinylpyrrolidone (powder) is less than 10 ppm. However, the high K polymer powder products obtained by the known preparation methods do not substantially meet the above-mentioned requirements for residual monomer content.
Disclosure of Invention
In view of the above circumstances, the present inventors have studied the control of residual monomers in the production process of polymer powders and found that the residual monomers grow in the process of obtaining polymer powders by post-treating the polymerization liquid obtained by the polymerization reaction.
Specifically, in the preparation of high-K polymer powder products, the polymer liquid is generally dried by vacuum belt drying and then pulverized, and the drying and pulverizing processes are accompanied by the phenomenon of increased residual monomer content, especially after the pulverizing process, the residual monomer content is increased significantly. The research shows that the reasons for increasing the residual monomers of the high-K polymer powder by the crushing treatment mainly include: 1. the degradation of the polymer in the crushing process generates residual monomers, and all the monomers generated by degradation are adhered to the surface of the powdery polymer through intermolecular force (such as hydrogen bonds and the like); 2. the residual monomer before crushing is mainly wrapped inside the large polymer particles, and after crushing, the originally wrapped monomer is released due to the crushing of the particles and is adhered to the surface of the powdery polymer.
In addition, the boiling point of the residual monomer of the high K-value polymer is relatively high, for example, the boiling point of the residual monomer NVP in the PVP powder and the NVP/NVCL copolymer powder is 148 ℃ (at 13.33 KPa), the glass transition temperature Tg of the PVP powder is 145-175 ℃ (the higher the Tg is), the boiling point of the residual monomer NVCL in the NVP/NVCL copolymer powder is 128 ℃ (at 21 mmHg), and the glass transition temperature Tg of the NVP/NVCL copolymer powder is 150-175 ℃. It can be seen that the monomer is removed by heating the high-K polymer to the boiling point of the residual monomer in a conventional residual monomer removal manner, and at this time, the high-K polymer is already in a completely viscous state, so that the monomer is wrapped inside and is more difficult to remove.
Based on the above findings, the present invention aims to provide a high-K low-residual monomer polymer powder and a preparation method thereof, which can make the residual monomer content in the high-K polymer powder lower than 10ppm and ensure that the K value of the polymer powder is basically unchanged so as to meet the quality requirements of high-K polymer products.
The first aspect of the invention provides a preparation method of high-K-value low-residue monomer polymer powder, which comprises the steps of carrying out monomer polymerization reaction to obtain polymer liquid, drying and crushing the polymer liquid to obtain polymer powder, and treating the polymer powder under the conditions of heating, negative pressure and dynamic mixing, or heating, nitrogen purging and dynamic mixing.
In the present invention, the polymer powder may be PVP powder or NVP/NVCL copolymer powder. In the process of crushing the two polymer powders, NVP monomer is increased, and the two polymer powders can be treated by the method.
In the present invention, the K value of the polymer powder is in the range of 45 to 100. The polymer powder within the K value range is mostly dried by adopting a vacuum belt type, the monomer exceeds the standard in the crushing process, and the preparation method is required to be adopted for processing so as to meet the requirement of the residual monomer amount.
Preferably, the heating temperature is 140-160 ℃, the negative pressure is-0.090-0.10 MPa, the stirring frequency is 10-60Hz, and the treatment time is 1-36 hr.
According to the present invention, the treatment may be carried out by a conventional apparatus in the art as long as the above-mentioned treatment conditions of heating, negative pressure, and dynamic mixing are satisfied. The device used for the treatment can be a rake dryer or a cone dryer, the treatment efficiency of the cone dryer is high, and the cone dryer is preferred.
Preferably, the heating temperature is 140-160 ℃, the induced air frequency of the nitrogen purging is 10-50Hz, and the boiling time is 1-8 hr.
According to the present invention, the treatment may be carried out by a conventional apparatus in the art as long as the treatment conditions of the above-mentioned heating, nitrogen purging, and dynamic mixing are satisfied. For example, the device used for the treatment may be a boiling fluidized bed, and when the treatment is carried out by using the boiling fluidized bed, the inlet air temperature is the temperature heated under the above-mentioned treatment conditions.
In addition, the preparation of the polymer liquid of the present invention and the drying and pulverization thereof are carried out by a conventional method in the art.
The second aspect of the present invention provides a high-K low-residual monomer polymer powder obtained by the above-mentioned production method.
Preferably, the polymer powder has a residual monomer content of less than 10ppm and an appearance of a yellowish to milky powder.
The invention breaks the adhesive force between the residual monomer and the polymer, such as hydrogen bond and the like, under the action of heating, negative pressure or nitrogen and dynamic mixing, so that the high boiling point monomer is displaced and even removed from the original system, thereby realizing the purpose of removing the residual monomer in the high K value polymer powder, ensuring that the content of the residual monomer in the high K value polymer powder is lower than 10ppm, not influencing the K value of the polymer powder, and meeting the requirement of the appearance of the obtained polymer powder.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
100kg of PVP powder (with a K value of 98.5 and a monomer NVP content of 24ppm) which is crushed in advance is added into a 200L rake dryer, the vacuum is pumped to-0.095 MPa, the temperature is raised to 140 ℃ (with a steam pressure of 0.3MPa), the stirring frequency of rake teeth is 25Hz, the time is kept for 6 hours, the temperature is reduced to room temperature, and the vacuum is removed. A milky white powder was obtained by sampling, and the test K value was 96.2 and the residual monomer NVP content was 5.7 ppm.
Example 2
100kg of PVP powder (with a K value of 98.5 and a monomer NVP content of 24ppm) which is crushed in advance is added into a 200L rake dryer, the vacuum is pumped to-0.095 MPa, the temperature is raised to 158 ℃ (steam pressure of 0.45MPa), the stirring frequency of rake teeth is 15Hz, the time is kept for 12 hours, the temperature is reduced to room temperature, and the vacuum is removed. A milky white powder was obtained by sampling, and the test K value was 95.9 and the residual monomer NVP content was 5.1 ppm.
Example 3
100kg of PVP powder (K value is 45.5, and the content of NVP in monomer is 18ppm) which is crushed in advance is added into a 200L rake dryer, the vacuum is pumped to-0.090 MPa, the temperature is raised to 150 ℃ (steam pressure is 0.42MPa), the stirring frequency of rake teeth is 50Hz, the time is kept for 36 hours, the temperature is lowered to room temperature, and the vacuum is removed. A sample was taken to give a pale yellow powder with a test K value of 45.1 and a residual monomer NVP content of 8.5 ppm.
Example 4
100kg of NVP/NVCL copolymer powder (the K value is 68.2, the contents of monomer NVP and NVCL are respectively 19ppm and 8ppm) which is crushed in advance is added into a 200L rake dryer, the rake dryer is vacuumized to-0.095 MPa, the temperature is raised to 145 ℃ (the steam pressure is 0.35MPa), the stirring frequency of rake teeth is 60Hz, the rake dryer is run for 24 hours in a timing mode, the temperature is lowered to 40 ℃, and then the vacuum is removed. A milky white powder was sampled and tested for a K value of 67.54 and residual monomer NVP and NVCL contents of 6.6ppm and 3.2ppm, respectively.
Example 5.
35kg of PVP powder (with a K value of 98.5 and a monomer NVP content of 24ppm) which is crushed in advance is put into a 50L conical dryer, the conical dryer is vacuumized to-0.090 MPa, the temperature is raised to 140 ℃ (the steam pressure is 0.3MPa), the stirring frequency of a crank arm is 35Hz, the conical dryer is timed to run for 1 hour, then the temperature is lowered to the room temperature, and the vacuum is removed. A milky white powder was obtained by sampling, and the test K value was 97.2 and the residual monomer NVP content was 3.7 ppm.
Example 6
36kg of NVP/NVCL copolymer powder (the K value is 52.5, the contents of monomer NVP and NVCL are 23ppm and 12ppm respectively) which is prepared by crushing in advance is added into a 50L conical dryer, the conical dryer is vacuumized to-0.093 MPa, the temperature is raised to 140 ℃ (the steam pressure is 0.3MPa), the stirring frequency of a crank arm is 40Hz, the conical dryer is cooled to room temperature after running for 6 hours in a timing mode, and the vacuum is removed. A milky white powder was sampled and tested for a K value of 51.7 and residual monomer NVP and NVCL contents of 6.68ppm and 3.37ppm, respectively.
Example 7
80kg of PVP powder (with a K value of 98.5 and a monomer NVP content of 24ppm) which is crushed in advance is added into a boiling fluidized bed (with a designed maximum treatment capacity of 150L), the nitrogen induced air frequency is 26Hz, the air inlet temperature is 160 ℃, the air outlet temperature is 140 ℃, the boiling fluidized desorption is carried out for 4 hours, the temperature is reduced to 60 ℃, the machine is stopped, and the nitrogen is stopped. The discharge gave a milky white powder with a test K value of 95.68 and a residual monomer NVP content of 4.9 ppm.
Example 8
70kg of NVP/NVCL copolymer powder (the K value is 52.5, the contents of monomer NVP and NVCL are respectively 23ppm and 12ppm) which is crushed in advance is added into a boiling fluidized bed (the designed maximum processing capacity is 150L), the induced air frequency of nitrogen is 40Hz, the air inlet temperature is 150 ℃, the air outlet temperature is 130 ℃, the boiling fluidized desorption is carried out for 4 hours, the temperature is reduced to 60 ℃, the machine is stopped, and the nitrogen is stopped. The discharge gave a milky white powder with a test K of 50 and residual monomer NVP and NVCL contents of 7.9ppm and 5.1ppm, respectively.
Comparative example 1
100kg of PVP powder (with a K value of 98.5 and a monomer NVP content of 24ppm) which is crushed in advance is added into a 200L rake dryer, the vacuum is pumped to-0.095 MPa, the temperature is raised to 140 ℃ (the steam pressure is 0.3MPa), the stirring frequency of rake teeth is 5Hz, the time is kept for 6 hours, and the temperature is reduced to room temperature and then the material is discharged. The material is changed into light yellow powder and has uneven color, K values and residual sheets of the powder with darker color and the powder with lighter color are respectively tested, and the K values and the residual sheets NVP are found to be uneven, wherein the K value is 96.7 at the highest and 93.2 at the lowest; the residual monomer NVP content was at most 18ppm and at least 13.7 ppm.
Comparative example 2
100kg of PVP powder (with a K value of 98.5 and a monomer NVP content of 24ppm) which is crushed in advance is added into a 200L rake dryer, the temperature is raised to 140 ℃ (the steam pressure is 0.3MPa), the stirring frequency of rake teeth is 25Hz, the time is kept for 6 hours, and then the temperature is reduced to the room temperature and the material is discharged. The batch turned into a dark yellow powder with a more uniform color distribution, a test K value of 76.8 and a residual monomer NVP content of 18 ppm.
Comparative example 3
Adding 80kg of PVP powder (with K value of 98.5 and monomer NVP content of 24ppm) which is crushed in advance into a boiling fluidized bed (with the designed maximum treatment capacity of 150L), introducing nitrogen at the induced air frequency of 8Hz, the air inlet temperature of 130 ℃, the air outlet temperature of 100 ℃, desorbing for 8 hours in a boiling fluidization manner, cooling to 60 ℃, stopping the machine, and stopping nitrogen. The discharge gave a pale yellow powder with a test K value of 94.3 and a residual monomer NVP content of 19.4 ppm.
Comparative example 4
35kg of PVP powder (with a K value of 98.5 and a monomer NVP content of 24ppm) which is crushed in advance is put into a 50L conical dryer, the conical dryer is vacuumized to-0.085 MPa, the temperature is raised to 140 ℃ (the steam pressure is 0.3MPa), the stirring frequency of a crank arm is 10Hz, the conical dryer is timed to run for 1 hour, then the temperature is lowered to the room temperature, and the vacuum is removed. A milky white powder was obtained by sampling, and the test K value was 97.2 and the residual monomer NVP content was 11.7 ppm.
The K values and the amounts of residual monomers and the like of the respective examples and comparative examples are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the residual monomer content of the high K value polymer powder prepared by the preparation method of the invention is lower than 10ppm, and simultaneously the K value of the polymer powder is ensured to be basically unchanged, the appearance of the polymer powder is light yellow powder or milk white powder, the requirements of relevant regulations on color are met, and the residual monomer content of the polymer powder obtained by the process parameters of the invention is lower and the K value is more stable.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.
Claims (9)
1. The preparation method of the high-K-value low-residue monomer polymer powder comprises the steps of carrying out monomer polymerization reaction to obtain polymer liquid, drying and crushing the polymer liquid to obtain polymer powder, and is characterized in that the polymer powder is treated under the conditions of heating, negative pressure and dynamic mixing, or heating, nitrogen purging and dynamic mixing.
2. The method of claim 1, wherein the polymer powder is PVP powder or NVP/NVCL copolymer powder.
3. The method of claim 1 or 2, wherein the polymer powder has a K value in the range of 45 to 100.
4. The method as claimed in claim 1, wherein the heating temperature is 140-160 ℃, the negative pressure is-0.090 MPa to-0.10 MPa, the stirring frequency is 10Hz to 60Hz, and the processing time is 1 hr to 36 hr.
5. The method according to claim 4, wherein the apparatus used for the treatment is a rake dryer or a cone dryer.
6. The method as claimed in claim 1, wherein the heating temperature is 140-160 ℃, the induced draft frequency of nitrogen purge is 10-50Hz, and the boiling time is 1-8 hr.
7. The process for preparing a high K low residual monomer polymer powder of claim 6 wherein the apparatus used for the process is a boiling fluidized bed.
8. A high K low residual monomer polymer powder obtained by the process according to any one of claims 1 to 7.
9. The high K low residual monomer polymer powder of claim 8, wherein the polymer powder has a residual monomer content of less than 10ppm and an appearance of a yellowish to milky white powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011185195.3A CN112225835A (en) | 2020-10-30 | 2020-10-30 | high-K low-residue monomer polymer powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011185195.3A CN112225835A (en) | 2020-10-30 | 2020-10-30 | high-K low-residue monomer polymer powder and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112225835A true CN112225835A (en) | 2021-01-15 |
Family
ID=74122902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011185195.3A Pending CN112225835A (en) | 2020-10-30 | 2020-10-30 | high-K low-residue monomer polymer powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112225835A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003137923A (en) * | 2001-11-01 | 2003-05-14 | Gantsu Kasei Kk | Method for drying polymer powder |
| CN101326200A (en) * | 2005-12-20 | 2008-12-17 | 诺瓦提斯公司 | Process for removing residual volatile monomers from a polymer in powder form |
| CN101492512A (en) * | 2009-02-07 | 2009-07-29 | 厦门大学 | Method for removing residual monomer from ethenyl pyrrolidone polymer |
| CN101633706A (en) * | 2009-08-20 | 2010-01-27 | 华南理工大学 | N-vinylpyrrolidinone polymer solution purification method |
| CN106674388A (en) * | 2015-11-11 | 2017-05-17 | 上海其福青材料科技有限公司 | Method for reducing N-vinyl pyrrolidone in polyvinylpyrrolidone |
| CN109021260A (en) * | 2018-07-28 | 2018-12-18 | 博爱新开源医疗科技集团股份有限公司 | A kind of drying means and polymer powder of high-k polymer solution |
| CN109851696A (en) * | 2019-01-14 | 2019-06-07 | 英德茂丰药业有限公司 | A method of reducing tertiary-amino-containing (methyl) acrylate copolymer residual monomer and solvent |
-
2020
- 2020-10-30 CN CN202011185195.3A patent/CN112225835A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003137923A (en) * | 2001-11-01 | 2003-05-14 | Gantsu Kasei Kk | Method for drying polymer powder |
| CN101326200A (en) * | 2005-12-20 | 2008-12-17 | 诺瓦提斯公司 | Process for removing residual volatile monomers from a polymer in powder form |
| CN101492512A (en) * | 2009-02-07 | 2009-07-29 | 厦门大学 | Method for removing residual monomer from ethenyl pyrrolidone polymer |
| CN101633706A (en) * | 2009-08-20 | 2010-01-27 | 华南理工大学 | N-vinylpyrrolidinone polymer solution purification method |
| CN106674388A (en) * | 2015-11-11 | 2017-05-17 | 上海其福青材料科技有限公司 | Method for reducing N-vinyl pyrrolidone in polyvinylpyrrolidone |
| CN109021260A (en) * | 2018-07-28 | 2018-12-18 | 博爱新开源医疗科技集团股份有限公司 | A kind of drying means and polymer powder of high-k polymer solution |
| CN109851696A (en) * | 2019-01-14 | 2019-06-07 | 英德茂丰药业有限公司 | A method of reducing tertiary-amino-containing (methyl) acrylate copolymer residual monomer and solvent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11090718B2 (en) | Method based on fluidizing for modifying and preparing low-cost titanium powders for 3D printing | |
| JP5161730B2 (en) | Polymer processing | |
| US2592763A (en) | Chlorinated uncompacted polyethylene | |
| Cao et al. | Synthesis of cross-linked poly (4-vinylpyridine) and its copolymer microgels using supercritical carbon dioxide: Application in the adsorption of copper (II) | |
| CN1400980A (en) | Ethylene high pressure polymerization while preventing undesired polymer deposits | |
| CN112225835A (en) | high-K low-residue monomer polymer powder and preparation method thereof | |
| CN105838000B (en) | A kind of preparation method of inner die PVDC resins | |
| US2993879A (en) | Process for the production of polyamides | |
| CN106750267A (en) | A kind of nanometer of resin of copolymer nylon 6/66 and preparation method thereof and its application in film packaging | |
| KR20180029027A (en) | Process for preparing poly(glycolide-co-lactide) copolymer microparticles | |
| CN113337105B (en) | Polymer powder and preparation method thereof | |
| CN101519465A (en) | Polymer treatment | |
| JPH02117904A (en) | Extraction | |
| CN106749908B (en) | The production method of low-residue single cross-linking polyethylene pyrrolidone | |
| EP3560995A1 (en) | Pbs resin composition and preparation method therefor | |
| CN113527548A (en) | Method for preparing high chlorinated polypropylene by aqueous phase suspension method | |
| CA1278639C (en) | Vinyl chloride monomer stripping process | |
| EP0735053A1 (en) | Removal of oligomers from substantially crystalline, alpha-olefin polymers | |
| CN100368442C (en) | N-vinyl amide polymer and production method thereof | |
| CN112940165B (en) | Preparation method of ethylene propylene rubber | |
| CN113336880A (en) | Method for removing VOC (volatile organic compounds) in polypropylene granules | |
| CN114456555A (en) | Low-VOC-content polycaprolactone resin and preparation method thereof | |
| CN1974923A (en) | Method for producing high polymer polyacrylamide adapted to paper-making black liquor processing | |
| CN114573744B (en) | Method for reducing residual styrene-acrylonitrile copolymer resin and application thereof | |
| CN117069880A (en) | Preparation method of crosslinked povidone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |