CN117362214A - Method for removing amine substances from N-vinyl pyrrolidone solution - Google Patents
Method for removing amine substances from N-vinyl pyrrolidone solution Download PDFInfo
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- nvp
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- vinyl pyrrolidone
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- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 150000001412 amines Chemical class 0.000 title claims abstract description 54
- 239000000126 substance Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 239000004793 Polystyrene Substances 0.000 claims abstract description 15
- 229920002223 polystyrene Polymers 0.000 claims abstract description 15
- 239000004005 microsphere Substances 0.000 claims abstract description 11
- 239000012043 crude product Substances 0.000 claims abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 32
- 239000000460 chlorine Substances 0.000 claims description 32
- 229910052801 chlorine Inorganic materials 0.000 claims description 32
- 238000004132 cross linking Methods 0.000 claims description 8
- SSDGMKHZMNTWLS-UHFFFAOYSA-N 1,3,5-trimethylpyrazol-4-amine Chemical compound CC1=NN(C)C(C)=C1N SSDGMKHZMNTWLS-UHFFFAOYSA-N 0.000 claims description 3
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical group CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 3
- QLUUXTUCKOZMEL-UHFFFAOYSA-N 2-ethyl-3,5-dimethylpyridine Chemical compound CCC1=NC=C(C)C=C1C QLUUXTUCKOZMEL-UHFFFAOYSA-N 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims 1
- 238000007265 chloromethylation reaction Methods 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000013118 MOF-74-type framework Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- LLLWMXQKXWIRDZ-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one Chemical compound C=CN1CCCC1=O.C=CN1CCCC1=O LLLWMXQKXWIRDZ-UHFFFAOYSA-N 0.000 description 1
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
Abstract
The invention discloses a method for removing amine substances from an N-vinyl pyrrolidone (NVP) solution. Firstly, under the condition that the temperature of the NVP crude product is kept at 60-75 ℃, a certain amount of chloromethylated polystyrene microspheres (chloride balls) are added into the NVP solution, and the chloride balls and amine substances in the NVP solution are fully reacted under stirring. After the operation is finished, the amine substances can be removed by filtering, and the qualified NVP product is obtained. The method is convenient to operate, green, pollution-free and energy-saving, and the content of residual amine substances can be reduced to below 30 ppm.
Description
Technical Field
The invention relates to the technical field of N-vinyl pyrrolidone production, in particular to a method for removing amine substances from an N-vinyl pyrrolidone solution.
Background
N-vinylpyrrolidone (N-vinyl pyrrolidone) is abbreviated as NVP and is an important organic synthetic raw material in the chemical industry. The organic solvent has good solubility as a polar organic solvent, can be completely mutually dissolved with water, has good stability, no corrosiveness and low volatilization. NVP was first produced as a thickener for artificial plasma during the second war period, after which german chemist Reppe first synthesized N-vinylpyrrolidone from acetylene in 1938, developing an industrial process route for acetylene synthesis of NVP. At present, two main synthesis methods of NVP are an acetylene method and a gamma-butyrolactone method, and the gamma-butyrolactone method has fewer industrial production due to higher cost, poor practical application effect and the like. Acetylene has been used in large scale industrial applications, and two of the most prominent production companies in the world today are the german BASF company and the american ISP company.
The most important application in NVP industry is to synthesize Polyvinylpyrrolidone (PVP) for short by monomer self-polymerization. When the NVP is produced and applied to PVP in the fields of food, medicine, cosmetics and the like, the purity of the NVP needs to be upgraded to a high purity level, the process is high in cost, expensive equipment is needed, and the process is time-consuming, and generally, a cooling crystallization method, a rectification method and the like are adopted. During purification by crystallization, NVP is cooled to below 14℃ to promote crystallization. As crystals form, they separate from the mother liquor. The process is repeated to achieve the desired level of purity. But since NVP is usually already very pure, great care must be taken to control the temperature to prevent the entire mass from solidifying rapidly or to prevent the NVP that has crystallized from melting back into the mother liquor. When the NVP is purified by the rectification method, the NVP is required to be distilled intermittently, but N-vinyl pyrrolidone is a heat-sensitive substance, the retention time of the material in a rectification tower is up to 30-40 hours, and a large amount of N-vinyl pyrrolidone is self-polymerized due to high temperature in the rectification process, so that the yield of the target product NVP is reduced, the production efficiency of enterprises is low, and the production cost of the enterprises is increased. Therefore, there is a need to find a method for separating and purifying NVP with better effect.
The chloromethylated Polystyrene (ChIoromethylated Polystyrene, CMPS) chloromethyl which is the product of the molecular chain of the linear Polystyrene (Polystyrene, PSt) with the para-position hydrogen atoms of benzene rings partially or completely replaced by chloromethyl has high chemical activity and can further generate various organic reactions and introduce various functional groups, so that the chloromethylated Polystyrene is a precursor of various functional polymer compounds, namely, the precursor is taken as a parent polymer, and the polymer compounds with various functions can be prepared through the macromolecular reactions. For example, a macromolecular initiator polymerized by using CMPS as an atom transfer radical can be used for synthesizing grafted, dendritic and hyperbranched star-shaped copolymers; the CMPS is used as a raw material to synthesize ion exchange resin, chelate resin and adsorption resin with special functional groups; the synthesizable catalyst support is useful for organic synthesis and combinatorial chemistry systems; can be used for preparing functional polymer microspheres for biomacromolecule immobilization, separation, purification, chromatographic stationary phase, and the like. Crosslinked chloromethylated polystyrene microspheres are also known as chloride spheres. Obviously, the chlorine ball has wide application prospect in a plurality of scientific fields.
Disclosure of Invention
In view of the above problems, the present invention relates to a method for removing amine substances from NVP, and more particularly, to a method for obtaining high-purity NVP by using chloromethylated polystyrene microspheres (chloride spheres) to react with amine substances in NVP to fix the same on the polystyrene microspheres, filtering the chloride spheres, and evaporating the solvent. The invention provides a method for removing amine substances in NVP, which is convenient to operate, green and pollution-free, and can obtain NVP products with the amine substances below 30 ppm.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for deaminating substances in an N-vinyl pyrrolidone (NVP) solution, comprising the steps of:
step a, adding chloromethylated polystyrene microspheres (chlorine balls) under the condition of keeping the contact temperature for a certain period, and starting a stirrer to rotate for 3-5 hours to enable the chlorine balls to fully react with amine substances;
b, filtering and collecting filtrate after stirring is completed, and obtaining an NVP product with the amine content below 30 ppm;
the amine substances are N-N-propyl maleimide (CAS 21746-40-7), 1,3, 5-trimethyl-4-aminopyrazole (CAS 28466-21-9), 2, 6-tetramethyl-4-piperidinol (CAS), 3, 5-dimethyl-2-ethylpyridine (CAS 2403-88-5) and 2-pyrrolidone (CAS 616-45-5);
the total content of amine substances in the NVP crude product is 0.5-2% (wt) of NVP;
the contact temperature of the NVP solution and the chloromethylated polystyrene microsphere is 60-75 ℃;
the chloromethyl polystyrene microsphere has 17-52 percent of chlorine content and 8-15 percent of crosslinking degree, and is sieved by a 300-400 mesh sieve;
the consumption of the chlorine ball is 2% (wt) -5% (wt) of the mass of the NVP crude product;
the method for removing the amine substances in the NVP is a method for removing the amine substances by filtration.
Wherein the chemical formula of chlorine ball for removing amine substances is as follows:
in the chemical formula, chlorine is chemically adsorbed into tertiary amine, and R1, R2 and R3 represent hydrocarbon groups connected with nitrogen atoms.
In the chemical formula, chlorine is chemically adsorbed to primary amine, and R1 represents a hydrocarbon group connected with a nitrogen atom.
In the chemical formula, chlorine is used for chemically adsorbing secondary amine, and R1 and R2 represent hydrocarbon groups connected with nitrogen atoms.
The invention has the beneficial effects that:
(1) Compared with the prior art, the invention has the following beneficial effects: (1) the operation is simple, and the production capacity is high; (2) low energy consumption and low cost; (3) The method is green and pollution-free, the content of amine substances can be reduced to below 30ppm, and the NVP product yield is maintained to be above 97%.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
Example 1:
50g of NVP, wherein the total content of amine substances is 1.25%, is added into a 1000ml round bottom flask; 2g of chlorine balls (chlorine content 17%, crosslinking degree 8%,400 mesh) are added, and the mass is 4% of the mass of NVP; rapidly stirring for 3h at 65 ℃; and filtering to remove chlorine balls after stirring is finished, and obtaining a liquid NVP product. The content of residual amine was 21ppm and the NVP yield was 98.8%.
Example 2:
50g of NVP, wherein the total content of amine substances is 0.8%, is added into a 1000ml round bottom flask; 2g of chlorine balls (chlorine content 17%, crosslinking degree 8%,400 mesh) are added, and the mass is 4% of the mass of NVP; rapidly stirring for 3h at 65 ℃; and filtering to remove chlorine balls after stirring is finished, and obtaining a liquid NVP product. The content of residual amine was 21ppm, and the NVP yield was 98.1%.
Example 3:
50g of NVP, wherein the total content of amine substances is 1.98%, is added into a 1000ml round bottom flask; 2.5g of chlorine balls (chlorine content 52%, crosslinking degree 15%,400 mesh) with mass 5% of NVP mass are added; rapidly stirring for 3h at 65 ℃; and filtering to remove chlorine balls after stirring is finished, and obtaining a liquid NVP product. The content of residual amine was 25ppm and the NVP yield was 97.8%.
Example 4:
50g of NVP, wherein the total content of amine substances is 1.54%, is added into a 1000ml round bottom flask; 1.5g of chlorine balls (chlorine content 20%, crosslinking degree 10%,400 mesh) is added, and the mass is 3% of the mass of NVP; rapidly stirring for 3h at 65 ℃; and filtering to remove chlorine balls after stirring is finished, and obtaining a liquid NVP product. The content of residual amine was 19ppm, and the NVP yield was 98.1%.
Example 5:
50g of NVP, wherein the total content of amine substances is 1.71%, is added into a 1000ml round bottom flask; 2.5g of chlorine balls (chlorine content 52%, crosslinking degree 17%,400 mesh) with mass 5% of NVP mass are added; rapidly stirring for 3h at 65 ℃; and filtering to remove chlorine balls after stirring is finished, and obtaining a liquid NVP product. The content of residual amine was 17ppm, and the NVP yield was 97.1%.
Example 6:
50g of NVP, wherein the total content of amine substances is 1.34%, is added into a 1000ml round bottom flask; 1.6g of chlorine balls (chlorine content 30%, crosslinking degree 11%,400 mesh) is added, and the mass is 3.2% of the mass of NVP; rapidly stirring for 4 hours at 70 ℃; and filtering to remove chlorine balls after stirring is finished, and obtaining a liquid NVP product. The content of residual amine substances was 23ppm, and the NVP yield was 98.8%.
Comparative example 1:
50g of NVP, wherein the total content of amine substances is 1.25%, is added into a 1000ml round bottom flask; 2.5g (400 mesh) of polyamide resin was added, the mass being 4% of the mass of NVP; rapidly stirring for 3h at 65 ℃; and filtering to remove the polyamide resin after stirring to obtain a liquid NVP product. The content of residual amine was 1100ppm and the NVP yield was 89.2%.
Comparative example 2:
50g of NVP, wherein the total content of amine substances is 1.98%, is added into a 1000ml round bottom flask; 2.5g of MOF-74 (Zn) (metal skeleton adsorbent, 400 mesh) was added, the mass was 5% of the mass of NVP; rapidly stirring for 3h at 65 ℃; after stirring, MOF-74 (Zn) was removed by filtration to obtain a liquid NVP product. The content of residual amine was 1500ppm and the NVP yield was 91.7%.
Comparative example 3:
50g of NVP, wherein the total content of amine substances is 1.54%, is placed in an environment of 10 ℃ for 5h to crystallize, the crystals are collected by filtration in the environment of 10 ℃, the filtrate is placed in the environment of 10 ℃ again to crystallize for 4 times, and the crystals crystallized for 4 times are collected to obtain the NVP product. The content of residual amine was 900ppm and the NVP yield was 81.7%.
Comparative example 4:
50g of NVP, wherein the total content of amine substances is 1.62%, is added into a 1000ml round bottom flask; 2g (400 mesh) of alumina powder was added, the mass being 4% of the mass of NVP; rapidly stirring for 3h at 65 ℃; after stirring, the alumina powder was removed by filtration to obtain a liquid NVP product. The content of residual amine was 2600ppm and the NVP yield was 89.2%.
Comparative example 5:
50g of NVP, wherein the total content of amine substances is 1.48%, is added into a 1000ml round bottom flask; adding 2g (400 meshes) of active carbon powder, wherein the mass of the active carbon powder is 4% of that of NVP; rapidly stirring for 3h at 65 ℃; and filtering to remove the active carbon powder after stirring to obtain a liquid NVP product. The content of residual amine was 1400ppm and the NVP yield was 89.2%.
In the above examples and comparative examples, the amine content was measured by GCMS (gas chromatography mass spectrometry) analysis and calculation of NVP products. The coconut shell activated carbon powder is produced by Xinghua charcoal science and technology Jiangsu Co., ltd; the polyamide adsorption resin is produced by Danbao resin Limited in Qingyuan county of Chuzhou of Anhui; alumina powder and metal organic framework material [ MOF-74 (Zn) ] are produced by Jiangsu Xianfeng nanomaterial technologies Co., ltd; the chlorine ball is produced by Jiangsu and new material forming Co.
The data of examples 1-5 and comparative examples 1-3 are shown in the following table.
In conclusion, the method can greatly reduce the content of amine substances in the NVP, so that the NVP reaches a high purity level, and the used chlorine ball has the advantages of chemical stability, green pollution, convenient recovery and no harm to the environment.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
1. A method for removing amine substances from an N-vinyl pyrrolidone solution, comprising the steps of:
step a, adding chloromethylation polystyrene microspheres under the condition of keeping the contact temperature constant, starting a stirrer to rotate for 3-5h, and enabling the chlorine spheres to fully react with amine substances;
and b, filtering and collecting filtrate after stirring is completed, and obtaining the NVP product with the amine content below 30 ppm.
2. The method for removing amine from an N-vinyl pyrrolidone solution according to claim 1, wherein the amine is N-propyl maleimide, 1,3, 5-trimethyl-4-aminopyrazole, 2, 6-tetramethyl-4-piperidinol, 3, 5-dimethyl-2-ethylpyridine, 2-pyrrolidone, or N-ethylpyrrolidone.
3. The method for removing amine substances from an N-vinyl pyrrolidone solution according to claim 1, wherein the total content of the amine substances is 0.5% -2% of the mass percentage of the NVP crude product.
4. A method for removing amines from an N-vinylpyrrolidone solution according to claim 1, wherein said contacting temperature is from 60 ℃ to 75 ℃.
5. The method for removing amine substances from an N-vinyl pyrrolidone solution according to claim 1, wherein the polystyrene microsphere has a chlorine content of 17% -52% and a crosslinking degree of 8% -15%, and is sieved through a 30-400 mesh sieve.
6. The method for removing amine substances from an N-vinyl pyrrolidone solution according to claim 1, wherein the chlorine balls are used in an amount of 2% -5% by mass of the crude NVP product.
7. A method for removing amines from an N-vinylpyrrolidone solution according to claim 1, wherein the polystyrene microspheres are separated from the NVP solution by filtration.
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| CN101633706A (en) * | 2009-08-20 | 2010-01-27 | 华南理工大学 | N-vinylpyrrolidinone polymer solution purification method |
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|---|---|---|---|---|
| CN101633706A (en) * | 2009-08-20 | 2010-01-27 | 华南理工大学 | N-vinylpyrrolidinone polymer solution purification method |
| CN107814867A (en) * | 2017-11-10 | 2018-03-20 | 湖南辰砾新材料有限公司 | A kind of PMMA fluorescent copolymers microballoon and preparation method thereof |
| CN114555659A (en) * | 2019-10-07 | 2022-05-27 | 法国加栢 | Nondegradable radiopaque embolic microspheres |
Non-Patent Citations (1)
| Title |
|---|
| SOYKAN, UGUR等: "A survey on surface morphology control of cross-linked poly(N-vinylpyrrolidone) polymer particle via inverse suspension polymerization", TURKISH JOURNAL OF CHEMISTRY, vol. 45, no. 5, 30 June 2021 (2021-06-30), pages 1505 - 1516 * |
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