CN116515025A - Crosslinked povidone and preparation method and application thereof - Google Patents
Crosslinked povidone and preparation method and application thereof Download PDFInfo
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- CN116515025A CN116515025A CN202310528857.XA CN202310528857A CN116515025A CN 116515025 A CN116515025 A CN 116515025A CN 202310528857 A CN202310528857 A CN 202310528857A CN 116515025 A CN116515025 A CN 116515025A
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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 99
- 229920000036 polyvinylpyrrolidone Polymers 0.000 title claims abstract description 47
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 title claims abstract description 47
- 229940069328 povidone Drugs 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000002904 solvent Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 24
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 45
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 claims description 44
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 40
- 229960000913 crospovidone Drugs 0.000 claims description 32
- 230000008030 elimination Effects 0.000 claims description 32
- 238000003379 elimination reaction Methods 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000004140 cleaning Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000004744 fabric Substances 0.000 claims description 22
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 11
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000010009 beating Methods 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000012465 retentate Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 19
- 239000002253 acid Substances 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 10
- 230000036571 hydration Effects 0.000 abstract description 8
- 238000006703 hydration reaction Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005554 pickling Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 35
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002791 soaking Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 6
- 241000482268 Zea mays subsp. mays Species 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 150000003857 carboxamides Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229960001300 metoprolol tartrate Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229940124531 pharmaceutical excipient Drugs 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WUBVEMGCQRSBBT-UHFFFAOYSA-N tert-butyl 4-(trifluoromethylsulfonyloxy)-3,6-dihydro-2h-pyridine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCC(OS(=O)(=O)C(F)(F)F)=CC1 WUBVEMGCQRSBBT-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F126/10—N-Vinyl-pyrrolidone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2339/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention relates to a crosslinked povidone, a preparation method and application thereof, wherein the raw materials for preparing the crosslinked povidone comprise 1-vinyl-2-pyrrolidone, ammonia water, urea, alkali metal hydroxide and a first solvent. The cross-linked povidone disclosed by the invention has the advantages of large particle size, quick water absorption, good hydration performance, no need of using a large amount of acid for pickling treatment, less waste, low process energy consumption, low cost, low pollution, environment friendliness, low impurity content of the formed cross-linked povidone and high yield.
Description
Technical Field
The invention relates to the technical field of crosslinked povidone, in particular to crosslinked povidone, and a preparation method and application thereof.
Background
The cross-linked povidone (PVPP) product is super absorbent resin and has strong water absorption and water retention capacity. The water absorption capacity of the water absorbing material can be several times or even tens times of the self weight, hydrogen bonds can be formed between the matrix and the absorbed water, the absorbed water can not run off even under a certain pressure, and the water absorbing material can be recycled. PVPP has excellent physiological safety, water absorbability, water insolubility, complexation property, etc.
The crosslinked povidone (PVPP) product forms a porous and granular nonionic product through a unique popcorn polymerization process, and has stronger interfacial activity. Popcorn polymerization is a special polymerization mode, the reaction mechanism of which is not clear, and the polymer obtained by the popcorn polymerization is highly crosslinked, but the crosslinking of the polymer is mainly formed by intertwining long molecular chains. At present, alkali metal hydroxide, purified water and 1-vinyl-2-pyrrolidone (NVP) are generally used for producing the crosslinked povidone through a popcorn polymerization method, but the method has the advantages of high impurity content and low yield due to side reaction in the process.
In the traditional PVPP preparation process, the controllable range of the particle size of PVPP is smaller and can be basically controlled within the range of less than 100 mu m, so that the application effect of PVPP serving as a clarifying agent and a stabilizing agent in the brewing and beverage industries is greatly limited, and the PVPP can be reused for a small number of times, so that the resource waste is caused; in addition, when the powder-free crosslinked povidone particles are used for tabletting, the particle size is too small, the compressibility is insufficient, and the production efficiency and the service life of equipment are seriously affected.
CN106883333a discloses a preparation method of large particle size cross-linked povidone, under the condition that the mass ratio of monomer NVP to water is 9:1, adding 3.0% alkali metal hydroxide, introducing nitrogen for protection, heating to 55 ℃ for initiating popcorn polymerization, and stirring at a speed of 60 revolutions per minute; when the temperature rises to 70 ℃, 0.5 to 5.0 percent of forming agent is added, and the stirring speed is reduced to 20 revolutions per minute; after the particles are molded, washing and drying are carried out, and finally, the crosslinked povidone with the particle size of 140-200 mu m is obtained; the molding agent is generally at least one of tert-butyl hydroperoxide, benzoyl peroxide, di-tert-butyl peroxide, azobisisobutyronitrile and tert-butyl peroxybenzoate. According to the technical scheme, the tertiary butyl hydroperoxide, benzoyl peroxide, di-tertiary butyl peroxide, azodiisobutyronitrile and tertbutyl perbenzoate added after polymerization are all common NVP initiators, are actually auxiliary agents for eliminating residues, and trigger unreacted NVP monomers in a crosslinking polymerization stage to react to generate PVP (polyvinyl pyrrolidone), and are actually the effect of a surfactant played by PVP, so that the surface tension of particles during forming is changed, and the purpose of PVPP preparation with large particle size is achieved. Whether or not this solution allows the preparation of PVPP of so-called large particle size, it is evident that the process disclosed does not guarantee yields, since PVP produced by the initiation of the reaction of unreacted NVP monomer during the cross-linking polymerization stage is water-soluble and is lost by dissolution in water during the subsequent washing treatment stage.
CN111378060a discloses a method for producing crosslinked povidone based on a popcorn polymerization mechanism of in-situ generation crosslinking agent, which belongs to the technical field of pharmaceutical excipients. The method comprises the following steps: 1) Polymerization reaction; 2) Soaking; 3) Centrifugal dehydration; 4) Drying to obtain the final product. However, the disclosed process requires a large amount of glacial acetic acid and peracetic acid to be treated by a soaking process, and the process is long in time consumption, and only the soaking process needs at least 20-60 hours and is relatively complex to treat; a large amount of acid soaking and cleaning are used, a large amount of industrial sewage of strong acid and strong alkali is generated, the process is high in pollution, high in energy consumption and low in economic benefit.
In view of the above, it is important to develop a crospovidone and a method for preparing the same, which overcome the above-mentioned drawbacks.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the crosslinked povidone, the preparation method and the application thereof, wherein the particle size of the crosslinked povidone is large, the water absorption is rapid, the hydration performance is good, the preparation method does not need to consume a large amount of acid for pickling treatment, the waste is less, the process energy consumption is low, the cost is low, the pollution is low, the environment is protected, the impurity content of the formed crosslinked povidone is low, and the yield is high.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a crospovidone, the raw materials for preparing the crospovidone include 1-vinyl-2-pyrrolidone, ammonia, urea, alkali metal hydroxide and a first solvent.
In the invention, urea is used as a catalyst and a modifier, ammonia water is used as a structural modifier and a crystal nucleus protective agent, and the formed crosslinked povidone has large particle size, excellent water absorption capacity, excellent disintegration performance and excellent hydration performance, and has excellent comprehensive performance.
Preferably, the mass ratio of the 1-vinyl-2-pyrrolidone, ammonia water, urea, alkali metal hydroxide and the first solvent is 100 (0.1-5.0): (1.0-5.0): (0.5-1.25): (30-40); wherein 0.1-5.0 can be 0.2, 0.5, 0.8, 1.0, 2.0, 3.0, 4.0, 5.0, etc.; 1.0 to 5.0 may be 1.0, 2.0, 3.0, 4.0, 5.0, etc.; 0.5-1.25 may be 0.6, 0.8, 1, 1.2, etc.; 30-40 may be 32, 34, 36, 38, etc.
Preferably, the ammonia is present in a mass concentration of 20.0% -30.0%, such as 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, etc.
Preferably, the alkali metal hydroxide comprises any one or a combination of at least two of lithium hydroxide, sodium hydroxide or potassium hydroxide, wherein typical but non-limiting combinations include: a combination of lithium hydroxide and sodium hydroxide, a combination of sodium hydroxide and potassium hydroxide, a combination of lithium hydroxide, sodium hydroxide and potassium hydroxide, and the like.
Preferably, the first solvent comprises water.
Preferably, the crosslinked povidone has a particle size of 100 to 500 μm (e.g., 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, etc.) at a ratio of 90% or more, e.g., 92%, 94%, 96%, 98%, etc., and more preferably 90.03% to 93.26%.
In a second aspect, the present invention provides a method for preparing the crospovidone according to the first aspect, the method comprising the steps of:
mixing 1-vinyl-2-pyrrolidone, ammonia water, urea, alkali metal hydroxide and a first solvent, and then carrying out polymerization reaction, pulping, cleaning and residue elimination treatment to obtain the crosslinked povidone.
In the invention, urea plays a double role of a catalyst and a modifier in preparation: in a first aspect, urea is thermally decomposed at high temperature in an alkaline polymerization solution environment to produce ammonia, and vinyl groups capable of raising NVP in the reactionPolymerization activity, accelerating the generation of a cross-linking agent, accelerating the chain-initiated cross-linking polymerization reaction, and improving the reaction rate; in the second aspect, the urea molecule is a small molecule with a carboxamide structure, and the reaction in the chain termination stage is modified during the polymerization reaction to form RH 2 -O-C(NH 2 ) 2 The end-capping structure of (2) can improve the water absorption rate and the adsorption performance. The residue elimination treatment is used for decomposing or reacting residual monomer impurities in a polymer system and improving the pH value of a product; the ammonia plays a role in the preparation: mainly plays a role in preventing or reducing the urea hydrolysis reaction in the high-temperature stage of polymerization, and indirectly plays a role in a structural modifier and a crystal nucleus protective agent; the preparation process of the invention adds 30-40% of water based on the monomer amount, compared with the prior art, the addition amount of the water is obviously higher, and mainly provides a water system environment for the agglomeration and growth of modified crosslinked PVPP crystal nucleus obtained by polymerization reaction, thereby improving the particle size of the crosslinked PVPP particles of the product. The preparation method disclosed by the invention does not need to consume a large amount of acid for acid washing treatment, and is low in waste production, low in process energy consumption, low in cost, low in pollution, environment-friendly and low in impurity content of the formed crosslinked povidone.
Preferably, the polymerization reaction includes a first temperature-increasing reaction, a second temperature-increasing reaction, and a temperature-decreasing reaction.
Preferably, the first temperature-rising reaction is carried out to 35-50 ℃, for example 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, etc.
Preferably, after the first temperature rise, oxygen is removed.
Preferably, the means for scavenging oxygen comprises passing an inert gas and evacuating at least once (e.g., twice, three times, four times, etc.).
Preferably, after the last inert gas introduction and vacuum pumping, inert gas is introduced into the system, and the pressure of the system is kept at 0-0.1MPa, for example, 0.02MPa, 0.04MPa, 0.06MPa, 0.08MPa and the like.
Illustratively, the inert gas includes nitrogen.
Illustratively, the oxygen scavenging specifically comprises: stirring is started, and vacuum pumping is carried out until the pressure reaches-0.06 to-0.1 MPa (for example, -0.07MPa, -0.08MPa, -0.09MPa and the like), and the stirring is maintained for 5-15min (for example, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min and the like); then nitrogen is introduced to pressurize to 0.2-0.3 MPa (for example, 0.22MPa, 0.24MPa, 0.26MPa, 0.28MPa, etc.), and the pressure is maintained for 5-15min (for example, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, etc.); after continuing the replacement for at least 1 time (e.g., two, three, four, etc.), nitrogen is introduced and pressurized to 0 to 0.1MPa (e.g., 0.02MPa, 0.04MPa, 0.06MPa, 0.08MPa, etc.).
Preferably, the system is subjected to a second warming at 800-1200 revolutions per minute (e.g., 900 revolutions per minute, 1000 revolutions per minute, 1100 revolutions per minute, etc.).
Preferably, the second temperature is raised to 120-130 ℃, e.g., 122 ℃, 124 ℃, 126 ℃, 128 ℃, etc.
Preferably, after the second temperature rise, the reaction is incubated.
Preferably, the incubation time is 30-90min, such as 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min, etc.
Preferably, after the incubation reaction, the temperature is lowered to 80-110 ℃ (e.g. 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃ etc.), and in the lowering, the temperature rises again, and the polymerization reaction starts.
In the invention, the temperature change is observed by natural cooling, and the temperature rises again in the natural cooling process, so that the cross-linking polymerization reaction is started.
Preferably, the polymerization reaction temperature is 80-120 ℃, for example 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, etc.
Preferably, the polymerization reaction pressure is 0.1 to 0.6MPa, for example 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, etc.
Preferably, the temperature of the material after the polymerization reaction is adjusted to 80-100 ℃ (e.g., 85 ℃, 90 ℃, 95 ℃, etc.), a second solvent is added to the system for mixing, and stirring and beating are performed.
Preferably, the second solvent used for beating is 300-500 parts by mass, for example 320 parts, 340 parts, 360 parts, 380 parts, 400 parts, 420 parts, 440 parts, 460 parts, 480 parts, etc., based on 100 parts by mass of the total of the 1-vinyl-2-pyrrolidone.
Preferably, the second solvent comprises water.
Preferably, the stirring beating speed is 50-150 rpm, for example 60 rpm, 80 rpm, 100 rpm, 120 rpm, 140 rpm, etc.
Preferably, the stirring and beating time is 15-30min, such as 16min, 18min, 20min, 22min, 24min, 26min, 28min, etc.
Preferably, the washing is performed in a washing filter provided with 400-500 mesh (e.g., 420 mesh, 440 mesh, 460 mesh, 480 mesh, etc.) filter cloth.
Preferably, the washing comprises vacuuming the pulped material to remove the first solvent and the second solvent.
Preferably, the cleaning further comprises mixing the material retained by the filter cloth with a third solvent and evacuating, the operation being performed at least once (e.g. two, three, four, five, etc.).
Preferably, the means for mixing the material retained by the filter cloth with the third solvent comprises stirring.
Preferably, the third solvent is used in the mixing in an amount of 300 to 500 parts, for example, 320 parts, 340 parts, 360 parts, 380 parts, 400 parts, 420 parts, 440 parts, 460 parts, 480 parts, etc., based on 100 parts by total mass of the 1-vinyl-2-pyrrolidone.
Preferably, the third solvent comprises water having a temperature of 60-80 ℃, for example 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, etc.
Preferably, the stirring speed is 50-150 rpm, such as 60 rpm, 80 rpm, 100 rpm, 120 rpm, 140 rpm, etc.
Preferably, the stirring time is 30-60min, such as 35min, 40min, 45min, 50min, 55min, etc.
Preferably, the materials trapped by the filter cloth after cleaning are subjected to residue elimination treatment.
Preferably, the residue elimination treatment comprises the steps of mixing the materials trapped by the cleaned filter cloth with a fourth solvent, preserving heat, and adding residue elimination auxiliary agent for treatment.
Preferably, the disabling aid comprises any one or a combination of at least two of hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, or t-butyl peracetate, wherein typical but non-limiting combinations include: combinations of hydrogen peroxide and peracetic acid, combinations of peracetic acid, t-butyl hydroperoxide and t-butyl peracetate, combinations of hydrogen peroxide, peracetic acid, t-butyl hydroperoxide and t-butyl peracetate, and the like.
Preferably, the fourth solvent is used in the residue elimination treatment in an amount of 300 to 500 parts, for example, 320 parts, 340 parts, 360 parts, 380 parts, 400 parts, 420 parts, 440 parts, 460 parts, 480 parts, etc.
Preferably, the fourth solvent comprises water.
Preferably, the temperature of the incubation is 60-80 ℃, e.g., 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, etc.
Preferably, the time of the disabling treatment is 6-12 hours, for example 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, etc.
Preferably, the residual amount of the residue elimination treatment to the system 1-vinyl-2-pyrrolidone is 10ppm or less, for example, 9ppm, 8ppm, 7ppm, 6ppm, 5ppm, 4ppm, etc.
Preferably, the method further comprises solvent removal and drying after the residue elimination treatment.
Preferably, the means for removing the solvent comprises centrifugation.
Preferably, the mass content of the water-soluble in the solvent-depleted to centrifuge retentate feed is less than or equal to 1.0%, such as 0.8%, 0.6%, 0.4%, 0.2%, etc.
As a preferable technical scheme, the preparation method comprises the following steps:
(1) Mixing an alkali metal hydroxide with a first solvent to form a hydroxide solution;
(2) Mixing 1-vinyl-2-pyrrolidone, ammonia water, urea and alkali metal hydroxide solution, heating to 35-50 ℃ for the first time, introducing inert gas and vacuumizing at least once, introducing inert gas into the system, keeping the pressure of the system at 0-0.1MPa, and finishing deoxidization;
(3) Heating at 800-1200 rpm, keeping the temperature at 120-130 ℃, reacting for 30-90min, cooling to 80-110 ℃, rising the temperature again during cooling, starting the polymerization reaction, controlling the temperature to 80-120 ℃, and controlling the system pressure to 0.1-0.6MPa until the polymerization reaction is finished;
(4) When the temperature of the system is regulated to 80-100 ℃, mixing the material after the polymerization reaction with a second solvent, stirring and pulping for 15-30min at 50-150 rpm;
(5) Transferring the pulped material to a cleaning filter with 400-500 meshes of filter cloth, and vacuumizing to remove the first solvent, the second solvent and soluble matters in the solvent; stirring and mixing the materials trapped by the filter cloth and the third solvent for 30-60min at 50-150 rpm, and vacuumizing, wherein the operation is performed at least once to finish cleaning;
(6) Mixing the material trapped by the filter cloth with a fourth solvent, preserving heat at 60-80 ℃ and carrying out residue elimination treatment for 6-12h until the residual amount of the 1-vinyl-2-pyrrolidone in the system is less than or equal to 10ppm, thereby completing the residue elimination treatment;
(7) And removing solvent from the material subjected to the residue elimination treatment and drying to obtain the crosslinked povidone.
In a third aspect, the present invention provides a dust-free crosslinked povidone comprising the crosslinked povidone of the first aspect.
In a fourth aspect, the present invention provides a water absorbent resin comprising the crospovidone of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The particle size of the crosslinked povidone is between 100 and 500 mu m, and the particle size accounts for 90.03 to 93.26 percent; after 60min of water absorption, the water absorption rate is above 810%, the disintegration time is within 21.53min, and the hydration capacity is above 8.1 by taking the crosslinked povidone as a disintegrating agent
(2) The physical and chemical indexes of the crosslinked povidone can meet the highest standard requirements of CP, EP, USP, BP and JP, the impurity A (NVP) is less than or equal to 10ppm, the soluble matters in water are less than or equal to 1.5%, and the peroxide is less than or equal to 400ppm.
(3) The preparation method disclosed by the invention does not need to consume a large amount of acid for acid washing treatment, and is low in waste production, low in process energy consumption, low in cost, low in pollution, environment-friendly, low in impurity content of the formed crosslinked povidone, and high in yield which is more than 95%.
Drawings
FIG. 1 is a graph of the water absorption rate of crospovidone described in example 3 and comparative examples 1-4.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a crospovidone, which is obtained by a preparation method comprising the following steps:
(1) Mixing 1kg of alkali metal hydroxide with 30kg of purified water to form a hydroxide solution;
(2) Mixing 100kg of 1-vinyl-2-pyrrolidone, 0.5kg of ammonia water (the mass concentration is 20.0%), 0.5kg of urea and an alkali metal hydroxide solution;
heating to 35 ℃, and introducing nitrogen to replace deoxidization. Stirring, vacuumizing to-0.06 MPa, and maintaining for 10min; then nitrogen is introduced to pressurize to 0.2MPa, and the pressure is maintained for 10min; after the operation and the replacement are continued for 2 times, nitrogen is introduced to pressurize to 0MPa, and the deoxidation is completed;
(3) Carrying out at 800 rpm, heating to 125 ℃, then carrying out heat preservation reaction for 30min, cooling to 80-110 ℃, starting the polymerization reaction when the temperature rises in the cooling process, controlling the temperature to fluctuate between 80-120 ℃, and controlling the system pressure to be not more than 0.6MPa until the polymerization reaction is finished;
(4) After cooling to 90 ℃ by cooling water, 300kg of water is added into the reaction kettle, and stirring and pulping are carried out for 30min at 50 revolutions per minute;
(5) And transferring the pulped material into a cleaning filter with 400-mesh filter cloth, starting stirring, vacuumizing, removing soluble substances dissolved in water and water together, and collecting in a polymerization kettle. Adding 60 ℃ hot water which is equal to that in the step (4) into the cleaning filter again, stirring for 30min at 50 r/min, and vacuumizing again to remove water and soluble matters in the solvent, thereby completing cleaning;
(6) Adding water equivalent to the water in the step (4) into the cleaning filter again, heating to 60 ℃ and preserving heat within the temperature range, adding hydrogen peroxide to perform residue elimination treatment for 12 hours until the residual amount of the 1-vinyl-2-pyrrolidone in the system is less than or equal to 10ppm, and finishing the residue elimination treatment;
(7) And (3) centrifugally dehydrating the material subjected to the residue elimination treatment, sampling and detecting 1.1% of water-soluble substances, and drying to obtain 98.5kg of crosslinked povidone with a yield of 98.5%.
Example 2
The embodiment provides a crospovidone, which is obtained by a preparation method comprising the following steps:
(1) Mixing 0.5kg of alkali metal hydroxide with 35kg of purified water to form a hydroxide solution;
(2) Mixing 100kg of 1-vinyl-2-pyrrolidone, 0.1kg of ammonia water (mass concentration is 25.0%), 0.125kg of urea and an alkali metal hydroxide solution;
heating to 45 ℃, and introducing nitrogen to replace deoxidization. Stirring, vacuumizing to-0.08 MPa, and maintaining for 10min; then nitrogen is introduced to pressurize to 0.25MPa, and the pressure is maintained for 10min; after the operation and replacement are continued for 3 times, nitrogen is introduced to pressurize to 0.05MPa, and the deoxidation is completed;
(3) Carrying out at 1200 rpm, after the temperature reaches 120 ℃, carrying out heat preservation reaction for 50min, cooling to 95 ℃, wherein when the temperature rises, the polymerization reaction starts, controlling the temperature to fluctuate between 80-120 ℃, and controlling the system pressure to be not more than 0.35MPa until the polymerization reaction ends;
(4) After cooling water to 95 ℃, 400kg of water is added into the reaction kettle, and stirring and pulping are carried out for 15min at 150 rpm;
(5) And transferring the pulped material into a cleaning filter with 400-mesh filter cloth, starting stirring, vacuumizing to remove water-soluble substances and water together, and collecting in a polymerization kettle. Adding 60 ℃ hot water which is equal to that in the step (4) into the cleaning filter again, stirring for 40min at 150 rpm, and vacuumizing again to remove water and water soluble substances to finish cleaning;
(6) Adding water equivalent to the water in the step (4) into the cleaning filter again, heating to 70 ℃, keeping the temperature within the temperature range, adding hydrogen peroxide and peracetic acid for residue elimination treatment for 10 hours until the residual amount of the 1-vinyl-2-pyrrolidone in the system is less than or equal to 10ppm, and finishing the residue elimination treatment;
(7) And (3) centrifugally dehydrating the material subjected to the residue elimination treatment, sampling and detecting 0.5% of soluble matters in water, and drying to obtain 96.7kg of crosslinked povidone with a yield of 96.7%.
Example 3
The embodiment provides a crospovidone, which is obtained by a preparation method comprising the following steps:
(1) 100kg of 1-vinyl-2-pyrrolidone, 1.0kg of ammonia water (mass concentration: 30.0%), 1.0kg of urea, 1.25kg of alkali metal hydroxide and 40kg of purified water were mixed;
(2) Heating to 50 ℃, and introducing nitrogen to replace deoxidization. Stirring, vacuumizing to-0.1 MPa, and maintaining for 10min; then nitrogen is introduced to pressurize to 0.3MPa, and the pressure is maintained for 10min; after the operation and the replacement are continued for 4 times, nitrogen is introduced to pressurize to 0.1MPa, and the deoxidation is completed;
(3) Carrying out at 1000 rpm, after the temperature reaches 130 ℃, carrying out heat preservation reaction for 90min, naturally cooling to 110 ℃, when the temperature rises to the temperature, starting the polymerization reaction, controlling the temperature to fluctuate between 80-120 ℃, controlling the system pressure not to exceed 0.6MPa, and ending the polymerization reaction;
(4) When the temperature of the system is regulated to 100 ℃, 500kg of water is added into the reaction kettle, and stirring and pulping are carried out for 20min at 100 revolutions per minute;
(5) And transferring the pulped material into a cleaning filter with 400-mesh filter cloth, starting stirring, vacuumizing to remove water-soluble substances and water together, and collecting in a polymerization kettle. Adding 80 ℃ hot water which is equal to the hot water in the step (4) into the cleaning filter again, stirring for 60min, and vacuumizing again to remove water and water soluble substances so as to finish cleaning;
(6) Adding water equivalent to the water in the step (4) into the cleaning filter again, heating to 70 ℃, keeping the temperature within the temperature range, adding tertiary butyl hydroperoxide and peracetic acid to perform residue elimination treatment for 12 hours until the residual amount of the 1-vinyl-2-pyrrolidone in the system is less than or equal to 10ppm, and finishing the residue elimination treatment;
(7) And (3) centrifugally dehydrating the material subjected to the residue elimination treatment, sampling and detecting 0.3% of soluble matters in water, and drying to obtain 98.3kg of crosslinked povidone, wherein the yield is 98.3%.
Examples 4 to 5
Examples 4 to 5 differ from example 3 in that the urea addition amounts were 0.1kg (example 4) and 1.1kg (example 5), respectively, and the remainder were the same as example 3. 95.5kg of the crospovidone prepared in the example 4 is obtained, and the yield is 95.5%; 96.2kg of the crospovidone is obtained in example 5, and the yield is 96.2%.
Examples 6 to 7
Examples 6 to 7 differ from example 3 in the amount of sodium hydroxide added, which was 0.4kg (example 6) and 1.3kg (example 7), respectively, and the remainder was the same as example 3. 97.5kg of the crospovidone prepared in the example 6 is obtained, and the yield is 97.5%; 96.2kg of the crospovidone is obtained in example 7, and the yield is 96.2%.
Examples 8 to 9
Examples 8 to 9 were different from example 3 in the amounts of ammonia added, respectively, of 0.05kg (example 8) and 1.1kg (example 9), and the remainder were the same as example 3. 95.5kg of the crospovidone prepared in the example 8 is obtained, and the yield is 95.5%; example 9 gave 99.4kg of crospovidone in 96.4% yield.
Comparative example 1
The present comparative example provides a crospovidone obtained by a preparation method comprising the steps of:
(1) 100kg of the monomer NVP in example 3, 1.25kg of sodium hydroxide and 20kg of purified water are added into a reaction kettle;
(2) Heating to 50 ℃, and introducing nitrogen to replace deoxidization. Stirring, vacuumizing to-0.1 MPa, and maintaining for 10min; then nitrogen is introduced to pressurize to 0.3MPa, and the pressure is maintained for 10min; after the operation and the replacement are continued for 2 times, nitrogen is introduced to pressurize to 0.3MPa, and the deoxidation is completed;
(3) Continuously heating to 130 ℃ while keeping the stirring state, preserving heat and reacting for 90min, and naturally cooling to 110 ℃;
observing and changing the temperature, and rising the temperature again in the natural cooling process to show that the cross-linking polymerization reaction starts; and after the temperature tends to be stable and does not continue to rise, the polymerization is finished.
(4) After cooling to 100 ℃, 500kg of water is added into the reaction kettle, and the mixture is fully stirred and pulped for 6 hours.
(5) And transferring the pulped material to a cleaning filter with 400-mesh filter cloth, starting stirring, vacuumizing, and removing the material penetrating through the 400-mesh filter cloth and water into a polymerization kettle together for collection. And (3) adding 80 ℃ hot water which is equal to that in the step (4) into the cleaning filter again, stirring for 60min, and vacuumizing again to remove water and materials, thereby completing cleaning.
(6) And (3) adding water which is equal to that in the step (4) into the cleaning filter again, heating to 70 ℃, keeping the temperature in the temperature range, and adding tert-butyl hydroperoxide and peracetic acid to perform residue elimination treatment for 12 hours. And vacuumizing to remove the material passing through the 400-mesh filter cloth and water into a polymerization kettle together for collection.
(7) Transferring the materials in the cleaning filter to a centrifuge, centrifugally dewatering, and drying to obtain 62kg PVPP XL specification coarse powder with the particle size of more than or equal to 40 mu m.
Comparative example 2
This comparative example was different from example 3 in that ammonia was not added, and the rest was the same as example 3.
Comparative example 3
This comparative example provides a crospovidone obtained by the preparation method disclosed in CN111378060a, comprising the steps of:
1. polymerization reaction:
1.1 feeding: NVP is as follows: 100kg of sodium hydroxide solution (sodium hydroxide: 1kg, process water: 15 kg) was weighed and put into a polymerization vessel, and stirring was started.
1.2 nitrogen substitution: and (3) after three times of nitrogen filling and vacuum, maintaining the pressure of the polymerization kettle to be 0.2MPa.
1.3 polymerization: heating the polymerization kettle to 140 ℃, and keeping the temperature for a period of time under the pressure of 0.55 MPa: 190 minutes, then cooling to the initiation temperature: polymerization was started at 115℃and the polymerization temperature was: the polymerization was completed after maintaining at 150℃for 1 hour.
1.4, cooling and discharging: opening cooling water to cool for 1 hour, and discharging the cooled cooling water into a soaking kettle containing 250kg of process water; the materials remained on the inner wall of the polymerization kettle are washed by 125kg of process water under stirring and are pumped into a soaking kettle.
2. Soaking (pH adjusting)
2.1 acid pickling: starting the soaking kettle to stir, heating to 60 ℃, adding 2kg of glacial acetic acid, stirring for two hours, stopping stirring, and soaking for 18 hours.
2.2, adjusting pH value and soaking: stirring is started, 6.25kg of peroxyacetic acid is added, the pH value is regulated to be below 4.2, stirring is closed after two hours, and standing and soaking are carried out for 18 hours.
2.3 adjusting pH: stirring was started and sodium hydroxide solution was added to bring the pH to 6.5.
3. Centrifugal dewatering
3.1 first centrifugal dehydration: and (3) adding the soaked materials into a medium-speed centrifugal machine, when the thickness of the material layer is about 10cm, starting the centrifugal machine to dehydrate at a high speed, dehydrating for 30 minutes, and discharging the materials into a storage tank.
3.2, after mixing, washing with water for the first time: 1400kg of process water is added into the mixing kettle A, the temperature is raised to 60 ℃, and the two kettles are respectively pumped into the mixing kettle A from the storage tank and are circularly stirred for 15 minutes.
3.3 second centrifugal dehydration: and (5) centrifugally dewatering the mixture.
3.4, after mixing, washing with water for the second time: 1400kg of process water was added to the mixing tank B, heated to 60℃and stirred for 15 minutes.
3.5 third centrifugal dehydration: and (5) centrifugally dewatering the mixture.
4. Flash drying: flash drying the dehydrated material by a flash dryer, wherein the parameters are as follows:
the air inlet temperature is 215 ℃, the air outlet temperature is 115 ℃, and the material layer temperature is 115 DEG C
The frequency of the blower with the negative pressure in the tower above-9 Pa and the frequency of the induced draft fan with the frequency of 48Hz and 48Hz
Stirring frequency 20Hz charging frequency 12Hz hot blast stove frequency 20Hz
When drying is carried out, the water content of the first barrel is detected, and the detection result is less than 3.5%.
5. And (3) screening: crushing and sieving the dried material in a clean area to obtain the product with the particle size of more than 40 mu m.
Comparative example 4
This comparative example provides a commercially available product, crospovidone available from basf.
Performance testing
The following tests were carried out on the crospovidone described in examples 1 to 9 and comparative examples 1 to 4:
(1) Water absorption performance: taking 5g of sample, adding the sample into a 200mL beaker, adding 100g of water, standing, respectively filtering and weighing 10min, 20min, 30min, 40min, 50min and 60min after adding water to obtain water absorption amounts of different times, calculating the water absorption rates of the sample in different time periods, and plotting the water absorption rates with time to obtain a water absorption rate curve.
(2) Disintegration time: the cross-linked povidone is taken as a disintegrating agent, the powder is directly tabletted to prepare the metoprolol tartrate tablets with the same specification, and the disintegration time of the tablets is compared according to the three disintegration time check method of the Chinese pharmacopoeia 2020 edition.
(3) Hydration ability: adding 2.0g of the crosslinked povidone into a 100mL centrifuge tube, adding 40mL of deionized water, and shaking vigorously until a suspension is obtained; after shaking again for 10 minutes, centrifugation was performed in a centrifuge for 15 minutes, and then the supernatant was decanted and the amount of residue was weighed. Hydration capacity = mass of residue/initial mass of sample.
(4) Impurity content: the test was carried out according to the method of the Chinese pharmacopoeia (2020 edition of four-part crospovidone).
The test results are summarized in table 1, table 2 and fig. 1.
TABLE 1
Analysis of Table 1 shows that the particle size of the crospovidone of the present invention is between 100 and 500 μm and the ratio is between 90.03 and 93.26%, which is significantly larger than that of comparative examples 1 to 4; after water absorption for 60min, the water absorption rate is above 810%, the cross-linked povidone is used as a disintegrating agent, the disintegration time is within 21.53min, and the hydration capacity is above 8.1; the crospovidone disclosed by the invention has excellent water absorption capacity, disintegration performance and hydration performance.
Analysis of the water absorption rates of the crospovidone described in comparative examples 1-4 and example 3, the water absorption performance of comparative examples 1-4 was inferior to that of example 3, and the comparison graph is shown in fig. 1, demonstrating that the performance of the crospovidone described in the present invention was better than that of the conventional method of the prior art or the commercially available product having excellent performance.
Analysis of examples 4-9 and example 3 shows that examples 4-9 perform less than example 3, demonstrating that the combination of monomer, ammonia, urea and alkali metal hydroxide in specific proportions results in a crosslinked povidone having better performance.
TABLE 2
As can be seen from the analysis of the data in Table 2, the physicochemical indexes of the crospovidone disclosed by the invention can meet the highest standard requirements of CP, EP, USP, BP and JP, the impurity A (NVP) is less than or equal to 10ppm, the water soluble matters are less than or equal to 1.5%, and the peroxide is less than or equal to 400ppm. The preparation method disclosed by the invention does not need to consume a large amount of acid for acid washing treatment, and is low in waste production, low in process energy consumption, low in cost, low in pollution, environment-friendly, low in impurity content of the formed crosslinked povidone, and high in yield which is more than 95%.
Analysis of the crospovidone described in comparative examples 1-4 and example 3, the properties of comparative examples 1-4 were inferior to example 3, demonstrating that the crospovidone described herein performed better than the prior art conventional process or the prior art commercial products with superior properties.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The preparation method of the crospovidone is characterized in that the raw materials for preparing the crospovidone comprise 1-vinyl-2-pyrrolidone, ammonia water, urea, alkali metal hydroxide and a first solvent.
2. The crospovidone of claim 1, wherein the mass ratio of 1-vinyl-2-pyrrolidone, ammonia, urea, alkali metal hydroxide and first solvent is 100 (0.1-5.0): (1.0-5.0): (0.5-1.25): (30-40);
preferably, the mass concentration of the ammonia water is 20.0% -30.0%;
preferably, the alkali metal hydroxide comprises any one or a combination of at least two of lithium hydroxide, sodium hydroxide or potassium hydroxide;
preferably, the first solvent comprises water;
preferably, in the crospovidone, the cross-linked povidone with the particle size of 100-500 μm accounts for more than or equal to 90 percent.
3. A process for the preparation of crospovidone according to claim 1 or 2, characterized in that it comprises the steps of:
mixing 1-vinyl-2-pyrrolidone, ammonia water, urea, alkali metal hydroxide and a first solvent, and then carrying out polymerization reaction, pulping, cleaning and residue elimination treatment to obtain the crosslinked povidone.
4. The production method according to claim 3, wherein the polymerization reaction comprises a first temperature-elevating reaction, a second temperature-elevating reaction, and a temperature-lowering reaction;
preferably, the first temperature-rising reaction is carried out to 35-50 ℃;
preferably, after the first temperature rise, deoxidizing;
preferably, the deoxidizing mode comprises the steps of introducing inert gas and vacuumizing at least once;
preferably, after the inert gas is introduced and vacuumized for the last time, introducing the inert gas into the system, and keeping the pressure of the system to be 0-0.1MPa;
preferably, the system is subjected to a second temperature rise at 800-1200 rpm;
preferably, the temperature is raised to 120-130 ℃ for the second time;
preferably, after the second temperature rise, the reaction is kept at a temperature;
preferably, the time of the heat preservation reaction is 30-90min;
preferably, after the heat preservation reaction, the temperature is reduced to 80-110 ℃, the temperature rises again in the process of reducing the temperature, and the polymerization reaction starts;
preferably, the temperature of the polymerization reaction is 80-120 ℃;
preferably, the polymerization reaction pressure is 0.1 to 0.6MPa.
5. The preparation method according to claim 3 or 4, wherein the temperature of the material after the polymerization reaction is adjusted to 80-100 ℃, and a second solvent is added into the system for mixing, stirring and beating;
preferably, the mass of the second solvent used for beating is 300-500 parts based on 100 parts of the total mass of the 1-vinyl-2-pyrrolidone;
preferably, the second solvent comprises water;
preferably, the stirring beating speed is 50-150 rpm;
preferably, the stirring and beating time is 15-30min.
6. The method according to any one of claims 3 to 5, wherein the washing is performed in a washing filter provided with 400-500 mesh filter cloth;
preferably, the cleaning comprises vacuuming the pulped material to remove the first solvent and the second solvent;
preferably, the cleaning further comprises mixing the material trapped by the filter cloth with a third solvent, and vacuumizing, wherein the operation is performed at least once;
preferably, the mode of mixing the material trapped by the filter cloth with the third solvent comprises stirring;
preferably, the third solvent is used in the mixing in an amount of 300 to 500 parts based on 100 parts by weight of the total mass of the 1-vinyl-2-pyrrolidone;
preferably, the third solvent comprises water having a temperature of 60-80 ℃;
preferably, the stirring speed is 50-150 rpm;
preferably, the stirring time is 30-60min.
7. The method according to any one of claims 3 to 6, wherein the material trapped by the washed filter cloth is subjected to a residue elimination treatment;
preferably, the residue elimination treatment comprises the steps of mixing the materials trapped by the cleaned filter cloth with a fourth solvent, preserving heat, and adding residue elimination auxiliary agent for treatment;
preferably, the residue removing auxiliary agent comprises any one or a combination of at least two of hydrogen peroxide, peracetic acid, tert-butyl hydroperoxide or tert-butyl peracetate;
preferably, the addition amount of the residue removing auxiliary agent is 0.1-1.0 part;
preferably, the addition amount of the fourth solvent used in the residue elimination treatment is 300-500 parts;
preferably, the fourth solvent comprises water;
preferably, the temperature of the heat preservation is 60-80 ℃;
preferably, the time of the residue elimination treatment is 6-12h;
preferably, the residual amount of the residue elimination treatment to the system 1-vinyl-2-pyrrolidone is less than or equal to 10ppm.
8. The method according to any one of claims 3 to 7, wherein the residue elimination treatment is followed by solvent removal and drying;
preferably, the means for removing the solvent comprises centrifugation;
preferably, the mass content of the water-soluble matters in the solvent removed to the centrifugal retentate feed liquid is less than or equal to 1.0%.
9. The preparation method according to any one of claims 3 to 8, characterized in that the preparation method comprises the steps of:
(1) Mixing an alkali metal hydroxide with a first solvent to form a hydroxide solution;
(2) Mixing 1-vinyl-2-pyrrolidone, ammonia water, urea and alkali metal hydroxide solution, heating to 35-50 ℃ for the first time, introducing inert gas and vacuumizing at least once, introducing inert gas into the system, keeping the pressure of the system at 0-0.1MPa, and finishing deoxidization;
(3) Heating at 800-1200 rpm, heating to 120-130deg.C, maintaining the temperature for 30-90min, and cooling to 80-110deg.C; in the cooling process, the temperature rises again, the polymerization reaction starts, the temperature is controlled to 80-120 ℃, the system pressure is controlled to 0.1-0.6MPa, and the polymerization reaction ends;
(4) When the temperature of the system is regulated to 80-100 ℃, mixing the material after the polymerization reaction with a second solvent, stirring and pulping for 15-30min at 50-150 rpm;
(5) Transferring the pulped material to a cleaning filter with 400-500 meshes of filter cloth, and vacuumizing to remove the first solvent, the second solvent and soluble matters in the solvent; stirring and mixing the materials trapped by the filter cloth and the third solvent for 30-60min at 50-150 rpm, and vacuumizing, wherein the operation is performed at least once to finish cleaning;
(6) Mixing the material trapped by the filter cloth with a fourth solvent, preserving heat at 60-80 ℃ and carrying out residue elimination treatment for 6-12h until the residual amount of the 1-vinyl-2-pyrrolidone in the system is less than or equal to 10ppm, thereby completing the residue elimination treatment;
(7) And removing solvent from the material subjected to the residue elimination treatment and drying to obtain the crosslinked povidone.
10. A dust-free crosslinked povidone, characterized in that the dust-free crosslinked povidone comprises the crosslinked povidone of claim 1 or 2.
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