CN116574206A - Crosslinked povidone and preparation method and application thereof - Google Patents
Crosslinked povidone and preparation method and application thereof Download PDFInfo
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- CN116574206A CN116574206A CN202310532255.1A CN202310532255A CN116574206A CN 116574206 A CN116574206 A CN 116574206A CN 202310532255 A CN202310532255 A CN 202310532255A CN 116574206 A CN116574206 A CN 116574206A
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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 40
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 title claims abstract description 40
- 229940069328 povidone Drugs 0.000 title claims abstract description 33
- 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 97
- 239000002904 solvent Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 44
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 claims abstract description 39
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 claims abstract description 39
- 229960000913 crospovidone Drugs 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004202 carbamide Substances 0.000 claims abstract description 18
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 67
- 238000006116 polymerization reaction Methods 0.000 claims description 50
- 239000004744 fabric Substances 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 39
- 238000004140 cleaning Methods 0.000 claims description 37
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 29
- 238000005374 membrane filtration Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000010009 beating Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000012465 retentate Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 3
- 238000010981 drying operation Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 23
- 239000002253 acid Substances 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 13
- 230000036571 hydration Effects 0.000 abstract description 10
- 238000006703 hydration reaction Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 17
- 238000001816 cooling Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- 238000002791 soaking Methods 0.000 description 11
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 7
- 241000482268 Zea mays subsp. mays Species 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000000149 penetrating effect Effects 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-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
- 238000001694 spray drying Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004925 denaturation Methods 0.000 description 2
- 230000036425 denaturation Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000003857 carboxamides Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010865 sewage Substances 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
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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, urea, alkali metal hydroxide and a first solvent. The crospovidone disclosed by the invention has excellent water absorption capacity, disintegration performance and hydration performance. The preparation method does not need to consume a large amount of acid for acid washing treatment, has the advantages of less waste, low process energy consumption, low cost, low pollution, environmental protection, low impurity content of the formed crosslinked 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.
CN113461843a discloses a method for preparing crosslinked povidone, after 50% -90%, 15.5% -26.8% and 0.45% -1.6% of NVP, water and sodium hydroxide (NaOH) are respectively placed into a reaction kettle according to mass percentages, then a crosslinking agent is added, oxygen in a bottle is removed by replacing nitrogen, a stirrer is started under the protection of nitrogen with the pressure of 0.1-0.5MPa, the temperature is kept at 110-150 ℃ for 150-230min, after the temperature is observed to have obvious temperature rise, the reaction is started until the temperature is no longer raised, the product is taken out after the popcorn polymerization reaction is finished, and the popcorn is washed and dried. The preparation method has high yield which reaches about 90%, but has the defects that the residual sodium hydroxide cannot be treated cleanly by a cleaning process, and other impurities such as residual NVP,2-p and the like have high content and cannot meet the requirements of pharmacopoeia grade.
CN111378060a discloses a synthesis method of crospovidone based on popcorn polymerization mechanism of in situ generation of cross-linking agent, comprising the following steps: 1) Polymerization reaction; 2) Soaking; 3) Centrifugal dehydration; 4) Drying to obtain the final product. The crosslinked povidone prepared by the method disclosed by the invention can be crushed and screened to prepare PVP XL specification coarse powder with the particle size of more than 40 mu m and PVP XL-10 specification fine powder with the particle size of 20-40 mu m, and the residual monomer NVP of the finished product is less than 10ppm and the peroxide is not more than 400ppm. 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 crosslinked povidone that overcomes the above drawbacks, and has a simple and efficient preparation process and a high water absorption rate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the crosslinked povidone, and the preparation method and the application thereof, wherein the crosslinked povidone has excellent water absorption capacity, disintegration performance and hydration performance. The preparation method does not need to consume a large amount of acid for acid washing treatment, has the advantages of less waste, low process energy consumption, low cost, low pollution, environmental protection, low impurity content of the formed crosslinked povidone and high yield.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a crospovidone prepared from 1-vinyl-2-pyrrolidone (NVP), urea, alkali metal hydroxide, and a first solvent.
In the invention, urea is used as a catalyst and a modifier, and the formed crosslinked povidone has excellent water absorption capacity, disintegration performance and hydration performance and excellent comprehensive performance.
Preferably, the mass ratio of the 1-vinyl-2-pyrrolidone, urea, alkali metal hydroxide and the first solvent is 100 (0.125-1.0): (0.5-1.25): (10-20), wherein 0.125-1.0 can be 0.2, 0.4, 0.6, 0.8 and the like; 0.5-1.25 may be 0.6, 0.8, 1, 1.2, etc.; 10-20 may be 12, 14, 16, 18, etc.
Preferably, the 1-vinyl-2-pyrrolidone is a raw material after crystallization and purification.
In the invention, the 1-vinyl-2-pyrrolidone after crystallization and purification is preferably used as a preparation raw material, so that the impurities are few, the monomer activity is high, and the side reaction impurity products are few.
Preferably, the first solvent comprises water.
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, urea, alkali metal hydroxide and a first solvent, and then carrying out polymerization reaction, pulping, cleaning, ozone treatment and membrane filtration concentration to obtain the crosslinked povidone.
In the invention, urea plays a double role of a catalyst and a modifier in preparation: in the first aspect, urea is heated and decomposed at high temperature in an alkaline polymerization liquid environment to generate ammonia, so that the polymerization activity of vinyl groups of NVP can be improved in the reaction, the generation of a cross-linking agent is accelerated, the chain-initiated cross-linking polymerization reaction is accelerated, and the reaction rate is improved; 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 ozone treatment has the function of oxidizing and decomposing residual monomers, aldehydes and hydrazine impurities in the polymer system; meanwhile, the ozone also plays a role in regulating the pH value. 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.
In the invention, two types of products (such as PVPP XL coarse powder with the particle size of more than or equal to 40 mu m and PVP XL-10 fine powder with the particle size of less than 40 mu m) can be obtained simultaneously by two modes of ozone treatment and membrane filtration concentration without sieving and grinding. Compared with the traditional crushing and screening process, the method has the advantages that the problems of broken chain degradation, local overheat denaturation and the like of the product in the crushing process are easily caused, and the product prepared by the method has a long winding molecular chain structure, and has remarkable performance advantages of water absorption, swelling, complexation and the like.
Preferably, the 1-vinyl-2-pyrrolidone further comprises crystallization purification prior to mixing.
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, the first temperature is raised to 35-50deg.C (e.g., 36deg.C, 38deg.C, 40deg.C, 42deg.C, 44deg.C, 46 deg.C, 48deg.C, etc.), and then deoxygenated.
Preferably, the means for scavenging oxygen comprises passing an inert gas and evacuating at least once (e.g., twice, three times, four times, etc.).
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 displacement for at least 1 time (e.g., two, three, four, etc.), nitrogen was introduced and pressurized to 0.3MPa.
Preferably, the second temperature is raised to 120-130 ℃, e.g., 122 ℃, 124 ℃, 126 ℃, 128 ℃, etc.
Preferably, the reaction is incubated after the second temperature is raised to 120-130 ℃ (e.g. 122 ℃, 124 ℃, 126 ℃, 128 ℃, etc.).
Preferably, the incubation time is 30-90min, such as 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min, etc.
Preferably, after the heat-retaining reaction, the temperature is lowered to 80-110 ℃ (e.g. 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃ and the like), and the polymerization reaction is ended after the temperature is raised and kept stable during the temperature lowering.
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; and after the temperature tends to be stable and does not continue to rise, the polymerization is finished.
Preferably, the temperature of the material after the polymerization reaction is adjusted to 90-100 ℃ (e.g., 92 ℃, 94 ℃, 96 ℃, 98 ℃ 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 time of stirring and beating is 3-6 hours, such as 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, etc.
Preferably, the cleaning is performed in a cleaning filter provided with 400-500 mesh (e.g. 420 mesh, 440 mesh, 460 mesh, 480 mesh, etc.) filter cloth.
Preferably, the cleaning comprises vacuuming the pulped material to remove the first solvent, the second solvent and the material passing through the filter cloth.
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 third solvent removed by vacuum and the material passing through the filter cloth are subjected to membrane filtration concentration.
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 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 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 time is 30-60min, such as 35min, 40min, 45min, 50min, 55min, etc.
Preferably, the material trapped by the filter cloth after cleaning is subjected to ozone treatment, and the mixed solution of the first solvent, the second solvent, the third solvent and the material penetrating through the filter cloth is subjected to membrane filtration concentration.
Preferably, the ozone treatment comprises the steps of mixing the materials trapped by the filter cloth after cleaning with a fourth solvent, preserving heat and introducing ozone for treatment.
Preferably, the fourth solvent is used in the ozone 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, and the like.
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 ozone treatment is performed for a period of time ranging from 6 to 12 hours, such as 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, etc.
Preferably, the ozone is treated to a residual level of system 1-vinyl-2-pyrrolidone of 10ppm or less, for example 9ppm, 8ppm, 7ppm, 6ppm, 5ppm, 4ppm, etc.
Preferably, the ozone is treated to a system pH of 5.0-7.5, such as 5.2, 5.6, 6, 6.4, 6.8, 7.4, etc.
Preferably, the membrane filtration concentration is performed using a ceramic membrane.
Preferably, the filter element of the ceramic membrane has a material passage aperture of 10-20mm (for example, 12mm, 14mm, 16mm, 18mm, etc.), a filtering precision of 5-50nm (for example, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, etc.), and a filter element length of 1-2m (for example, 1.2nm, 1.4nm, 1.6nm, 1.8nm, etc.).
Preferably, the membrane filtration is concentrated to a residual amount of 1-vinyl-2-pyrrolidone of 10ppm or less (e.g., 9ppm, 8ppm, 7ppm, 6ppm, 5ppm, 4ppm, etc.), and a water soluble of 1.5% or less (e.g., 1.4%, 1.2%, 1%, 0.8%, etc.).
Preferably, the materials after ozone treatment and membrane filtration concentration are subjected to solvent removal and drying independently to obtain the cross-linked povidone with two particle sizes.
Preferably, the means for removing the solvent comprises centrifugation.
Preferably, the mass content of the water-soluble in the solvent removed to the centrifuge retentate feed is less than or equal to 1.5% (e.g., 1.4%, 1.2%, 1%, 0.8%, etc.).
As a preferable technical scheme, the preparation method comprises the following steps:
(1) Crystallizing and purifying 1-vinyl-2-pyrrolidone;
mixing an alkali metal hydroxide with a first solvent to form a hydroxide solution;
(2) Mixing the crystallized and purified 1-vinyl-2-pyrrolidone, urea and alkali metal hydroxide solution, heating to 35-50 ℃ for the first time, introducing inert gas and vacuumizing, and carrying out at least one time to finish deoxidization;
(3) After the temperature is raised to 120-130 ℃ for the second time, the temperature is kept for reaction for 30-90min, the temperature is reduced to 80-110 ℃, and after the temperature is raised and kept stable during the temperature reduction, the polymerization reaction is finished;
(4) When the temperature of the system is regulated to 90-100 ℃, mixing the materials after the polymerization reaction with a second solvent, stirring and pulping for 3-6h;
(5) Transferring the pulped material to a cleaning filter with 400-500 meshes of filter cloth, and vacuumizing to remove water and the material passing through the filter cloth; stirring and mixing the materials trapped by the filter cloth with a third solvent at 60-80 ℃ for 30-60min, vacuumizing, and performing the operation at least once to finish cleaning;
(6) Mixing the material trapped by the filter cloth with a fourth solvent, preserving heat at 60-80 ℃, introducing ozone for treatment for 6-12h until the residual amount of the 1-vinyl-2-pyrrolidone in the system is less than or equal to 10ppm and the pH value is 4.5-6.5, and finishing the ozone treatment;
performing membrane filtration and concentration on the mixed solution of the first solvent, the second solvent, the third solvent and the material which passes through the filter cloth after vacuum removal until the residual amount of the system 1-vinyl-2-pyrrolidone is less than or equal to 10ppm and the pH value is 5.0-7.5, thereby completing the membrane filtration and concentration;
(7) And removing the solvent and drying the materials subjected to ozone treatment and membrane filtration concentration independently to obtain the cross-linked povidone with two particle sizes.
In a third 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 crospovidone disclosed by the invention has excellent water absorption capacity, disintegration performance and hydration performance. After the water absorption of the crospovidone is 60min, the water absorption rate is above 810%, the disintegration time is within 19.78min, and the hydration capacity is above 8.1 by taking the crospovidone 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%.
(4) The preparation method disclosed by the invention does not need to be subjected to crushing and screening treatment, can be used for simultaneously obtaining products with two specifications (such as PVPP XL coarse powder with the particle size of more than or equal to 40 mu m and PVP XL-10 fine powder with the particle size of less than 40 mu m), and belongs to the industry initiative. Compared with the traditional crushing and screening process, the cross-linked povidone winding molecular chain structure has the advantages of obvious performance advantages such as water absorption, swelling, complexation and the like, and the problems of broken chain degradation, local overheat denaturation and the like of products in the crushing process are easily caused.
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) Crystallizing and purifying monomer 1-vinyl-2-pyrrolidone (NVP), wherein the activity of the monomer after crystallization and purification is 6.0;
mixing 0.5kg of sodium hydroxide with 10kg of purified water to form a hydroxide solution, and adding 100kg of crystallized and purified monomer NVP and 0.125kg of urea into a reaction kettle;
(2) 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 0.3MPa, and the deoxidation is completed;
(3) Continuously heating to 120 ℃ while keeping the stirring state, preserving heat and reacting for 30min, and naturally cooling to 80 ℃;
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 90 ℃ by cooling water, 300kg of water is added into the reaction kettle, and the mixture is fully stirred and pulped for 3 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 60 ℃ hot water which is equal to that in the step (4) into the cleaning filter again, stirring for 30min, 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 60 ℃, keeping the temperature in the temperature range, introducing ozone for treatment for 6 hours, and sampling and detecting 1ppm of residual NVP and pH value of 5.5. And vacuumizing to remove the material passing through the 400-mesh filter cloth and water into a polymerization kettle together for collection.
Transferring the materials in the cleaning filter to a centrifuge, centrifugally dehydrating, sampling and detecting 1.1% of soluble matters in water, and drying to obtain 45kg of PVPP XL specification coarse powder with the particle size of more than or equal to 40 mu m.
(7) And (3) carrying out membrane filtration, circulating and concentrating on the mixed solution of the water removed in vacuum and the material passing through the filter cloth, detecting residual monomer NVP not more than 10ppm, and stopping filtering and concentrating, wherein soluble matters in water are not more than 1.0%, and spray drying to obtain 50kg of PVPP XL-10 fine powder with the particle size less than 40 mu m.
Example 2
The embodiment provides a crospovidone, which is obtained by a preparation method comprising the following steps:
(1) Crystallizing and purifying monomer 1-vinyl-2-pyrrolidone (NVP), wherein the activity of the purified monomer is 7.0;
adding 100kg of crystalline purified monomer NVP, 0.56kg of urea, 0.875kg of sodium hydroxide and 15kg of purified water into a reaction kettle;
(2) 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 the replacement are continued for 2 times, nitrogen is introduced to pressurize to 0.3MPa, and the deoxidation is completed;
(3) Continuously heating to 125 ℃ while keeping the stirring state, preserving heat and reacting for 60min, and naturally cooling to 95 ℃;
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 95 ℃ by cooling water, 400kg of water is added into the reaction kettle, and the mixture is fully stirred and pulped for 4.5 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 70 ℃ hot water which is equal to that in the step (4) into the cleaning filter again, stirring for 45min, 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 65 ℃, keeping the temperature in the temperature range, introducing ozone for treatment for 9 hours, and sampling and detecting 2ppm of residual NVP and pH value of 6.0. And vacuumizing to remove the material passing through the 400-mesh filter cloth and water into a polymerization kettle together for collection.
Transferring the materials in the cleaning filter to a centrifuge, centrifugally dehydrating, sampling and detecting 0.5% of soluble matters in water, and drying to obtain 46kg of PVPP XL specification coarse powder with the particle size of more than or equal to 40 mu m.
(7) And (3) carrying out membrane filtration, circulating and concentrating on the mixed solution of the water removed in vacuum and the material passing through the filter cloth, detecting residual monomer NVP not more than 10ppm, and stopping filtering and concentrating, wherein soluble matters in water are not more than 1.0%, and spray drying to obtain 52kg of PVP XL-10 fine powder with the particle size less than 40 mu m.
Example 3
The embodiment provides a crospovidone, which is obtained by a preparation method comprising the following steps:
(1) Crystallizing and purifying monomer 1-vinyl-2-pyrrolidone (NVP), wherein the activity of the purified monomer is 8.5;
adding 100kg of purified monomer NVP, 1.0kg of urea, 1.25kg of sodium hydroxide and 20kg of purified water in the step (1) 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.
(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, introducing ozone for 12 hours, sampling and detecting 0ppm of residual NVP, and controlling the pH to be 6.5. And vacuumizing to remove the material passing through the 400-mesh filter cloth and water into a polymerization kettle together for collection.
Transferring the materials in the cleaning filter to a centrifuge, centrifugally dehydrating, sampling and detecting 0.5% of soluble matters in water, and drying to obtain 48kg of PVPP XL specification coarse powder with the particle size of more than or equal to 40 mu m.
(7) Filtering and concentrating the material filtered by the cleaning filter in a mixed solution reaction kettle of the water removed in vacuum and the material passing through the filter cloth, detecting residual monomer NVP less than or equal to 10ppm, and stopping filtering and concentrating, and spray drying to obtain 48kg of PVP XL-10 fine powder with the particle size less than 40 mu m, wherein the content of soluble matters in water is less than or equal to 1.0%.
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.
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.
Comparative example 1
The present comparative example provides a crospovidone obtained by a preparation method comprising the steps of:
(1) 100kg of the crystalline purified 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 introducing ozone for 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.
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.
(7) The mixture of water removed in vacuum and the material passing through the filter cloth is concentrated by membrane filtration and circulation, the concentration parameters and time are the same as those of example 3, and 28kg of PVP XL-10 fine powder with the particle size less than or equal to 40 μm is obtained by spray drying.
Comparative example 2
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 screening the dried material in a clean area to obtain a product with the particle size of more than 40 mu m and the brand XL; particle size less than 40 μm and more than 20 μm, and product with the trade name XL-10.
Comparative example 3
This comparative example provides a commercially available product, crospovidone, purchased from a new source.
Comparative example 4
This comparative example provides a commercially available B product, crospovidone available from Basoff.
Performance testing
The following tests were carried out on the crospovidone described in examples 1 to 7 and comparative examples 1 to 4 (> 40 μm sample):
(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
| Water absorption/%, 60min | Disintegration time/min | Hydration ability | |
| Example 1 | 825 | 18.26 | 8.2 |
| Example 2 | 830 | 19.78 | 8.5 |
| Example 3 | 865 | 16.46 | 8.8 |
| Example 4 | 840 | 18.67 | 8.5 |
| Example 5 | 845 | 17.56 | 8.6 |
| Example 6 | 830 | 19.32 | 8.2 |
| Example 7 | 810 | 16.85 | 8.1 |
| Comparative example 1 | 360 | 48.53 | 3.8 |
| Comparative example 2 | 560 | 39.66 | 5.5 |
| Comparative example 3 | 610 | 33.29 | 6.3 |
| Comparative example 4 | 670 | 37.86 | 6.9 |
Analysis table 1 shows that after the povidone of the invention absorbs water for 60min, the water absorption rate is above 810%, the povidone is taken as a disintegrating agent, the disintegrating time is within 19.78min, 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 4-7 and example 3 shows that examples 4-7 perform less than example 3, demonstrating that the combination of monomer, urea and alkali metal hydroxide in specific proportions results in a crosslinked povidone with 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, urea, alkali metal hydroxide and a first solvent.
2. The crospovidone of claim 1, wherein the mass ratio of 1-vinyl-2-pyrrolidone, urea, alkali metal hydroxide and first solvent is 100 (0.125-1.0): 0.5-1.25): 10-20;
preferably, the 1-vinyl-2-pyrrolidone is a raw material after crystallization and purification;
preferably, the first solvent comprises water.
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, urea, alkali metal hydroxide and a first solvent, and then carrying out polymerization reaction, pulping, cleaning, ozone treatment and membrane filtration concentration to obtain the crosslinked povidone.
4. The method of claim 3, wherein the 1-vinyl-2-pyrrolidone is further purified by crystallization prior to mixing;
preferably, the polymerization reaction comprises a first temperature rising reaction, a second temperature rising reaction and a temperature lowering reaction;
preferably, the first temperature-rising reaction is carried out to 35-50 ℃;
preferably, after the first temperature rise to 35-50 ℃, deoxidizing;
preferably, the deoxidizing mode comprises the steps of introducing inert gas and vacuumizing at least once;
preferably, the temperature is raised to 120-130 ℃ for the second time;
preferably, after the temperature is raised to 120-130 ℃ for the second time, 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 ℃, and the polymerization reaction is finished after the temperature is raised and kept stable during the temperature reduction.
5. The preparation method according to claim 3 or 4, wherein the temperature of the material after the polymerization reaction is adjusted to 90-100 ℃, 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 and beating time is 3-6h.
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 vacuumizing the pulped material to remove the first solvent, the second solvent and the material passing through the filter cloth;
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 addition amount of the third solvent used for the mixing is 300-500 parts;
preferably, the third solvent comprises water having a temperature of 60-80 ℃;
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 ozone treatment, and the mixture of the first solvent, the second solvent, the third solvent and the material passing through the filter cloth is subjected to membrane filtration concentration;
preferably, the ozone treatment comprises the steps of mixing the materials trapped by the filter cloth after cleaning with a fourth solvent, preserving heat and introducing ozone for treatment;
preferably, the fourth solvent is used in the ozone treatment in an amount of 300 to 500 parts;
preferably, the fourth solvent comprises water;
preferably, the temperature of the heat preservation is 60-80 ℃;
preferably, the ozone treatment time is 6-12 hours;
preferably, the ozone treatment is carried out until the residual amount of the 1-vinyl-2-pyrrolidone in the system is less than or equal to 10ppm;
preferably, the ozone treatment is carried out to a system pH of 5.0-7.5;
preferably, the membrane filtration concentration is performed by using a ceramic membrane;
preferably, the filter element of the ceramic membrane is a material channel with the aperture of 10-20mm, the filtering precision of 5-50nm and the filter element length of 1-2m;
preferably, the membrane is filtered and concentrated to a residual amount of 1-vinyl-2-pyrrolidone of less than or equal to 10ppm and a water soluble content of less than or equal to 1.5%.
8. The preparation method according to claim 7, wherein the materials after ozone treatment and membrane filtration concentration are each independently subjected to solvent removal and drying operations to obtain cross-linked povidone of two particle sizes;
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 1.5%.
9. The preparation method according to any one of claims 3 to 8, characterized in that the preparation method comprises the steps of:
(1) Crystallizing and purifying 1-vinyl-2-pyrrolidone;
mixing an alkali metal hydroxide with a first solvent to form a hydroxide solution;
(2) Mixing the crystallized and purified 1-vinyl-2-pyrrolidone, urea and alkali metal hydroxide solution, heating to 35-50 ℃ for the first time, introducing inert gas and vacuumizing, and carrying out at least one time to finish deoxidization;
(3) After the temperature is raised to 120-130 ℃ for the second time, the temperature is kept for reaction for 30-90min, the temperature is reduced to 80-110 ℃, and after the temperature is raised and kept stable during the temperature reduction, the polymerization reaction is finished;
(4) When the temperature of the system is regulated to 90-100 ℃, mixing the materials after the polymerization reaction with a second solvent, stirring and pulping for 3-6h;
(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 the material passing through the filter cloth; stirring and mixing the materials trapped by the filter cloth and the third solvent for 30-60min, vacuumizing, and performing the operation at least once to finish cleaning;
(6) Mixing the material trapped by the filter cloth with a fourth solvent, preserving heat at 60-80 ℃, introducing ozone for treatment for 6-12h until the residual amount of the 1-vinyl-2-pyrrolidone in the system is less than or equal to 10ppm and the pH value is 5.0-7.5, and finishing the ozone treatment;
performing membrane filtration and concentration on the mixed solution of the first solvent, the second solvent, the third solvent and the material which passes through the filter cloth after vacuum removal until the residual amount of the system 1-vinyl-2-pyrrolidone is less than or equal to 10ppm and the pH value is 5.0-7.5, thereby completing the membrane filtration and concentration;
(7) And removing the solvent and drying the materials subjected to ozone treatment and membrane filtration concentration independently to obtain the cross-linked povidone with two particle sizes.
10. A water absorbent resin, characterized in that the water absorbent resin comprises the crospovidone of claim 1 or 2.
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