CN106749908B - The production method of low-residue single cross-linking polyethylene pyrrolidone - Google Patents
The production method of low-residue single cross-linking polyethylene pyrrolidone Download PDFInfo
- Publication number
- CN106749908B CN106749908B CN201710158141.XA CN201710158141A CN106749908B CN 106749908 B CN106749908 B CN 106749908B CN 201710158141 A CN201710158141 A CN 201710158141A CN 106749908 B CN106749908 B CN 106749908B
- Authority
- CN
- China
- Prior art keywords
- consersion unit
- deionized water
- added
- monomer
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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
- C08F226/06—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 by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
-
- 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
- C08F2/00—Processes of polymerisation
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/08—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkali metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/006—Removal of residual monomers by chemical reaction, e.g. scavenging
-
- 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
- C08F2400/00—Characteristics for processes of polymerization
- C08F2400/02—Control or adjustment of polymerization parameters
Abstract
The present invention proposes a kind of production method of low-residue single cross-linking polyethylene pyrrolidone, comprising steps of 1) deionized water is added into consersion unit, n-vinyl pyrrolidone monomer is added under stirring, 2) consersion unit is vacuumized, and with remaining air in indifferent gas displacement consersion unit；3) addition initiator and crosslinking agent, 4) heating consersion unit temperature is to 130~140 DEG C, heat preservation 3~5 hours；5) after reaction was completed, consersion unit is cooled down, the material in consersion unit is mixed with hot deionized water, pH adjusting agent, residual dose of drop, carries out vacuum filters pressing, washing.The present invention is suitably matched by preferred raw material, initiator, crosslinking agent, residual dose of drop, PH regulator, solvent and monomer, suitable reaction temperature, pressure and time, adjust the degree of cross linking of cross-linking polyethylene pyrrolidone, reaction conversion ratio is increased to greater than 98%, and washed with vacuum filters pressing, hot water, 5ppm or less is singly reduced to by residual.
Description
Technical field
The invention belongs to field of organic polymer compound, and in particular to a kind of nitrogenous heterocyclic organic compound producer
Method.
Background technique
Cross-linking polyethylene pyrrolidone, referred to as (PVPP), CTFA title: Crosslinked
Polyvinylpyrrolidone, No. CAS:: 25249-54-1, molecular formula: (C6H9NO)n, structural formula are as follows:
Cross-linking polyethylene pyrrolidone is that one kind made of n-vinyl pyrrolidone cross-linked polymeric is not soluble in water, strong
The cross-linked polymer of acid, highly basic and common organic solvents is that linear polyethylene base pyrrolidone molecule chain passes through physics or change
Method is cross-linked with each other high molecular weight material together.The cross-linking polyethylene pyrrolidone obtained using distinct methods, it
The degree of cross linking it is different, certain performances are also different, and the cross-linking polyethylene pyrrolidone of low crosslinking degree is superabsorbency resin, in
Etc. the degrees of cross linking cross-linking polyethylene pyrrolidone be water absorbent gel, the cross-linking polyethylene pyrrolidone of high-crosslinking-degree is insoluble
Object, it also has other than with the good characteristics such as absorption complexing, physiological compatibility possessed by polyvinylpyrrolidone
The performances such as water-insoluble, water suction, water-retaining property, as a kind of important macromolecule fine chemical product, its excellent performance makes it
Have wide practical use in fields such as medicine, cosmetics, food.In the widely applied tablet disintegrant of field of medicaments, sustained release
Agent；Moisturizer, stabilizer can be done in cosmetic field, can remove beer, fruit wine, the polyphenol substance in beverage in field of food,
The non-biostability of wine body is improved, clarifying agent and stabilizer as wine, beverage extend its shelf-life, and it is transparent to improve its
Degree, color and taste.
The currently used cross-linking method of cross-linking polyethylene pyrrolidone has: (1) polyvinylpyrrolidone self-crosslinking method；
(2) n-vinyl pyrrolidone self-crosslinking polymerization；(3) crosslinking agent and n-vinyl pyrrolidone copolymerzation with cross-linking method.Polyethylene
Base pyrrolidones self-crosslinking method is to use persulfate, hydrazine, hydrogen peroxide treatment cross-linking polyethylene pyrrolidone, or having peroxide
With α-ω-alkadienes processing in the presence of compound.But the cross-linked polymer being obtained by only has slightly cross-linked and generates soft gel
With the cross-linking polyethylene pyrrolidone of low crosslinking degree.N-vinyl pyrrolidone copolymerzation with cross-linking method is n-vinyl pyrrolidone
Aqueous solution is copolymerized with crosslinking agent bifunctional and n-vinyl pyrrolidone initiator, generates cross-linking polyethylene pyrroles
Alkanone, the degree of cross linking are less than the cross-linking polyethylene pyrrolidone that n-vinyl pyrrolidone self-crosslinking polymerization generates.
N-vinyl pyrrolidone self-crosslinking polymerization, also referred to as maize polymerize (popcorn polymerization) or
Proliferous polymerization (proliferous polymerization), it is heating N- vinylpyridine in the presence of alkali metal hydroxide
Pyrrolidone generates bifunctional monomer and then completes cross-linked polymeric with n-vinyl pyrrolidone.It can lead to high-crosslinking-degree
Cross-linking polyethylene pyrrolidone generation, be it is completely insoluble in water, be widely used as the clarifying agent of beer and beverages, medicine
Object disintegrating agent and antidiarrheic etc..
N-vinyl pyrrolidone self-crosslinking polymerization is the advanced of current production high-crosslinking-degree polyvinylpyrrolidone
Technique, its mechanism are assumed to be free radical polymerization, and free radical is generated by the fracture for having generated polymer, in practical preparation
When do not need plus radical initiator.
But in process of production, have the following problems: (1) selection of process conditions influences the conversion ratio of reaction very big,
Carry out reaction can not；(2) conversion ratio reacted directly affects the residual list of product；(3) reaction conversion ratio is low, needs
A large amount of deionized water washs product, increases the processing cost and wastewater treatment difficulty of product；(4) washing of product is set
Standby and technique influences the dosage of the residual list of product and deionized water very big.
Summary of the invention
For shortcoming existing for this field, the purpose of the present invention is drawn using certain by Optimizing Technical
Agent, crosslinking agent, residual dose of drop are sent out, the cross-linking polyethylene pyrrolidone degree of cross linking is adjusted, improves n-vinyl pyrrolidone conversion ratio,
It is proposed a kind of production method of low-residue single cross-linking polyethylene pyrrolidone.
Realize the technical solution of the object of the invention are as follows:
A kind of production method of low-residue single cross-linking polyethylene pyrrolidone, comprising steps of
1) deionized water is added into consersion unit, n-vinyl pyrrolidone monomer is added under stirring,
2) consersion unit is vacuumized, and with remaining air in indifferent gas displacement consersion unit, consersion unit is kept to have
The micro-positive pressure of 0.01~0.5MPa；
3) peroxide is added, the one or more of azo or alkali metal hydroxide are mixed into initiator, and
Bifunctional compound crosslinking agent；
4) heating consersion unit temperature keeps the temperature 3~5 hours to 130~140 DEG C；
5) after reaction was completed, consersion unit is cooled down, by the material and hot deionized water, pH value adjusting in consersion unit
Residual dose of agent, drop mixing, carry out the filters pressing of level-one vacuum；
6) hot deionized water is added in filter cake, carries out secondary vacuum filters pressing, filtration cakes torrefaction is broken for particle.
Wherein, the deionized water quality that step 1) is added is the 10~25% of n-vinyl pyrrolidone monomer mass, institute
State n-vinyl pyrrolidone monomer mass content >=99.85%, pH value≤9.5.
The monomer preferably uses the n-vinyl pyrrolidone monomer of CNSG Anhui Hongsifang Co., Ltd.
Wherein, the indifferent gas that step 2) is added is nitrogen or argon gas.
Wherein, the initiator and crosslinking agent that step 3) is added are peroxide, azo or alkaline hydrated oxide, are selected from
Hydrogen peroxide, tert-butyl hydroperoxide, tert-butylperoxy pivalate, azodiisobutyronitrile, azobisisoheptonitrile, azo first
Alkane, two butyramide of azo, sodium hydroxide, potassium hydroxide etc. it is one or more, crosslinking agent is bifunctional compound, be selected from two
Ethenylbenzene, N-N '-methylene-bisacrylamide, dimethyl allene vinyl acetate, divinylbenzene etc. it is one or more.
The initiator and cross-linked dosage of addition are the 0.2~0.4% of n-vinyl pyrrolidone monomer mass, wherein being crosslinked
Agent is initiator quality 0.5~5%, adjusts the degree of cross linking of the also adjustable cross-linking polyethylene pyrrolidone of ratio of crosslinking agent.
Further, after step 4) keeps the temperature 3~5 hours, stop the heating to consersion unit, be cooled to consersion unit
At 100 DEG C, whether the temperature and pressure of observing response equipment has unexpected rising, if there is flying up, illustrates have reaction to send out
It is raw, then carry out 1 hour (not needing to heat) of reaction；If do not flown up, continue to be naturally cooling to observe temperature and
Pressure is flown up, and control reaction carries out 1 hour.
Wherein, the value that observation pressure is flown up is to reach 0.3~0.5MPa；Reaction is dropped after carrying out 1 hour with recirculated water
Temperature.
Wherein, in the step 5), based on the quality of n-vinyl pyrrolidone monomer, going for 3~5 times of mass-heats is added
Ionized water, adjusts pH value 5~8 with pH adjusting agent by residual dose of 0.01~0.04% drop, and the temperature of hot deionized water is 85~
90℃.Wherein, the pH adjusting agent can be one or more organic and or inorganic acids, selected from hydrochloric acid, sulfuric acid, acetic acid,
One of citric acid is a variety of.
Wherein, residual dose of the drop is peroxide or azo-initiator, is selected from hydrogen peroxide, tert-butyl hydroperoxide
Hydrogen, tert-butylperoxy pivalate, azodiisobutyronitrile, azobisisoheptonitrile, azomethane, one in two butyramide of azo
Kind is a variety of.
Wherein, the vacuum pressure of the level-one vacuum filters pressing is -0.05~-0.1MPa, filtering to solid content 40~60%.
Wherein, in step 6), based on the quality of n-vinyl pyrrolidone monomer, 3~5 times of mass-heats are added in filter cake
Deionized water, the vacuum pressure of the step secondary vacuum filters pressing are -0.05~-0.1MPa, are filtered to solid content 40~60%,
The temperature of the deionized water of heat is 85~90 DEG C.
The beneficial effects of the present invention are:
(1) present invention is suitably matched by preferred raw material, initiator, crosslinking agent, solvent and monomer, suitable reaction temperature
Degree and the time, and vacuumize plus controlled atmosphere under, reaction conversion ratio can be increased to greater than 98%.
(2) PH regulator is added in washing, pressure-filtering process and disappears residual dose by the present invention, further increases conversion ratio, reduces
Residual list.
(3) present invention using vacuum press filter heating water multistage washed, filters pressing, preferably two-stage, the residual list of product can be made
≤ 5ppm, and reduce the dosage of deionized water.
(4) product quality reaches Chinese Pharmacopoeia 2015 editions, United States Pharmacopeia USP38 editions and European Pharmacopoeia EP8 editions requirements.
Detailed description of the invention
Fig. 1 is a kind of flow sheet of low-residue single cross-linking polyethylene pyrrolidone of the present invention.
Specific embodiment
The present invention is now illustrated with following embodiment, but is not intended to limit the scope of the invention.Hand used in embodiment
Section uses the means of this field routine unless otherwise instructed.
Embodiment 1:
(1) 200 kilograms of deionized water is added in the reactor, starts blender stirring after adding deionized water, stirs
Mix revolving speed 35rpm.
(2) 1000 kilograms of n-vinyl pyrrolidone (CNSG Anhui Hongsifang Co., Ltd's production), content is added
>=99.85%, light component content≤0.10%, PH≤9.5；
(3) evacuated pressure is vented to micro-positive pressure, is repeated with nitrogen pressurized reactor to 0.5MPa to -0.09MPa
Twice；
(4) add 3 kilograms of initiator sodium hydroxide, 0.2 kilogram of azodiisobutyronitrile, crosslinking agent N-N '-methylene bisacrylamide
In 0.03 kilogram of amide to reactor；
(5) steam heating response device is opened to 135 DEG C, and is maintained 4 hours；
(6) steam is closed, when reactor drop being allowed to be naturally cooling to 100 DEG C, whether observing response occurs, when temperature and pressure is prominent
So rise, wherein pressure rises to 0.3~0.5MPa, illustrates that reaction occurs and (do not need to keep the temperature or heat), otherwise continues to cool down, see
Examine whether reaction occurs；
(7) after reaction occurs, reaction 60 minutes is maintained, then starts to add circulating water；
(8) when temperature drops to 100 DEG C hereinafter, adding deionized water in reactor, and reactor content is put into head tank；
(9) 4 tons of 85~90 DEG C of deionized waters, pH adjusting agent and 0.2 kilogram of residual dose of two isobutyl of azo that disappear is added to head tank
Nitrile, adding acetic acid control pH value is 5~8, starting stirring；
(10) start filter press feed pump, head tank material dnockout to first order vacuum press filter washed, filters pressing,
Vacuum pressure control -0.09MPa, solid content >=50%；
(11) material feed slurry tank after filters pressing, 4 tons of 85~90 DEG C of deionized waters are added in slurry tank, and stir；
(12) start slurry delivery pump, dnockout to secondary vacuum filter press washed, filters pressing, vacuum pressure control-
0.09MPa, solid content >=50%；
(13) after filters pressing, material collection to feed bin；
(14) start second level filter press conveyer, convey material to cross-linking polyethylene pyrrolidone drying tower；
(15) air, which enters cross-linking polyethylene pyrrolidone drying tower through filter cleaning heating, carries out interior and material
The exchange of matter and heat completes evaporation and drying, to obtain the satisfactory powdered dry powder particle of water content；
(16) powdered dry powder particle is crossed through vibrating screen through being crushed to required partial size and is sieved to feed bin；
(17) feed bin material is packaged machine and is packed.
Embodiment 2
(1) 220 kilograms of deionized water is added in the reactor, starts blender stirring after adding deionized water, stirs
Mix revolving speed 35rpm.
Step (2) to (17) is operated with embodiment 1.
Embodiment 3
(1) 200 kilograms of deionized water is added in the reactor, starts blender stirring after adding deionized water, stirs
Mix revolving speed 25rpm.
Step (2) to (17) is operated with embodiment 1.
Embodiment 4
Step (1) is operated with embodiment 1.
(2) 1000 kilograms of commercially available n-vinyl pyrrolidone of addition, content >=99.80%, light component content≤
0.15%, PH≤10.5；
Step (3) to (17) is operated with embodiment 1.
Embodiment 5
Step (1) to (2) is operated with embodiment 1.
(3) evacuated pressure is vented with indifferent gas pressurized reactor to 0.5MPa to micro-positive pressure to -0.07MPa, then is weighed
Again twice；
Step (4) to (17) is operated with embodiment 1.
Embodiment 6
Step (1) to (3) is operated with embodiment 1.
(4) add 3 kilograms of initiator sodium hydroxides to reactor；
Step (5) to (17) is the same as embodiment 1.
Embodiment 7
Step (1) to (4) is operated with embodiment 1.
(5) steam heating response device is opened to 115 DEG C, and is maintained 4 hours；
Step (6) to (17) is the same as embodiment 1.
Embodiment 8
Step (1) to (8) is operated with embodiment 1.
(9) 4 tons of 90 DEG C of deionized waters, PH regulator and 0.2 kilogram of residual dose of hydrogen peroxide that disappear is added to head tank, controls PH
Value is 5~8, starting stirring；
Step (10) to (17) is operated with embodiment 1.
Embodiment 9
Step (1) to (9) is operated with embodiment 1.
(10) start filter press feed pump, head tank material dnockout to first order vacuum press filter washed, filters pressing,
It does not vacuumize, obtained filter cake solid content 20~30%；
Step (11) is the same as embodiment 1；
(12) start slurry delivery pump, dnockout to second level filter press washed, filters pressing, is not vacuumized, filter cake solid content
20~30%；
Step (13) to (17) is operated with embodiment 1.
The target level of product quality of cross-linking polyethylene pyrrolidone is shown in Table 1
Table 1: quality standard
The product that above embodiments 1~9 obtain is tested, and the results are shown in Table 2.
2 examination and test of products result of table
| Embodiment | Reaction conversion ratio % | Residual list ppm |
| Embodiment 1 | 98.12 | 4.2 |
| Embodiment 2 | It does not react | |
| Embodiment 3 | 93.81 | 14.8 |
| Embodiment 4 | 95.63 | 10.2 |
| Embodiment 5 | 96.18 | 8.6 |
| Embodiment 6 | 92.26 | 17.2 |
| Embodiment 7 | 88.78 | 27.5 |
| Embodiment 8 | 97.36 | 6.4 |
| Embodiment 9 | 98.12 | 8.5 |
From the point of view of above-mentioned data comparison, raw material, oxygen content, initiator and crosslinking agent, disappear residual dose additional amount, reaction temperature
Degree, speed of agitator, filters pressing vacuum degree all to reaction conversion ratio, it is residual singly have a significant impact, especially deionized water proportion influence
It is bigger, it can directly result in and not react.
Test result under different working conditions shows the high-quality n-vinyl pyrrolidone using my company's production,
Using unique initiator, crosslinking agent and the residual dose of proportion that disappear, it can adjust and hand over using automation control by Optimizing Technical
Join the degree of cross linking of polyvinylpyrrolidone, improves n-vinyl pyrrolidone conversion ratio.Using high-efficient purification equipment and technique
Scheme carries out purified treatment to the crude product after polymerization, can get low residual single cross-linking polyethylene pyrrolidone, and residual list≤
5ppm is better than domestic and international latest edition medicine grade standard.Safe operation, conveniently, stablize, no exhaust gas and solid waste generate, and water consumption is few,
Waste water passes through biochemical treatment, meets country's environment-protection wastewater discharge standard related with place.
Above embodiment be only preferred embodiments of the present invention will be described, not to the scope of the present invention into
Row limits, and without departing from the spirit of the design of the present invention, this field ordinary engineering and technical personnel is to technical side of the invention
The all variations and modifications that case is made, should fall within the scope of protection determined by the claims of the present invention.
Claims (6)
1. a kind of production method of low-residue single cross-linking polyethylene pyrrolidone, which is characterized in that comprising steps of
1) deionized water is added into consersion unit, n-vinyl pyrrolidone monomer is added under stirring, addition is gone
Ion water quality is the 20% of n-vinyl pyrrolidone monomer mass, the n-vinyl pyrrolidone monomer mass content >=
99.85%, pH value≤9.5；The speed of agitator is 35rpm；
2) consersion unit is evacuated to -0.09MPa, and with remaining air in indifferent gas displacement consersion unit, keeps reaction
Equipment has the micro-positive pressure of 0.01~0.5MPa, and the indifferent gas is nitrogen or argon gas；
3) peroxide, azo and alkaline hydrated oxide is added as initiator and bifunctional compound as friendship
Join agent；
The peroxide be selected from one of hydrogen peroxide, tert-butyl hydroperoxide, tert-butylperoxy pivalate or
It is a variety of；The azo be selected from one of azodiisobutyronitrile, azobisisoheptonitrile, azomethane, two butyramide of azo or
It is a variety of；The alkaline hydrated oxide is selected from one or both of sodium hydroxide, potassium hydroxide；The crosslinking agent is selected from N-N '-
One or both of methylene-bisacrylamide, divinylbenzene；
4) heating consersion unit temperature keeps the temperature 3~5 hours to 130~140 DEG C；
5) after reaction was completed, consersion unit is cooled down, by the material and hot deionized water, pH adjusting agent, drop in consersion unit
Residual dose of mixing, carries out the filters pressing of level-one vacuum；
6) hot deionized water is added in filter cake, carries out secondary vacuum filters pressing, filtration cakes torrefaction is broken for particle；
After the step 4) keeps the temperature 3~5 hours, stop the heating to consersion unit, when consersion unit is cooled to 100 DEG C, sees
Whether the temperature and pressure for examining consersion unit has unexpected rising, if there is flying up, illustrates there is reaction, then carries out anti-
It answers 1 hour；If do not flown up, continue to be naturally cooling to observe flying up for temperature and pressure, control reaction
It carries out 1 hour；The value that observation pressure is flown up reaches 0.3~0.5MPa；Reaction uses circulating water cooling after carrying out 1 hour.
2. production method according to claim 1, which is characterized in that the step 3) initiator and crosslinking agent quality are N-
The 0.2~0.4% of vinylpyrrolidone monomer quality, wherein crosslinking agent is the 0.5~5% of initiator quality.
3. production method according to claim 1, which is characterized in that in the step 5), by n-vinyl pyrrolidone
The quality meter of monomer is added the hot deionized water of 3~5 times of quality, residual dose of 0.01~0.04% drop, is adjusted with pH adjusting agent
PH value 5~8, the temperature of hot deionized water are 85~90 DEG C, and the pH adjusting agent is organic and or inorganic acids, are selected from salt
One of acid, sulfuric acid, acetic acid, citric acid are a variety of.
4. described in any item production methods according to claim 1~3, which is characterized in that residual dose of the drop is peroxide
Or azo-initiator, selected from hydrogen peroxide, tert-butyl hydroperoxide, tert-butylperoxy pivalate, azodiisobutyronitrile,
One of azobisisoheptonitrile, azomethane, two butyramide of azo are a variety of.
5. described in any item production methods according to claim 1~3, which is characterized in that the vacuum of the level-one vacuum filters pressing
Pressure is -0.05~-0.1MPa, filtering to solid content 40~60%.
6. described in any item production methods according to claim 1~3, which is characterized in that in step 6), by N- vinyl pyrrole
The deionized water of 3~5 times of mass-heats, the vacuum of the step secondary vacuum filters pressing are added in filter cake for the quality meter of alkanone monomer
Pressure is -0.05~-0.1M Pa, filtering to solid content 40~60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710158141.XA CN106749908B (en) | 2017-03-16 | 2017-03-16 | The production method of low-residue single cross-linking polyethylene pyrrolidone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710158141.XA CN106749908B (en) | 2017-03-16 | 2017-03-16 | The production method of low-residue single cross-linking polyethylene pyrrolidone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106749908A CN106749908A (en) | 2017-05-31 |
| CN106749908B true CN106749908B (en) | 2019-05-14 |
Family
ID=58966213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710158141.XA Active CN106749908B (en) | 2017-03-16 | 2017-03-16 | The production method of low-residue single cross-linking polyethylene pyrrolidone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106749908B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073614A (en) * | 1990-10-18 | 1991-12-17 | Isp Investments Inc. | Strongly swellable, moderately crosslinked polyvinylpyrrolidone |
| JP2008255146A (en) * | 2007-04-02 | 2008-10-23 | Nippon Shokubai Co Ltd | Method for producing polyvinyl pyrrolidone |
| CN102382227A (en) * | 2011-08-12 | 2012-03-21 | 天津博纳艾杰尔科技有限公司 | Swelling copolymerization preparation method of N-vinyl pyrrolidone and divinylbenzene monodisperse microsphere |
| CN105906768A (en) * | 2016-04-20 | 2016-08-31 | 贵州省欣紫鸿药用辅料有限公司 | Synthesis method of crospovidone |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3315105B2 (en) * | 2000-02-10 | 2002-08-19 | 株式会社日本触媒 | Method for producing vinylpyrrolidone polymer |
-
2017
- 2017-03-16 CN CN201710158141.XA patent/CN106749908B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073614A (en) * | 1990-10-18 | 1991-12-17 | Isp Investments Inc. | Strongly swellable, moderately crosslinked polyvinylpyrrolidone |
| JP2008255146A (en) * | 2007-04-02 | 2008-10-23 | Nippon Shokubai Co Ltd | Method for producing polyvinyl pyrrolidone |
| CN102382227A (en) * | 2011-08-12 | 2012-03-21 | 天津博纳艾杰尔科技有限公司 | Swelling copolymerization preparation method of N-vinyl pyrrolidone and divinylbenzene monodisperse microsphere |
| CN105906768A (en) * | 2016-04-20 | 2016-08-31 | 贵州省欣紫鸿药用辅料有限公司 | Synthesis method of crospovidone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106749908A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5380808A (en) | Process for producing water-absorbing resins | |
| US8252873B1 (en) | Process for the production of a superabsorbent polymer | |
| WO1998005420A1 (en) | Water-absorbent and process for preparing the same | |
| RU2008142840A (en) | A COPOLYMER OF STYRENE AND MALEIC ANHYDRIDE / ACID (OPTIONS), A PRODUCT BASED ON IT, A METHOD FOR PRODUCING A COPOLYMER OF STYRENE AND MALEIC ANHYDRIDE / ACID | |
| CN103766695B (en) | Polydextrose with controllable molecular weight and rapid preparation method thereof | |
| CN104292393A (en) | Method for preparing grafted copolymer by adopting supercritical carbon dioxide | |
| CN106749908B (en) | The production method of low-residue single cross-linking polyethylene pyrrolidone | |
| EP1263813A1 (en) | Method for adjusting the particle size of popcorn polymers during popcorn polymerization | |
| CN102617743A (en) | Preparation method for hydroxyethyl starch | |
| CN107254010B (en) | Complexing system and complexing method for producing high-stability povidone iodine | |
| CN105622826A (en) | Novel synthesis technology of sodium polyacrylate super absorbent resin | |
| CN109180839A (en) | A kind of preparation method of araboxylan | |
| CN100390224C (en) | Method for eliminating residual monomer N-vinyl-pyrrolidone in polymer | |
| CN106674388A (en) | Method for reducing N-vinyl pyrrolidone in polyvinylpyrrolidone | |
| CN107189115A (en) | A kind of preparation method of crosslinked poly amylose microballoon | |
| CN109467644B (en) | Maleic anhydride modified polypropylene and preparation method thereof | |
| JP6250066B2 (en) | Depolymerization of alginate | |
| US9745448B2 (en) | Method for producing vinyl amine unit-containing polymer solution | |
| CN103819603B (en) | The preparation method of the super absorbent resin that extractable matter is low | |
| CN102532364A (en) | Acrylamide ultrahigh molecular weight polymerization reaction initiator | |
| JP2014000013A (en) | Crushed garlic product, active oxygen scavenger, and manufacturing method of crushed garlic product | |
| CN107573459A (en) | A kind of preparation method by the use of rice straw as the super absorbent resin of raw material | |
| CN116396431A (en) | Salt-resistant carbomer and preparation method thereof | |
| CN115651224A (en) | Production method of dustless crosslinked polyvidone | |
| CN101372523A (en) | Method for producing easy granulation high hygroscopicity resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |