CN100463938C - Preparation process of porous polypropylene microparticle - Google Patents
Preparation process of porous polypropylene microparticle Download PDFInfo
- Publication number
- CN100463938C CN100463938C CNB2007100626566A CN200710062656A CN100463938C CN 100463938 C CN100463938 C CN 100463938C CN B2007100626566 A CNB2007100626566 A CN B2007100626566A CN 200710062656 A CN200710062656 A CN 200710062656A CN 100463938 C CN100463938 C CN 100463938C
- Authority
- CN
- China
- Prior art keywords
- reactor
- polypropylene
- organic solvent
- porous polypropylene
- solution
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to superfine polymer powder material, and is especially the preparation process of superfine porous polypropylene powder. The preparation process includes mixing polypropylene material, pore forming agent and organic solvent in reactor A, heating to 100-150 deg.c and maintaining for 1-10 hr; controlling the temperature of the same organic solvent in the reactor B below room temperature; adding the polypropylene solution from the reactor A to the reactor B and lowering the temperature to room temperature; liquid-solid separation and vacuum drying to obtain the superfine porous polypropylene powder. The superfine porous polypropylene powder has specific surface area of 2-130 sq m/g, pore size of 100-200 nm and particle size of 1-10 micron, and may be used in preparing adsorbing polymer resin, modifying resin, etc.
Description
Technical field
The present invention relates to the field of polymer superfine powdery material, is a kind ofly to control the crystalling propylene granulation process by physical method, the production method of preparation porous polypropylene microparticle.
Background technology
At present, the main method at industrial preparation porous polymer particulate is a suspension polymerization.This method is to generate in the process of polymkeric substance in the polymer monomer polymerization, by the controlled polymerization reaction system, adds suitable pore-creating agent, makes porous polymer particle.The shortcoming of this method is the polymerization reaction system complexity, need be to all multifactor controls such as monomer, linking agent, pore-creating agent, initiator and water compositions, otherwise just can not get needed porous polymer.In actual production, it mainly is to be used for producing the powdered polypropylene masterbatch that polypropylene industrial adopts suspension polymerization, rather than porous polypropylene microparticle, therefore, yet there are no the industrial method of preparation porous polypropylene.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of porous polypropylene microparticle is a kind of by physical method control crystalling propylene granulation process, the production method of preparation porous polypropylene microparticle.
The preparation method of porous polypropylene microparticle of the present invention is characterized in that, may further comprise the steps:
1) with the polypropylene is raw material, it is dropped among the reactor A, the organic solvent that contains pore-creating agent is housed in the still in advance, this pore-creating agent is 0.01%～10% of an organic solvent quality, under whipped state, material to 100-150 ℃ in the heating kettle is incubated 1-10 hours then, polypropylene is dissolved in fully forms polypropylene solution in the organic solvent, polyacrylic charging capacity is 2-30% of an organic solvent quality;
2) be equipped with in advance in the reactor B with reactor A in form identical organic solvent, its temperature is controlled at below the room temperature.Under stirring action, with the rapid thorough mixing of solvent among polypropylene solution among the reactor A and the reactor B, the mixture temperature is reduced to below 70 ℃, the organic solvent that will contain porous polypropylene microparticle again mixes the slurry temperature and is reduced to room temperature;
3) carry out liquid-solid separation to mixing slurry, remove the organic solvent on porous polypropylene microparticle surface;
4) porous polypropylene microparticle that obtains after the liquid-solid separation is sent into vacuum drying oven, remove organic solvent remaining in the hole.
It is 2-130m that the present invention makes specific surface area
2/ g, the aperture between 100-200nm, the porous polypropylene microparticle finished product of particle diameter between 1-10 μ m.
Pp material is isotactic or syndiotactic polypropylene, and molecular weight is 20,000-200,000.Polyacrylic charging capacity is 2-30% of an organic solvent quality, and in this charging capacity scope, the polypropylene consumption is few more, and the polypropylene particle diameter that obtains is more little.
Organic solvent is selected in hydrochloric ether and aromatic solvent, as chloroform and benzene etc.These solvents can both dissolve polypropylene at a certain temperature.
Pore-creating agent is selected in nonionic surface active agent, requires tensio-active agent well to dissolve each other with the organic solvent that adopts, as sorbester p17.The consumption of pore-creating agent is 0.1-10% of an organic solvent quality, and in this amount ranges, the pore-creating agent of interpolation is many more, and the particulate aperture and the particle diameter that obtain are more little.The mechanism of action of pore-creating agent is as follows: in polypropylene solution, pore-creating agent is adsorbed on the polypropylene molecular chain, when solution cooling crystalling propylene is separated out, the space steric effect that pore-creating agent forms not only can be grown by the impact polypropylene crystalline, formation has the crystal of defective, but also can disturb whole block between the crystal, thereby form the porous particulate.
The mixing of solvent among polypropylene solution among the reactor A and the reactor B can be that still A solution changes among the still B, also can be that still B solvent changes among the still A, its objective is mixeding liquid temperature is reduced to 50 ℃-70 ℃ rapidly, separates out porous polypropylene microparticle.
The organic solvent that contains porous polypropylene microparticle mixes slurry, can adopt the method for press filtration, vacuum filtration or centrifugation to carry out liquid-solid separation, not oozing organic solvent after separating effect is piled up with porous polypropylene microparticle is minimum requirements, and the organic solvent of separating is applied mechanically after reclaiming.
The porous polypropylene microparticle filter cake is 40-90 ℃ in temperature, vacuum tightness vacuum-drying under 0.02-0.09MPa.The organic solvent condensation that is evaporated is applied mechanically after reclaiming.
The preparation method of porous polypropylene microparticle of the present invention is the industrialized preparing process that the steps such as vacuum-drying with porous polypropylene microparticle constitute that separates of being separated out small porous particle, porous polypropylene microparticle and organic solvent by preparation, dissolving, the cooling of polypropylene solution, polypropylene crystallization in organic solvent of polypropylene in organic solvent of the organic solvent that contains pore-creating agent.The present invention can be according to the different requirements of product, the concentration of pore-creating agent in the mass ratio of adjusting polypropylene and organic solvent and the organic solvent, and making specific surface area is 2-130m
2/ g, the aperture between 100-200nm, the porous polypropylene microparticle finished product of particle diameter between 1-10 μ m.This product can be used for preparing polymer polymeric adsorbent, modified resin, and as the raw materials for production of water method Chlorinated Polypropylene III etc.
Description of drawings
The overall electromicroscopic photograph of the porous polypropylene microparticle of Fig. 1: embodiment 1 preparation.
The local electromicroscopic photograph of the porous polypropylene microparticle of Fig. 2: embodiment 1 preparation.
Embodiment
Below the present invention will be described in more detail by specific embodiment.Embodiment only is to a kind of explanation of the present invention, and is not construed as limiting the invention.Embodiment is the practical application example, is easy to grasp and checking for those skilled in the art.If make certain change on basis of the present invention, its essence does not exceed scope of the present invention so.
Embodiment 1:
In the enamel reaction still A of 2000L and B, all add the chloroform of 800L and the sorbester p17 of 6kg, open and stir, sorbester p17 is dissolved in the chloroform uniformly.Then, in reactor A, drop into isotactic or syndiotactic polypropylene 36kg, elevated temperature to 100 ℃-120 ℃ gradually under condition of stirring, and be incubated 1 hour, make polypropylene be dissolved in fully and form polypropylene solution in the chloroform.In reactor A, in the material insulation, in the chuck of reactor B, feed recirculated cooling water, make the solution temperature in the still remain on below 20 ℃ standby.
After the insulation of polypropylene solution finishes among the reactor A, solution is maintained under the holding temperature, then, open reactor A bottom valve, the depended on pressure difference changes polypropylene solution the reactor B over to from reactor B bottom through pipeline.Under condition of stirring, the solution among polypropylene solution and the reactor B mixes and cools to rapidly below 70 ℃, and polypropylene decrease temperature crystalline in mixing solutions is separated out small porous particle and formed liquid-solid mixed slurry.
After mixed slurry among the question response still B is cooled to room temperature, carry out liquid-solid separation by totally-enclosed whizzer, isolated chloroform recovery set is used.Then, the porous polypropylene microparticle of surface drying is sent into vacuum drying oven, 60 ℃, vacuum tightness 0.09MPa is following carries out vacuum-drying, removes chloroform remaining in the hole, making specific surface area is 90-130m
2/ g, the aperture between 150-200nm, the porous polypropylene microparticle finished product of particle diameter between 4-8 μ m.The chloroform condensation that is evaporated is applied mechanically after reclaiming.
Embodiment 2:
In the enamel reaction still A of 2000L and B, all add the chloroform of 800L and the sorbester p17 of 60kg, open and stir, sorbester p17 is dissolved in the chloroform uniformly.Then, in reactor A, drop into isotactic or syndiotactic polypropylene 360kg, elevated temperature to 110 ℃-120 ℃ gradually under condition of stirring, and be incubated 2 hours, make polypropylene be dissolved in fully and form polypropylene solution in the chloroform.In reactor A, in the material insulation, in the chuck of reactor B, feed recirculated cooling water, make the solution temperature in the still remain on below 20 ℃ standby.
After the insulation of polypropylene solution finishes among the reactor A, solution is maintained under the holding temperature, then, open reactor A bottom valve, the depended on pressure difference changes polypropylene solution the reactor B over to from reactor B bottom through pipeline.Under condition of stirring, the solution among polypropylene solution and the reactor B mixes and cools to rapidly below 70 ℃, and polypropylene decrease temperature crystalline in mixing solutions is separated out small porous particle and formed liquid-solid mixed slurry.
After mixed slurry among the question response still B is cooled to room temperature, carry out liquid-solid separation by the method for vacuum filtration, isolated chloroform recovery set is used.Then, the porous polypropylene microparticle of surface drying is sent into vacuum drying oven, carry out vacuum-drying under 50 ℃, vacuum tightness 0.07MPa, remove chloroform remaining in the hole, making specific surface area is 50-90m
2/ g, the aperture between 120-160nm, the porous polypropylene microparticle finished product of particle diameter between 6-10 μ m.The chloroform condensation that is evaporated is applied mechanically after reclaiming.
Embodiment 3:
In the enamel reaction still A of 2000L and B, all add the chloroform of 800L and the sorbester p17 of 12kg, open and stir, sorbester p17 is dissolved in the chloroform uniformly.Then, in reactor A, drop into isotactic or syndiotactic polypropylene 120kg, elevated temperature to 110 ℃-120 ℃ gradually under condition of stirring, and be incubated 2 hours, make polypropylene be dissolved in fully and form polypropylene solution in the chloroform.In reactor A, in the material insulation, in the chuck of reactor B, feed recirculated cooling water, make the solution temperature in the still remain on below 20 ℃ standby.
After the insulation of polypropylene solution finishes among the reactor A, solution is maintained under the holding temperature, then, open reactor A bottom valve, the depended on pressure difference changes polypropylene solution the reactor B over to from reactor B bottom through pipeline.Under condition of stirring, the solution among polypropylene solution and the reactor B mixes and cools to rapidly below 70 ℃, and polypropylene decrease temperature crystalline in mixing solutions is separated out small porous particle and formed liquid-solid mixed slurry.
After mixed slurry among the question response still B is cooled to room temperature, carry out liquid-solid separation by the method for press filtration, isolated chloroform recovery set is used.Then, the porous polypropylene microparticle of surface drying is sent into vacuum drying oven, carry out vacuum-drying under 40 ℃, vacuum tightness 0.06MPa, remove chloroform remaining in the hole, making specific surface area is 80-110m
2/ g, the aperture between 140-180nm, the porous polypropylene microparticle finished product of particle diameter between 5-9 μ m.The chloroform condensation that is evaporated is applied mechanically after reclaiming.
Embodiment 4:
In the enamel reaction still A of 2000L and B, all add the benzene of 800L and the sorbester p17 of 6kg, open and stir, sorbester p17 is dissolved in the benzene uniformly.Then, in reactor A, drop into isotactic or syndiotactic polypropylene 36kg, elevated temperature to 110 ℃-120 ℃ gradually under condition of stirring, and be incubated 2 hours, make polypropylene be dissolved in fully and form polypropylene solution in the benzene.In reactor A, in the material insulation, in the chuck of reactor B, feed recirculated cooling water, make the solution temperature in the still remain on below 20 ℃ standby.
After the insulation of polypropylene solution finishes among the reactor A, maintain solution under the holding temperature and maintenance strong mixing condition, then, with pump the low-temperature solvent in the reactor B is added rapidly among the reactor A, the temperature of polypropylene mixing solutions is reduced to rapidly below 70 ℃, and polypropylene is separated out porous polypropylene microparticle because of decrease temperature crystalline and is formed liquid-solid mixed slurry in mixing solutions.
After mixed slurry is cooled to room temperature among the question response still A, carry out liquid-solid separation by totally-enclosed whizzer, isolated benzene recovery set is used.Then, the porous polypropylene microparticle of surface drying is sent into vacuum drying oven, carry out vacuum-drying under 70 ℃, vacuum tightness 0.07MPa, remove benzene remaining in the hole, making specific surface area is 2-20m
2/ g, the aperture between 120-150nm, the porous polypropylene microparticle finished product of particle diameter between 1-5 μ m.The benzene condensation that is evaporated is applied mechanically after reclaiming.
Embodiment 5:
All add the benzene of 800L in the enamel reaction still A of 2000L and B, reactor A also adds the polyoxyethylenated castor oil of 0.64kg, opens and stirs, and polyoxyethylenated castor oil is dissolved in the benzene uniformly.Then, in reactor A, drop into isotactic or syndiotactic polypropylene 13kg, elevated temperature to 140 ℃-150 ℃ gradually under condition of stirring, and be incubated 10 hours, make polypropylene be dissolved in fully and form polypropylene solution in the benzene.In reactor A, in the material insulation, in the chuck of reactor B, feed recirculated cooling water, make solution temperature in the still remain on 20 ℃ standby.
After the insulation of polypropylene solution finishes among the reactor A, solution is maintained under the holding temperature, then, open reactor A bottom valve, the depended on pressure difference changes polypropylene solution the reactor B over to from reactor B bottom through pipeline.Under condition of stirring, the solution among polypropylene solution and the reactor B mixes and cools to rapidly below 70 ℃, and polypropylene decrease temperature crystalline in mixing solutions is separated out small porous particle and formed liquid-solid mixed slurry.
After mixed slurry among the question response still B is cooled to room temperature, carry out liquid-solid separation by the method for vacuum filtration, isolated benzene recovery set is used.Then, the porous polypropylene microparticle of surface drying is sent into vacuum drying oven, carry out vacuum-drying under 90 ℃, vacuum tightness 0.01MPa, remove chloroform remaining in the hole, making specific surface area is 15-35m
2/ g, the aperture between 100-120nm, the porous polypropylene microparticle finished product of particle diameter between 1-5 μ m.The chloroform condensation that is evaporated is applied mechanically after reclaiming.
Embodiment 6:
The benzene that in the enamel reaction still A of 2000L and B, all adds 800L,, reactor A also adds the sorbester p17 of 64kg, opens and stirs, and sorbester p17 is dissolved in the benzene uniformly.Then, in reactor A, drop into isotactic or syndiotactic polypropylene 130kg, elevated temperature to 110 ℃-120 ℃ gradually under condition of stirring, and be incubated 2 hours, make polypropylene be dissolved in fully and form polypropylene solution in the benzene.In reactor A, in the material insulation, in the chuck of reactor B, feed recirculated cooling water, make the solution temperature in the still remain on below 20 ℃ standby.
After the insulation of polypropylene solution finishes among the reactor A, solution is maintained under the holding temperature, then, open reactor A bottom valve, the depended on pressure difference changes polypropylene solution the reactor B over to from reactor B bottom through pipeline.Under condition of stirring, the solution among polypropylene solution and the reactor B mixes and cools to rapidly below 70 ℃, and polypropylene decrease temperature crystalline in mixing solutions is separated out small porous particle and formed liquid-solid mixed slurry.
After mixed slurry among the question response still B is cooled to room temperature, carry out liquid-solid separation by the method for press filtration, isolated chloroform recovery set is used.Then, the porous polypropylene microparticle of surface drying is sent into vacuum drying oven, carry out vacuum-drying under 40 ℃, vacuum tightness 0.07MPa, remove chloroform remaining in the hole, making specific surface area is 30-60m
2/ g, the aperture between 110-140nm, the porous polypropylene microparticle finished product of particle diameter between 1-5 μ m.The chloroform condensation that is evaporated is applied mechanically after reclaiming.
Claims (5)
1. the preparation method of a porous polypropylene microparticle is characterized in that, may further comprise the steps:
1) with the polypropylene is raw material, it is dropped among the reactor A, the organic solvent that contains the pore-creating agent sorbester p17 is housed in the still in advance, this pore-creating agent is 0.01%～10% of an organic solvent quality, under whipped state, material to 100-150 ℃ in the heating kettle is incubated 1-10 hours then, polypropylene is dissolved in fully forms polypropylene solution in the organic solvent, polyacrylic charging capacity is 2-30% of an organic solvent quality;
2) be equipped with in advance in the reactor B with reactor A in form identical organic solvent, its temperature is controlled at below the room temperature, under stirring action, with the rapid thorough mixing of solvent among polypropylene solution among the reactor A and the reactor B, the mixture temperature is reduced to below 70 ℃, again this mixture temperature is reduced to room temperature;
3) carry out liquid-solid separation to mixing slurry, remove the organic solvent on porous polypropylene microparticle surface;
4) porous polypropylene microparticle that obtains after the liquid-solid separation is sent into vacuum drying oven, remove organic solvent remaining in the hole, resulting porous polypropylene microparticle specific surface area is 2-130m
2/ g, the aperture is between 100-200nm, and particle diameter is between 1-10 μ m.
2. the preparation method of porous polypropylene microparticle according to claim 1, it is characterized in that: described pp material is isotactic or syndiotactic polypropylene, molecular weight is 20,000-200,000.
3. the preparation method of porous polypropylene microparticle according to claim 1, it is characterized in that: described organic solvent is hydrochloric ether or aromatic hydrocarbons.
4. the mixing of solvent among the preparation method of preparation porous polypropylene microparticle according to claim 1, the polypropylene solution that it is characterized in that reactor A in this production method and reactor B is that still A solution changes among the still B, and perhaps still B solvent changes among the still A.
5. the preparation method of porous polypropylene microparticle according to claim 1, it is characterized in that: the drying temperature of porous polypropylene microparticle is 40-90 ℃ in the step 4), vacuum tightness is 0.01-0.09MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100626566A CN100463938C (en) | 2007-01-12 | 2007-01-12 | Preparation process of porous polypropylene microparticle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100626566A CN100463938C (en) | 2007-01-12 | 2007-01-12 | Preparation process of porous polypropylene microparticle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN100999597A CN100999597A (en) | 2007-07-18 |
| CN100463938C true CN100463938C (en) | 2009-02-25 |
Family
ID=38258427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100626566A Expired - Fee Related CN100463938C (en) | 2007-01-12 | 2007-01-12 | Preparation process of porous polypropylene microparticle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100463938C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105707980B (en) * | 2016-03-08 | 2020-02-04 | 云南中烟工业有限责任公司 | Preparation method of cellulose acetate open-cell microporous foam material filter tip spice rod |
| KR20230152081A (en) * | 2021-03-30 | 2023-11-02 | 아사히 가세이 가부시키가이샤 | Resin pellet composition and method for producing the same, and method for producing microporous membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4247498A (en) * | 1976-08-30 | 1981-01-27 | Akzona Incorporated | Methods for making microporous products |
| JPH03185028A (en) * | 1989-12-14 | 1991-08-13 | Junjiro Aoki | Production of cellular polymer microsphere |
-
2007
- 2007-01-12 CN CNB2007100626566A patent/CN100463938C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4247498A (en) * | 1976-08-30 | 1981-01-27 | Akzona Incorporated | Methods for making microporous products |
| JPH03185028A (en) * | 1989-12-14 | 1991-08-13 | Junjiro Aoki | Production of cellular polymer microsphere |
Non-Patent Citations (2)
| Title |
|---|
| 聚丙烯加热改性制备大孔吸附树脂的工艺及其应用. 郑旭煦，殷中意，唐金晶，陈小军，牟志容.化学研究与应用，第15卷第6期. 2003 |
| 聚丙烯加热改性制备大孔吸附树脂的工艺及其应用. 郑旭煦，殷中意，唐金晶，陈小军，牟志容.化学研究与应用，第15卷第6期. 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100999597A (en) | 2007-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Feng et al. | Fabrication of a hydrogen‐bonded organic framework membrane through solution processing for pressure‐regulated gas separation | |
| Rose et al. | MOF processing by electrospinning for functional textiles | |
| Moreton et al. | High MOF loading in mixed-matrix membranes utilizing styrene/butadiene copolymers | |
| JP2019210478A (en) | Cyclodextrin polymer and method for producing same | |
| CN100463938C (en) | Preparation process of porous polypropylene microparticle | |
| JP2012072534A (en) | Hollow fiber porous body of natural zeolite, zeolite membrane composite porous body and method for manufacturing the same | |
| CN112023981A (en) | Covalent triazine organic framework material and preparation method and application thereof | |
| US11870058B2 (en) | Method of forming a composition and the composition formed therefrom | |
| CN105883750A (en) | Mesoporous carbon and preparation method thereof | |
| CN112705053A (en) | Preparation method and application of acid-resistant zeolite molecular sieve membrane | |
| CN102050461A (en) | Multi-level structure mesoporous zeolite material and preparation method thereof | |
| CN108314788B (en) | Method for preparing copolymer/HKUST-1 hybrid material by in-situ polymerization | |
| KR100870344B1 (en) | Refining Method and Apparatus for High Purity 2,6-Naphthalene Dicarboxylic acid | |
| Li et al. | Surface Engineering Layered Metal–Organic Framework to Enhance Processability and Stability in Water | |
| CN105664860A (en) | MOF type hierarchical porous material IPD-mesonMOF-12 | |
| CN110698326B (en) | Synthesis method of 1-hydroxypyrene | |
| JP2008208277A (en) | Method for producing organic compound crystal | |
| Zhu et al. | Shape‐Controlled Synthesis of Covalent Organic Frameworks Enabled by Polymerization‐Induced Phase Separation | |
| CN103275251B (en) | Preparation method for chlorinated polypropylene resin | |
| CN113274980B (en) | Vanadium oxide-organic molecular cage-based porous liquid and preparation method and application thereof | |
| EA039625B1 (en) | Method for the multi-seeding synthesis of zeolite crystals with controlled grain size | |
| CN113272053A (en) | Metal-organic framework extrusion material and manufacturing method thereof | |
| JP2007512404A (en) | Very low density polymer mousse and method of manufacture | |
| JP2014105130A (en) | Silica structure and method for manufacturing the same | |
| CN114195608B (en) | Purification method of Suzuki reaction monomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090225 Termination date: 20140112 |