CN100572402C - Preparation method of linear polyolefin porous materials - Google Patents
Preparation method of linear polyolefin porous materials Download PDFInfo
- Publication number
- CN100572402C CN100572402C CNB200610049726XA CN200610049726A CN100572402C CN 100572402 C CN100572402 C CN 100572402C CN B200610049726X A CNB200610049726X A CN B200610049726XA CN 200610049726 A CN200610049726 A CN 200610049726A CN 100572402 C CN100572402 C CN 100572402C
- Authority
- CN
- China
- Prior art keywords
- polymerization
- polyoxyethylene glycol
- preparation
- precipitation
- monomer
- 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 a kind of preparation method of linear polyolefin porous materials.Polymerization single polymerization monomer adopts olefin monomer, as esters of acrylic acid, vinylbenzene, vinyl cyanide, vinyl acetate and functional monomer, based on polyoxyethylene glycol, or dissolve in the mixed solvent of compatibility appropriate solvent (or precipitation agent) composition, under azo class and peroxide organic initiators, suitable temp and atmosphere, carry out radical polymerization, but be different from solution polymerization, also be different from precipitation polymerization, exist polyreaction to promote the characteristics that are separated, after be solidified into piece, remove polyoxyethylene glycol etc., obtain line type polyolefin cellular material.The polymer porous material that makes is continuously whole, and pore structure is the duct of open communication, and mean pore size is at micron to nano grade, and the pore structure size can be regulated and control by polyoxyethylene glycol (PEG) and blending agent.Chemically modified is carried out in the duct, can be widely used in separation, filtration, absorption, chelating and the intelligent membrane material material etc. of industries such as instrumental analysis, water treatment, biological medicine.
Description
Technical field
The present invention relates to a kind of method of polymer of linear olefin porous material.
Background technology
In recent years, the technology of preparing of polymer porous material has obtained develop rapidly, developed the multiple moulding process and the method that can in polymeric matrix, produce small hole, as phase separation method, stretching method, nuclear track method, sintering process, thermal decomposition method, suspension polymerization, the macromolecular structure template, the colloidal crystal template, little foaming technique or the like, the material that adopts these method preparations is because the vesicular structure of its bigger serface, has very important using value in a lot of fields, comprise the insulation lagging material, wrapping material, sorbing material, the sustained release material, the skeleton equivalent material, aspects such as chromatogram integral post material become a class important function macromolecular material.
Continuity along with scientific technological advance, high-molecular porous material has been proposed higher technical requirements, as controllability of the functionalization of porous material, environment friendly, microporous structure etc., satisfy these requirements, must work out and have more versatility and variable preparation method, and develop a greater variety of new polymers porous materials.
As everyone knows; radical polymerization is the effective ways of the various vinyl polymers of scale operation; about vinyl polymer more than 70% is all by the incompatible realization of radical polymerization; its advantage is: multiple alkenyl monomer is especially had very high homopolymerization and copolymerization activity to the monomer that has polarity and non-defencive function group; the polymerizing condition gentleness; less demanding to reaction system very helps suitability for industrialized production.Just at present, the radical polymerization that can prepare porous material mainly is suspension polymerization, but granular disintegration is generally had in suspension polymerization, it is so-called porous microsphere, be difficult to obtain the block porous polymer material of whole successive, some other method such as phase separation method, stretching method are by physical means existing polymkeric substance to be made porous membrane, though and little foaming technique can obtain blocky porous material, but need depend on special physical process (as the supercritical co gasification), the technology application surface is narrow.In general, this field lack a kind of not only convenient but also flexibly method prepare the block porous polymer material of whole successive.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of linear polyolefin porous materials at existing background technology, just can obtain the polymer porous material of arbitrary shape in this way, they have certain mechanical strength, low density and high specific surface area, as long as regulate the composition and the ratio of polymerisation medium, a lot of olefinic monomers can be aggregated into desired porous block polymkeric substance, this method tool has an enormous advantage, it is flexible and changeable, simple and easy to do, and has the speciality of the how empty material of preparation arbitrary shape.
The present invention solves the problems of the technologies described above the technical scheme that is adopted, a kind of preparation method of linear polyolefin porous materials, the steps include: to add the olefin monomer that contains initiator, dissolving obtains settled solution in medium, under suitable temp and atmosphere, carry out polyreaction, it is characterized in that described medium adopts polyoxyethylene glycol as medium, described polyreaction is in the medium of polyoxyethylene glycol or by regulating solvent or the composition of precipitation agent and the ratio of solvent or precipitation agent and medium polyoxyethylene glycol, change above polymerization methods, the olefinic monomer polymerization is not neither also carried out in the precipitation polymerization mode with solution polymerization, but obtain the bulk polymer porous material by the controlled polymerization methods that is separated, the described controlled polymerization methods that is separated, be that phenomenon of phase separation is arranged in polymerization process, in the polymerization process, precipitation does not form, form the frozen glue shape block of illiquidity after the polymerization, medium can spontaneously not separated out from block and is standard, at last the bulk polymer porous material is put into water, remove polyoxyethylene glycol and solvent or precipitation agent, obtain line type polyolefin cellular material.
Described polyreaction is a precipitation polymerization, the solvent of corresponding selective polymer, with the polyoxyethylene glycol compatibility, polyreaction is reacted in the controlled mode of being separated of ceitical region, solvent and its ratio are selected and can be obtained by experiment, usual solvents adopts as N,N-DIMETHYLACETAMIDE, dimethyl formamide or water-soluble solvents such as N-Methyl pyrrolidone, dioxane, is convenient to washing and removes, and the weight ratio of polyoxyethylene glycol and solvent was good at 2.5: 1 to 10: 1; It is solution polymerization, the precipitation agent of corresponding selective polymer, with the polyoxyethylene glycol compatibility, polyreaction is reacted in the controlled mode of being separated of ceitical region, solvent and its ratio are selected and can be obtained by experiment, and usually, precipitation agent can adopt the inorganic salt in the polyoxyethylene glycol of may be dissolved in as lithium chloride, thiocyanation salt, perchlorate, three fluoro sulfonates or iodized salt, the weight ratio of precipitation agent and polyoxyethylene glycol was good at 1: 10 to 1: 20 with lithium chloride.
Described controlled being separated can be summarized by experiment, do not occur precipitation forms more than 6 hours or is not that to keep solution state be foundation with polymerization, is convenient to the actual production operation.
Olefin monomer among the described preparation method is important free yl polymerizating monomer commonly used.As: esters of acrylic acid such as methyl acrylate (MA), methyl methacrylate (MMA), butyl methacrylate (BMA) etc., vinylbenzene (S), vinyl cyanide (AN), vinyl acetate and functional monomer such as Hydroxyethyl acrylate, hydroxypropyl acrylate and acrylamide etc.
Initiator among the described preparation method is traditional radical polymerization initiator, no particular requirement.Can select azo class and peroxide organic initiators for use.Select activation energy or suitable initiator of transformation period according to polymerization temperature, make free radical formation speed and rate of polymerization moderate.As Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide (BPO) etc.
The polymer porous material that described preparation method obtains, its structure is the duct of open communication, and mean pore size is at micron or submicron order, and the pore structure size can be regulated and control by polyoxyethylene glycol (PEG) and blending agent.The molecular weight of polyoxyethylene glycol is more suitable between 400-2000, as optional PEG400, PEG600, PEG1000, PEG1500, PEG2000, is excellent with PEG1000 especially.
Described line type polyolefin cellular material can be made arbitrary shape, contains the group that can react in a large number, is fit to that number of chemical is carried out in the duct and modifies with functionalization.Separation, filtration, absorption, the chelating that can be widely used in industries such as instrumental analysis, water treatment, biological medicine.As fixing, the cell cultures of micro-filtration and intelligent film, heavy metal removal, chromatogram integral post stationary phase, enzyme, medicament slow release, chemical sensor etc.
Compare with the technology of preparing of existing polymer porous material, the invention has the advantages that:
(1) the preparation forming technique is simple, and shape is not limit.Plastic polymer materials is extensive, preparation method's highly versatile.
It mainly is dielectric solvent with the polyoxyethylene glycol, or according to polarity compatibility appropriate solvent (or precipitation agent) composition mixed solvent, basically do not change other reaction conditions of olefin monomer radical polymerization, as temperature and atmosphere, easy to operate, moulding is simple, applicable to the big class of line type polyolefin radical polymerization, forms porous material.
(2) line type polyolefin radical polymerization aperture of porous material of the present invention is evenly distributed, and the aperture is adjustable, good reproducibility.
Line type polyolefin Raolical polymerizable of the present invention is different from solution polymerization, also is different from precipitation polymerization, and being separated of producing gradually in polymerization process is to take place with controllable mode, avoided the formation of polymer precipitation.The line type polyolefin radical polymerization porous material of making is continuously whole, and the aperture is easy to control.
(3) line type polyolefin cellular material of the present invention can be used as the solid support material of preparation functionalization, intelligent material.
There is the group that can react in a large number in the line type polyolefin cellular material chemical structure of the present invention, can carries out number of chemical to the duct and modify, be convenient to further functionalization, intellectuality.The separation, filtration, absorption, the chelating that are widely used in industries such as instrumental analysis, water treatment, biological medicine.As fixing, the cell cultures of micro-filtration and intelligent film, heavy metal removal, chromatogram integral post stationary phase, enzyme, medicament slow release, chemical sensor etc.
Description of drawings
The synoptic diagram of Fig. 1 controlled radical polymerization mode that is separated of the present invention
The pore forming process of Fig. 2 line type polyolefin cellular material of the present invention and mechanism synoptic diagram
The sem photograph of the line type polyolefin cellular material structure that forms among Fig. 3 embodiment 1
Embodiment
Following examples describe in further detail the present invention.
Slowly add the olefin monomer that contains initiator: 10 gram vinylbenzene (S) dissolve in 30 gram cetomacrogol 1000s and 10 gram dioxane media, obtain settled solution, 60 ℃ of isothermal reaction polymerizations at least 6 hours, soltion viscosity constantly increases, and engenders phenomenon of phase separation then, and system becomes oyster white gradually when being separated, be condensed into frozen glue shape block at last, it is put into water, dissolve and remove polyoxyethylene glycol etc., obtain line type polyolefin cellular material.Polymerization process such as decomposition of initiator activation energy is too high or the transformation period is long, then rate of decomposition is low excessively, and polymerization time will be prolonged.But activation energy is crossed low or the transformation period is too short, then causes too fastly, and difficult control of temperature might cause implode; Or the initiator premature decomposition finishes.Promptly stop polymerization in the low-conversion stage.Generally should select transformation period and polymerization time with the order of magnitude or suitable initiator.Present embodiment selects for use a small amount of dibenzoyl peroxide (BPO) to be initiator.
Its pore structure as shown in Figure 2, the aperture is as shown in table 1.
Comparative example 1
Slowly the 10 gram vinylbenzene (S) that contain initiator dibenzoyl peroxide (BPO) are added in the 40 gram cetomacrogol 1000s, obtain settled solution,, form precipitation polymerization, can not obtain porous material 60 ℃ of isothermal reactions.
Comparative example 2
Slowly the 10 gram vinylbenzene (S) that contain initiator dibenzoyl peroxide (BPO) are added in the 40 gram benzene, obtain settled solution,, form solution polymerization, can not obtain porous material 60 ℃ of isothermal reactions.
Slowly add the olefin monomer that contains initiator dibenzoyl peroxide (BPO): 10 gram vinylbenzene (S) dissolve in 30 gram cetomacrogol 1000s and dioxane blending agent, obtain settled solution, 60 ℃ of isothermal reaction polymerizations at least 6 hours, soltion viscosity constantly increases, and engenders phenomenon of phase separation then, forms white gels, final curing becomes piece, solid is put into water, dissolve and remove polyoxyethylene glycol etc., obtain line type polyolefin cellular material.The weight of dioxane is respectively 6 grams, 8 grams, 12 grams, and all the other conditions and operation are identical with embodiment 1, make corresponding line type polyolefin cellular material, and the aperture is as shown in table 1.
Table 1:
| |
|
Embodiment 3 | |
|
| PEG1000(g) | 30 | 30 | 30 | 30 |
| Dioxane (g) | 10 | 6 | 8 | 12 |
| Mean pore size (μ m) | 0.65 | 0.95 | 0.78 | 0.45 |
Slowly add the olefin monomer that contains initiator Diisopropyl azodicarboxylate (AIBN): 10 gram vinyl cyanide (AN) dissolve in 30 gram cetomacrogol 1000s and 8 gram dimethyl formamide (DMF) media, obtain settled solution, 65 ℃ of isothermal reaction polymerizations at least 6 hours, soltion viscosity constantly increases, and engenders phenomenon of phase separation then, forms white gels, final curing becomes piece, solid is put into water, dissolve and remove polyoxyethylene glycol etc., obtain line type polyolefin cellular material.Mean pore size is 0.45 μ m.
Comparative example 3
Slowly the 10 gram vinyl cyanide (AN) that contain initiator Diisopropyl azodicarboxylate (AIBN) are added in the 40 gram cetomacrogol 1000s, obtain settled solution,, form precipitation polymerization, can not obtain porous material 65 ℃ of isothermal reactions.
Slowly add the olefin monomer that contains initiator Diisopropyl azodicarboxylate (AIBN): 10 gram methyl acrylates (MA) dissolve in the mixed solvent that 40 gram 7wt%LiCl/PEG400 form, obtain settled solution, 60 ℃ of isothermal reaction polymerizations at least 6 hours, soltion viscosity constantly increases, and engenders phenomenon of phase separation then, forms white gels, final curing becomes piece, solid is put into water, dissolve and remove poly(oxyethylene glycol) 400 etc., obtain line type polyolefin cellular material.Mean pore size is 0.35 μ m.
Comparative example 4
Slowly the 10 gram methyl acrylates (MA) that contain initiator Diisopropyl azodicarboxylate (AIBN) are added in the 40 gram cetomacrogol 1000s, obtain settled solution,, form solution polymerization, can not obtain porous material 60 ℃ of isothermal reactions.
Slowly add the olefin monomer that contains initiator Diisopropyl azodicarboxylate (AIBN): 10 gram methyl methacrylates (MMA) dissolve in the mixed solvent that 35 gram 7wt%LiCl/PEG400 form, obtain settled solution, 60 ℃ of isothermal reaction polymerizations at least 6 hours, engender phenomenon of phase separation, form white gels, final curing becomes piece, and solid is put into water, dissolving is also removed poly(oxyethylene glycol) 400 etc., obtains line type polyolefin cellular material.Mean pore size is 0.45 μ m.
Slowly add the olefin monomer that contains initiator Diisopropyl azodicarboxylate (AIBN): 10 gram butyl methacrylate are dissolved in the mixed solvent that 36 gram 7wt%LiCl/PEG400 form, obtain settled solution, 60 ℃ of isothermal reaction polymerizations at least 6 hours, engender phenomenon of phase separation, form white gels, final curing becomes piece, and solid is put into water, dissolving is also removed poly(oxyethylene glycol) 400 etc., obtains line type polyolefin cellular material.Mean pore size is 0.30 μ m.
From embodiment 6～8 and comparative example as can be seen, be separated though use poly(oxyethylene glycol) 400 that polymerization system is produced separately, system becomes solution polymerization, adds behind the anhydrous LiCl of 7wt% resulting viscous solution and just can produce and be separated.The existence of LiCl has reduced the solubility property of poly(oxyethylene glycol) 400, makes it can't be as the good solvent of polymkeric substance.The molecular weight that medium is described has very big influence to polymerization, and then the mean pore size of impact polymer porous material.The polymerization mechanism of line type polyolefin radical polymerization porous material of the present invention meets the mechanism of free-radical polymerization of common olefin monomer, but polymerization methods is a kind of new radical polymerization embodiment between solution polymerization and precipitation polymerization, is based on a kind of novel controlled radical polymerization mode that is separated.As shown in Figure 1, the symbol meaning is that 1. vinylbenzene, 2. vinyl cyanide, 3. alpha-methyl styrenes, 4. methyl acrylates, 5. methyl methacrylates, 6. ethyl propenoates, 7. methacrylic acid 2-hydroxyl ethyl esters, 8. butyl methacrylate 1 ' 2 ' 3 ' 4 ' 5 ' 6 ' 7 ' 8 ' are for after regulating polymerisation medium among the figure, the controlled polymerization methods that is separated takes place in corresponding monomer, form the ceitical region, common monomer polymerization, polymkeric substance that generates and monomer do not dissolve each other the mode with precipitation polymerization are carried out, as the polymerization of common monomer 1,2,3; Polymkeric substance and monomer or polymerisation medium dissolve each other the mode with solution polymerization are carried out, as the polymerization of common monomer 4,5,6,7,8.Experiment is found, need only the composition and the ratio of regulating the polymerisation medium polyoxyethylene glycol or containing the polyethylene glycol medium of solvent (or precipitation agent), can change above polymerization methods, a lot of olefinic monomer polymerizations are not neither also carried out in the precipitation polymerization mode with solution polymerization, but in the ceitical region (shadow region among the figure), obtain the bulk polymer porous material by the controlled radical polymerization mode that is separated, as this zone 1 ', 2 ', 3 ', 4 ', 5 ', 6 ', 7 ', 8 ' shown in.Ceitical region of the present invention can be summed up by experiment, does not occur precipitation forms more than 6 hours or is not that to keep solution state be foundation with polymerization.Different polymerisation medium content and proportioning influence outward appearance, rerum natura and the pore property of ceitical region interpolymer material.This mode can obtain the whole successive bulk polymer porous material of arbitrary shape, and they have certain mechanical strength, low density and high specific surface area.
The pore forming process of line type polyolefin radical polymerization porous material of the present invention and pore-forming mechanism as shown in Figure 2, the available mechanism explain that is separated.The polyreaction of Fa Shenging at a certain temperature, the polymkeric substance of generation is insoluble to reaction mixture, causes polymer precipitation, is separated.Polyoxyethylene glycol is except the solvent as polymerization reaction monomer, also as the high molecular precipitation agent of polyreaction, has thickening viscosifying action preferably, and satisfactory stability, make the abundant polymerization of system and keep the hydrophilic/hydrophobic balance, when polyreaction proceeded to a certain degree, solvent was transformed into precipitation agent, and the back produces phenomenon of phase separation being aggregated to a certain degree to force system.Relative pore-creating agent, monomer is the good solvent of polymkeric substance, therefore in sedimentary polymkeric substance (nuclear), monomeric concentration is higher than whole polymerization system, its reaction rate accelerates, what promptly nuclear was grown up speeds up.The skeleton that has just constituted vesicular structure is assembled in the internuclear generation of different size.The coarsening rate of nuclear is fast more, formed porous material, the possibility height that macropore generates.Equally, be separated and take place more early, the aperture is big more.Fig. 3 is the sem photograph (wherein Bai Se part is a polymkeric substance, and the part of black is a hole) of prepared porous material, and this porous material is assembled by polymer globules and formed as can be seen, and internal structure evenly and continuously; Polymer globules connects mutually and part is gathered into bigger bunch, bunch has formed the skeleton structure of gel, bunch and bunch between, bead and bunch between, the irregular space between bead and the bead formed the hole of porous material.The composition of pore-creating agent and content equally can be with the mechanism explains that is separated to the influence of the pore structure of porous material, that is: the amount of the Weak solvent of contained polymkeric substance increases in the pore-creating agent, is separated in advance, easily form macropore, the amount of good solvent increases, and the hysteresis that is separated is difficult for forming macropore.Therefore, the aperture of porous material can be by changing the mean pore size that porous material was controlled and regulated to polyoxyethylene glycol content, molecular weight and blending agent proportioning and concentration in system.
Comprehensively described, know-why of the present invention is based on a kind of novel controlled radical polymerization mode that is separated.The used phase disengagement method of preparation high molecule micropore filter membrane is combined with radical polymerization, thereby obtained in polymerization process, to produce gradually the complex process that is separated, be separated is to take place with controllable mode, avoided the formation of polymer precipitation, so this is a kind of new radical polymerization embodiment between solution polymerization and precipitation polymerization.Just can obtain the polymer porous material of arbitrary shape in this way, they have certain mechanical strength, low density and high specific surface area.Experiment is found, as long as regulate the composition and the ratio of polymerisation medium, a lot of olefinic monomers can be aggregated into desired porous block polymkeric substance.Obviously, this method tool has an enormous advantage, and it is flexible and changeable, simple and easy to do, and has the speciality of the how empty material of preparation arbitrary shape, will produce promoter action to the how empty Development of Materials of polymkeric substance.
Claims (8)
1. preparation method of linear polyolefin porous materials, the steps include: to add the olefin monomer that contains initiator, dissolving obtains settled solution in medium, under temperature of reaction and atmosphere, carry out polyreaction, it is characterized in that described medium adopts polyoxyethylene glycol as medium, described polyreaction is in the medium of polyoxyethylene glycol, by regulating the composition of solvent or precipitation agent, perhaps by regulating the ratio of solvent or precipitation agent and medium polyoxyethylene glycol, change above polymerization methods, the olefinic monomer polymerization is not neither also carried out in the precipitation polymerization mode with solution polymerization, but obtain the bulk polymer porous material by the controlled polymerization methods that is separated, the described controlled polymerization methods that is separated, be that phenomenon of phase separation is arranged in polymerization process, in the polymerization process, precipitation does not form, form the frozen glue shape block of illiquidity after the polymerization, medium can spontaneously not separated out from block and is standard, at last the bulk polymer porous material is put into water, remove polyoxyethylene glycol and solvent or precipitation agent, obtain line type polyolefin cellular material.
2. preparation method according to claim 1 is characterized in that described solvent adopts N,N-DIMETHYLACETAMIDE, dimethyl formamide or N-Methyl pyrrolidone, dioxane water-soluble solvent; And precipitation agent adopts the inorganic salt in the polyoxyethylene glycol of may be dissolved in of lithium chloride, thiocyanation salt, perchlorate, three fluoro sulfonates or iodized salt.
3. preparation method according to claim 1 is characterized in that described controlled be separated by experiment sum up, and does not occur precipitation forms more than 6 hours or is not that to keep solution state be foundation with polymerization.
4. preparation method according to claim 1, it is characterized in that described polyreaction is radical polymerization, polymerization single polymerization monomer is an olefin monomer, adopt methyl acrylate, methyl methacrylate or the butyl methacrylate of esters of acrylic acid, the functional monomer who perhaps adopts vinylbenzene, vinyl cyanide, vinyl acetate or Hydroxyethyl acrylate, hydroxypropyl acrylate or acrylamide.
5. preparation method according to claim 1 is characterized in that described initiator selects azo class or peroxide oil soluble organic initiators for use.
6. preparation method according to claim 1 is characterized in that described porous material presents block whole shape continuously.
7. preparation method according to claim 1, it is characterized in that its structure of described porous material is the duct of open communication, mean pore size at micron to submicron order, the pore structure size is regulated and control by polyoxyethylene glycol PEG and blending agent, and the molecular weight of described polyoxyethylene glycol is more suitable between PEG400-2000.
8. preparation method according to claim 7, the molecular weight that it is characterized in that described polyoxyethylene glycol is optimum with PEG1000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610049726XA CN100572402C (en) | 2006-03-07 | 2006-03-07 | Preparation method of linear polyolefin porous materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610049726XA CN100572402C (en) | 2006-03-07 | 2006-03-07 | Preparation method of linear polyolefin porous materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101033272A CN101033272A (en) | 2007-09-12 |
| CN100572402C true CN100572402C (en) | 2009-12-23 |
Family
ID=38730031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610049726XA Expired - Fee Related CN100572402C (en) | 2006-03-07 | 2006-03-07 | Preparation method of linear polyolefin porous materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100572402C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418837B (en) * | 2015-12-20 | 2017-08-25 | 华南理工大学 | A kind of be separated causes the preparation method of porous super hydrophobic coating material |
-
2006
- 2006-03-07 CN CNB200610049726XA patent/CN100572402C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101033272A (en) | 2007-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jennings et al. | Block copolymer synthesis by controlled/living radical polymerisation in heterogeneous systems | |
| Sanson et al. | Synthesis of nanogels/microgels by conventional and controlled radical crosslinking copolymerization | |
| CN107056999B (en) | Preparation method of fluorine-containing porous material based on amphiphilic fluorine-containing macromolecular block substance stable high internal phase emulsion | |
| CN101735414B (en) | Porous polymer whole separating material and preparation method thereof | |
| CN102838709B (en) | Atom transferred free radical precipitation polymerization method prepares monodispersed polymer microsphere resin | |
| CN106632925A (en) | Preparation method for amphiphilic segmented copolymer with pH value and temperature sensitivities | |
| CN105037626B (en) | A kind of preparation method of the big particle diameter polymer microballoon of macropore | |
| CN103665387A (en) | Method for preparing accurate polymer network | |
| CN101591403A (en) | The preparation method of reversible addition-fragmentation chain transfer emulsion polymerization | |
| CN103435731A (en) | Preparation method of porous polymer microspheres | |
| CN113402699B (en) | Method for synthesizing block copolymer brush by utilizing microfluidics | |
| CN110804143A (en) | Method for preparing block polymer nanoparticles based on controllable free radical polymerization | |
| CN103214625A (en) | Thermo-sensitive grafted hydrogel with function of resisting protein adsorption and preparation method thereof | |
| CN101816909A (en) | Preparation method of poly(phenylethylene-acrylic acid) magnetic polymer microsphere | |
| CN104744650A (en) | Preparation and application of hybrid copolymer containing POSS (polyhedral oligomeric silsesquioxane) base | |
| CN107418125A (en) | A kind of method that multiphase polymer material is prepared using segmented copolymer latex | |
| CN104761673A (en) | Carbomer and preparation method thereof | |
| JP2021524872A (en) | High melt index thermoplastic elastomer and its manufacturing method | |
| CN100572402C (en) | Preparation method of linear polyolefin porous materials | |
| CN107236078B (en) | A kind of preparation method of flexibility soft monomer colloidal photon crystal lotion | |
| CN104628948B (en) | Acrylate-type poly-chain transfer agent as well as preparation method and application of poly-chain transfer agent in preparation of columnar polymer brush | |
| CN103394305A (en) | pH-responsive star-shaped polymer emulsifier and preparation method thereof | |
| CN109293827B (en) | Process for the preparation of bead-like cationic polyacrylamide retention aids and their use for retention of pulp slurries | |
| JP2003509549A (en) | One-step seeding polymerization to produce large polymer particles with narrow particle size distribution | |
| KR100257293B1 (en) | Method for manufacturing porous polymer particle |
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: 20091223 Termination date: 20130307 |