CN113980241A - Purification method and application of macromolecular surface modifier - Google Patents
Purification method and application of macromolecular surface modifier Download PDFInfo
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- CN113980241A CN113980241A CN202111189176.2A CN202111189176A CN113980241A CN 113980241 A CN113980241 A CN 113980241A CN 202111189176 A CN202111189176 A CN 202111189176A CN 113980241 A CN113980241 A CN 113980241A
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- surface modifier
- macromolecular surface
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- 239000004721 Polyphenylene oxide Substances 0.000 description 1
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/82—Post-polymerisation treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The invention relates to a purification method and application of a macromolecular surface modifier. The purification and application comprise: (1) dissolving a macromolecular surface modifier; (2) purifying the macromolecular surface modifier; (3) blending the macromolecular surface modifier with the matrix material; (4) and (3) preparing the modified material. According to the invention, the purified macromolecular surface modifier and the matrix material have better solubility and transparency, and the material added with the macromolecular surface modifier can obtain corresponding surface energy change and simultaneously has better stability and reusability.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a purification method and application of a macromolecular surface modifier.
Background
The macromolecular surface modifier is a polymer with the molecular weight of more than 1000, and compared with the micromolecular modifier, the macromolecular surface modifier has the advantages of multiple structures, controllable molecular weight, various functional groups, functional diversity and the like. In recent years, due to the potential industrial and commercial utility of macromolecular surface modifiers, the development of macromolecular surface modifiers of different types and structures has been pursued and extensively studied by researchers as an industrially important raw material. The macromolecular surface modifier is applied to base materials without specific surface hydrophobic, oleophobic, hydrophilic and lipophilic properties, and is used for carrying out surface modification on the base materials to obtain corresponding modified materials.
In the prior art, common polymerization methods for synthesizing macromolecular surface modifiers include ring-opening polymerization, Group Transfer Polymerization (GTP), Atom Transfer Radical Polymerization (ATRP), and reversible addition fragmentation-chain transfer polymerization (RAFT). The invention CN103131079B discloses a microporous membrane and a battery diaphragm containing the microporous membrane. The microporous membrane takes polyolefin as a main raw material, and macromolecular surface modifiers are dispersed in the microporous membrane; one end of the macromolecular surface modifier is provided with a polyolefin chain segment which is hydrophilic to a matrix, and the other end is provided with a polyester or polyether block or graft chain segment which is electrophilic electrolyte. The invention CN1970649B discloses a macromolecular surface modifier for modifying ceramic nanometer surfaces, which is an oligomer with the molecular weight of 3000-9000 and is obtained by the free radical initiated copolymerization of monomers such as (methyl) acrylic esters, vinyl siloxane and (methyl) acrylic acid, maleic anhydride, styrene, vinyl acetate, acrylonitrile and the like in an organic solvent. The invention CN101508754B discloses surface modified sericite, which is sericite powder obtained by coating and modifying sericite with a terpolymer by a liquid phase method, and the surface modified sericite is used as a modifier in the preparation of rubber/sericite composite materials. The three macromolecular surface modifiers related to the invention are applied to respective fields, and the purification and the use of the macromolecular surface modifier in the field of separation membranes are not related.
The macromolecular surface modifier prepared by different methods relates to the problems of subsequent purification, including cutting with different molecular weights and removing insoluble components (including raw materials, high polymers, byproducts and the like), and the product performance can be ensured to be stable only by purifying the macromolecular modifier through a proper post-treatment process. Therefore, an efficient and simple process technology is urgently needed to solve the common problem in the technical field of purification and post-treatment of the macromolecular surface modifier.
Disclosure of Invention
In view of the above, it is necessary to provide a purification method and application of a macromolecular surface modifier.
In order to achieve the purpose, the invention adopts the following technical scheme:
a purification method of a macromolecular surface modifier comprises the following steps:
s1: dissolving a macromolecular surface modifier in a solvent;
s2: performing membrane filtration on the dissolved macromolecular surface modifier to remove insoluble impurities to obtain a purified macromolecular surface modifier solution;
the addition ratio of the macromolecular surface modifier to the solvent is 1: 3 to 13.
Further, the temperature of the dissolving operation of S1 is 25 to 80 ℃.
Preferably, the temperature of the dissolving operation of S1 is 40-60 ℃.
Further, the solvent of S1 includes at least one of dimethylformamide, dimethylacetamide, diethyl ether, dioxane, tetrahydrofuran, acetone, dichloromethane, dimethyl sulfoxide, methanol, ethanol, and water.
Further, the membrane filtration manner described in S2 includes dead-end filtration and cross-flow filtration.
Furthermore, the aperture of the filtering membrane of S2 is 0.1-1 μm.
The purified macromolecular surface modifier is applied to preparing modified materials such as medical materials, medical instruments, membrane materials and the like.
The method for preparing the modified material by adopting the purified macromolecular surface modifier comprises the following steps:
s11: mixing the purified macromolecular surface modifier solution with a matrix material;
s21: preparing the mixed solution of S11 to obtain a modified material;
the mass percentage of the macromolecular surface modifier solution mixed with the matrix material is 0.1-50%.
Preferably, the mass percentage of the macromolecular surface modifier mixed with the matrix material is 5-15%.
Further, the base material of S11 includes at least one of polysulfones, polyamides, polyolefins, polyhaloolefins, polycarbonates, polyacrylonitriles, cellulose acetate, and polyether sulfones.
Further, the method for preparing the modified material from the mixed solution of S21 includes a thermal phase method, a non-solvent phase separation method, an evaporation phase separation method, and an injection molding extrusion method.
As some examples thereof, the macromolecular surface modifying agent comprises the following structure (1): g- [ B-A]n-B-G(1)
Wherein:
a is a hydroxyl-containing backbone segment;
b is an isocyanate group-containing segment;
g is a surface active group;
n is an integer of 1 to 10.
Further, the hydroxyl-containing matrix segment comprises poly (ethylene glycol hydroxy-terminated adipate); polydiallyl phthalate; hydroxyl-terminated polybutadiene; poly (diethylene glycol) adipic acid; poly (hexamethylene carbonate) diol; poly (ethylene-co-1, 2-butene) glycol; hydroxy-terminated polytetramethylene ether; hydroxyl-terminated hydrogenated polybutadiene; 1, 6-hexanediol phthalic anhydride polyester polyol; one or more of poly (2, 2-dimethyl-1, 3-propyl carbonate).
Further, the isocyanate group-containing segment includes isophorone diisocyanate; tetramethylxylylene diisocyanate; dicyclohexylmethane diisocyanate; hexamethylene diisocyanate; one or more of trimeric isophorone diisocyanate.
Further, the surface active group comprises alkyl monoalcohol of C1-C15; fluorinated alkyl mono-alcohols of C1 to C15; C1-C15 alkyl polyol; fluorinated alkyl polyols of C1-C15; C1-C15 alkylamine; one or more of C1-C15 fluorinated alkyl amines.
Preferably, in the macromolecular surface modifier, n is 1 or 2.
Further, the macromolecular surface modifier has a molecular weight of 1000-10000.
Further, the molecular weight of the hydroxyl-containing matrix segment A is between 1000 and 3500 Dalton.
Further, the molecular weight of the surface active group G is between 100 and 1500 daltons.
As some examples, the macromolecular surface modifier can be synthesized by the following method:
s01, respectively dissolving a hydroxyl-containing matrix chain segment A, an isocyanate-containing chain segment B and a catalyst in a solvent;
s02, mixing a hydroxyl-containing matrix chain segment A, an isocyanate-containing chain segment B and a catalyst solution under a nitrogen atmosphere and under anhydrous conditions at a certain temperature, and reacting;
s03, adding the surface active group G into the mixed material in the S02 under the nitrogen atmosphere, mixing and reacting.
Further, the catalyst of S01 is an organometallic catalyst.
Preferably, the metal catalyst comprises one of an organotin catalyst, an organobismuth catalyst and an organozinc catalyst.
Further, the solvent described in S01 is an organic high boiling point solvent.
Preferably, the organic high boiling point solvent comprises one of dimethylacetamide, dimethylsulfoxide, toluene, dimethylformamide and chlorobenzene.
Further, the temperature of S02 is 50-80 ℃. When the temperature is too low, the reaction is incomplete, and when the temperature is too high, reaction byproducts and polymers are increased.
Further, A, B of S02 and the catalyst were mixed for 0.1 to 1 hour.
Further, the reaction time of S02 is 5 to 15 hours.
Further preferably, the reaction time of S02 is 5 to 8 hours. When the temperature at which the surface active group G is added is too low, the reaction is incomplete, and when the temperature is too high, by-products and polymers are increased.
Further, the mixing time of the mixed material of S03 and G is 0.1-1 hour.
Further, the temperature at which S03 is added to the surface active group G is 30 to 60 ℃.
Further, the mixing reaction time of S03 is 12-20 hours.
Further, the molar (mass) ratio of the hydroxyl group-containing base segment a, the isocyanate group-containing segment B, and the surface active group G is 1: 1-3: 1-6.
The content of the catalyst is 1-10 wt% of the hydroxyl matrix chain segment A.
Further, the method comprises the steps of adding a poor solvent into the material obtained after the S03 reaction to precipitate a product, filtering, washing and drying to obtain the product.
Further, the poor solvent comprises one or more of water, methanol, ethanol and acetonitrile.
Further, the cleaning agent used for cleaning comprises one or more of tetrahydrofuran, methanol, water, ethanol, ethylene diamine tetraacetic acid, sodium ethylene diamine tetracetate, acetonitrile and acetone.
The invention has the beneficial effects that:
(1) the purification method of the macromolecular surface modifier provided by the invention can effectively and selectively remove polymers, high polymers and insoluble components in a crude product and retain the main components of the oligomeric macromolecular surface modifier;
(2) the purified macromolecular surface modifier provided by the invention enables the obtained modified material to obtain corresponding modification, and meanwhile, the purified macromolecular surface modifier and the matrix material have better solubility and transparency, and better stability and reusability.
Drawings
FIG. 1 is a graph of a modified Polyethersulfone (PES) membrane contact angle test;
FIG. 2 is a diagram of a polyethersulfone membrane contact angle test;
FIG. 3 is a graph showing contact angle test of a modified polyvinylidene fluoride (PVDF) film;
FIG. 4 is a graph showing a contact angle test of a polyvinylidene fluoride film.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be further clearly and completely described below with reference to the embodiments of the present invention. It should be noted that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Macromolecular surface modifier:
(1) synthesizing a macromolecular surface modifier A:
all vessels used for the synthesis of macromolecular surface-modifying agents were thoroughly dried at 110 ℃. A1000 ml glass-dried three-necked flask was charged with 72mmol of hydroxy-terminated poly (2, 2-dimethyl-1, 3-propyl carbonate), and the contents of the vessel were thoroughly purged with ultrapure nitrogen to dry and remove water overnight. 525ml of dimethylacetamide was measured out using a 1000ml measuring cylinder, sealed with a rubber stopper, and the solvent was pushed with ultrapure nitrogen. Dimethylacetamide was pushed into a three-necked flask with a double-ended needle to be miscible with hydroxy-terminated poly (2, 2-dimethyl-1, 3-propyl carbonate) and stirred uniformly. The temperature was maintained at 65-70 ℃ while stirring. To a 250ml glass-dried three-necked flask was added 151mmol of isophorone diisocyanate. 150ml of dimethylacetamide was measured out using a 250ml measuring cylinder, sealed with a rubber stopper and pushed with ultrapure nitrogen into the solvent. Dimethyl acetamide is pushed into a three-neck flask by a double-ended needle to be mixed and dissolved with isophorone diisocyanate and stirred uniformly. To a 50ml glass dried round bottom flask was added 8g (10% w/w weight of the hydroxyl terminated starting material) of organotin reagent, 26ml of dimethylacetamide was measured out using a 50ml graduated cylinder, sealed with a rubber stopper, and the solvent was pushed with ultrapure nitrogen. Dimethylacetamide was pushed into a round bottom flask with a double ended needle to be miscible with the organotin reagent and stirred uniformly. The solution containing isophorone diisocyanate was pushed through a double-ended needle with nitrogen into the solution containing hydroxyl terminated poly (2, 2-dimethyl-1, 3-propyl carbonate), followed immediately by the addition of the solution containing organotin reagent. The mixture system was stirred uniformly and maintained at 70 ℃ for 5 hours.
In another 50ml dry round bottom flask was added 180mmol perfluoropentanol, sealed with a rubber stopper and the reagent was pushed in with ultra pure nitrogen. Perfluoropentanol was added to the mixture system through a double-ended needle, and the mixture system was kept under uniform stirring at 45 ℃ for 18 hours. Finally synthesizing the macromolecular surface modifier A. The system was cooled to room temperature and was a milky white turbid liquid. Distilled water is added to the turbid solution to generate precipitate, and the precipitate is washed with isopropanol/ethylene diamine tetraacetic acid solution to remove unreacted raw materials, catalyst and solvent. Gradually heating and vacuum drying in an oven at 40-120 deg.C. The final product is obtained.
The structural formula of the macromolecular surface modifier A is as follows:
(2) macromolecular surface modifier B: the macromolecular surface modifier was obtained according to the preparation method of the free radical initiated polymerization process of the example in CN 1970649B.
Example 1
And (3) placing the raw material of the macromolecular surface modifier A in an oven at the temperature of 40-120 ℃ to gradually raise the temperature and carry out vacuum drying for 12 hours. Weighing 100g of dried macromolecular surface modifier according to the weight ratio of 1 (macromolecular surface modifier) to 10 (dioxane): 1 (dimethylformamide), fully stirring and uniformly dissolving at 60 ℃, and keeping for 12 hours.
The homogeneous solution was passed through a 0.22 μm organic microfiltration membrane by dead-end filtration. Collecting the filtrate as purified macromolecular surface modifier solution.
Example 2
And (3) placing the raw material of the macromolecular surface modifier A in an oven at the temperature of 40-120 ℃ to gradually raise the temperature and carry out vacuum drying for 6 hours. Weighing 100g of dried macromolecular surface modifier, and mixing the weighed macromolecular surface modifier with the following weight ratio of 1 (macromolecular surface modifier) to 5 (acetone): 1 (dichloromethane), fully stirring, mixing and dissolving the three components uniformly at 40 ℃, and keeping for 6 hours.
The homogeneous solution was passed through a 0.45 μm organic microfiltration membrane by dead-end filtration. Collecting the filtrate as purified macromolecular surface modifier solution.
Example 3
And (3) placing the raw material of the macromolecular surface modifier B in an oven at the temperature of 40-120 ℃ to gradually raise the temperature and carry out vacuum drying for 10 hours. Weighing 100g of dried macromolecular surface modifier, and mixing the components in a weight ratio of 1 (macromolecular surface modifier) to 4 (dimethylacetamide): 1 (methanol), fully stirring, mixing and dissolving the three components uniformly at 60 ℃, and keeping for 12 hours.
The homogeneous solution was passed through a 200nm ceramic membrane by cross-flow filtration. Collecting the filtrate as purified macromolecular surface modifier solution.
Example 4
And (3) placing the raw material of the macromolecular surface modifier B in an oven at the temperature of 40-120 ℃ to gradually raise the temperature and carry out vacuum drying for 4 hours. Weighing 100g of dried macromolecular surface modifier according to the weight ratio of 1 (macromolecular surface modifier) to 2.5 (diethyl ether): 0.5 (tetrahydrofuran), stirring thoroughly at 30 deg.C, dissolving uniformly, and holding for 10 hr.
The homogeneous solution was passed through a 500nm ceramic membrane by cross-flow filtration. Collecting the filtrate as purified macromolecular surface modifier solution.
Example 5
And (3) placing the raw material of the macromolecular surface modifier B in an oven at the temperature of 40-120 ℃ to gradually heat and carry out vacuum drying for 3 hours. Weighing 100g of dried macromolecular surface modifier according to the weight ratio of 1 (macromolecular surface modifier) to 3 (ethanol): 3 (water), fully stirring and uniformly dissolving the three components at 50 ℃, and keeping for 12 hours.
The homogeneous solution was passed through a 200nm ceramic membrane by cross-flow filtration. Collecting the filtrate as purified macromolecular surface modifier solution.
Example 6
The solution of the macromolecular surface modifier purified in example 1 was mixed with other matrix materials in the following ratio 1 (polyethersulfone): 1 (PVP): 1 (macromolecular surface modifier solution) 6 (dimethylacetamide): 1 (acetone), fully stirring and uniformly dissolving at 45 ℃, and keeping for 12 hours.
After stirring and dissolving uniformly, stopping stirring, and standing for 6 hours. An organic microporous membrane, labeled microporous membrane a1, was prepared using a non-solvent induced phase separation process.
Example 7
The solution of the macromolecular surface modifier purified in example 2 was mixed with other matrix materials in the following ratio 1 (polyethersulfone): 1 (PVP): 1 (macromolecular surface modifier solution): 6 (dimethylacetamide): 1 (acetone), fully stirring and uniformly dissolving at 45 ℃, and keeping for 12 hours.
After stirring and dissolving uniformly, stopping stirring, and standing for 6 hours. An organic microporous membrane, labeled microporous membrane a2, was prepared using a non-solvent induced phase separation process.
Example 8
The solution of macromolecular surface modifier purified from example 3 was mixed with other matrix materials as described in 1 (polyvinylidene fluoride): 1.5 (PVP): 0.5 (macromolecular surface modifier solution): 6.5 (dimethylacetamide): 0.5 (dioxane), fully stirring and uniformly dissolving at 60 ℃, and keeping for 12 hours.
After stirring and dissolving uniformly, stopping stirring, and standing for 6 hours. An organic microporous membrane, labeled microporous membrane B1, was prepared using a non-solvent induced phase separation process.
Example 9
The solution of macromolecular surface modifier purified from example 4 was mixed with other matrix materials as described in 1 (polyvinylidene fluoride): 1 (PVP): 1 (macromolecular surface modifier solution): 6 (dimethylacetamide): 1 (dioxane), fully stirring and uniformly dissolving at 60 ℃, and keeping for 12 hours.
After stirring and dissolving uniformly, stopping stirring, and standing for 6 hours. An organic microporous membrane, labeled microporous membrane B2, was prepared using a non-solvent induced phase separation process.
Example 10
Selecting unpurified macromolecular surfactants, and respectively preparing modified materials under other conditions according to the conditions of the examples 6 and 8, wherein the modified materials are sequentially marked as A0B 0; meanwhile, PES membranes and PVDF membranes without macromolecular surface modifiers were prepared, and the modified materials prepared according to examples 7 and 9 under the other conditions were labeled as a3 and B3, respectively, and contact angle tests were performed, and the results were as follows:
TABLE 1 test groups
| Numbering | A1 | A2 | B1 | B2 |
| Angle/° degree | 99.1 | 90.6 | 73.5 | 74.1 |
TABLE 2 control group
| Numbering | A0 | A3 | B0 | B3 |
| Angle/° degree | 94.1 | 66.6 | 72.2 | 71.8 |
Example 11
A1 g/L BSA solution membrane flux test (1Bar) was carried out using a purified modifier-modified separation membrane A1, an unpurified modifier-modified separation membrane A0 and an unmodified separation membrane A3, respectively, and then flux recovery was tested by washing with 0.3mol/L NaOH for 3 hours. The results are shown in the following table:
table 3 membrane flux test data
And (3) knotting: after the purified macromolecular surface modifier is added into the membrane material, the membrane material obtains corresponding hydrophobic (or hydrophilic) performance compared with the unmodified membrane material, and has better anti-pollution capacity and cleaning regeneration capacity; although unpurified macromolecular modifiers can achieve similar results, the presence of impurities can result in lower porosity and lower flux in the membrane material.
Claims (10)
1. A purification method of a macromolecular surface modifier comprises the following steps:
s1: dissolving a macromolecular surface modifier in a solvent;
s2: performing membrane filtration on the dissolved macromolecular surface modifier to remove insoluble impurities to obtain a purified macromolecular surface modifier solution;
the addition ratio of the macromolecular surface modifier to the solvent is 1: 3 to 13.
2. The method for purifying a macromolecular surface modifying agent according to claim 1, wherein the temperature of the dissolving operation of S1 is 25-80 ℃.
3. The method of claim 1, wherein the solvent of S1 comprises at least one of dimethylformamide, dimethylacetamide, diethyl ether, dioxane, tetrahydrofuran, acetone, dichloromethane, dimethylsulfoxide, methanol, ethanol, and water.
4. The method for purifying a macromolecular surface modifying agent according to claim 1, wherein the membrane filtration means of S2 comprises dead-end filtration and cross-flow filtration.
5. The method for purifying a macromolecular surface modifying agent according to claim 1, wherein the pore size of the filtration membrane in S2 is 0.1 to 1 μm.
6. The purified macromolecular surface modifier obtained by the method according to any one of claims 1 to 5, and application thereof in preparing medical materials, medical instruments and membrane material modified materials.
7. A method for preparing a modified material by using the purified macromolecular surface modifier obtained by the method of any one of claims 1 to 5, which is characterized by comprising the following steps:
s11: mixing the purified macromolecular surface modifier solution with a matrix material;
s21: preparing the mixed solution of S11 to obtain a modified material;
the mass percentage of the macromolecular surface modifier solution mixed with the matrix material is 0.1-50%.
8. The method for preparing modified material according to claim 7, wherein the mass percentage of the macromolecular surface modifier mixed with the matrix material is 5-15%.
9. The method according to claim 7, wherein the matrix material of S11 comprises at least one of polysulfones, polyamides, polyolefins, polyhaloolefins, polycarbonates, polyacrylonitriles, cellulose acetate, and polyether sulfones.
10. The method of claim 7, wherein the method for preparing the modified material from the mixed solution of S21 comprises a thermal phase method, a non-solvent phase separation method, an evaporation phase separation method, and an injection extrusion method.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5985016A (en) * | 1997-10-30 | 1999-11-16 | Hewlett-Packard Company | Purification of macromolecular chromophores (MMCs) using membrane processes for ink-jet inks |
| CN1970649A (en) * | 2006-12-08 | 2007-05-30 | 安徽大学 | Large molecule surface modifier for ceramic nanometer surface modification |
| US20080228253A1 (en) * | 2006-12-14 | 2008-09-18 | Sanjoy Mullick | Surface modifying macromolecules with high degradation temperatures and uses thereof |
| CN101508754A (en) * | 2009-03-18 | 2009-08-19 | 滁州格锐矿业有限责任公司 | Macromolecule surface modifier and surface modified sericite, and uses thereof |
| JP2017214494A (en) * | 2016-05-31 | 2017-12-07 | 株式会社トプコン | Surface modifier, surface modification method using the same, and surface-modified article |
| CN108070367A (en) * | 2017-12-22 | 2018-05-25 | 长江大学 | A kind of sulfonate modified hyperbranched surfactant and preparation method |
| CN108219389A (en) * | 2017-11-22 | 2018-06-29 | 上海锦湖日丽塑料有限公司 | Macromolecular coupling agent is modified fiber glass reinforced PBT composite material and preparation method thereof |
| CN110891997A (en) * | 2017-07-14 | 2020-03-17 | 费森尤斯医疗保健控股公司 | Method for providing surface modification compositions with improved byproduct removal |
-
2021
- 2021-10-12 CN CN202111189176.2A patent/CN113980241B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5985016A (en) * | 1997-10-30 | 1999-11-16 | Hewlett-Packard Company | Purification of macromolecular chromophores (MMCs) using membrane processes for ink-jet inks |
| CN1970649A (en) * | 2006-12-08 | 2007-05-30 | 安徽大学 | Large molecule surface modifier for ceramic nanometer surface modification |
| US20080228253A1 (en) * | 2006-12-14 | 2008-09-18 | Sanjoy Mullick | Surface modifying macromolecules with high degradation temperatures and uses thereof |
| CN101508754A (en) * | 2009-03-18 | 2009-08-19 | 滁州格锐矿业有限责任公司 | Macromolecule surface modifier and surface modified sericite, and uses thereof |
| JP2017214494A (en) * | 2016-05-31 | 2017-12-07 | 株式会社トプコン | Surface modifier, surface modification method using the same, and surface-modified article |
| CN110891997A (en) * | 2017-07-14 | 2020-03-17 | 费森尤斯医疗保健控股公司 | Method for providing surface modification compositions with improved byproduct removal |
| CN108219389A (en) * | 2017-11-22 | 2018-06-29 | 上海锦湖日丽塑料有限公司 | Macromolecular coupling agent is modified fiber glass reinforced PBT composite material and preparation method thereof |
| CN108070367A (en) * | 2017-12-22 | 2018-05-25 | 长江大学 | A kind of sulfonate modified hyperbranched surfactant and preparation method |
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