CN114106398A - Preparation method of macroporous resin - Google Patents
Preparation method of macroporous resin Download PDFInfo
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- CN114106398A CN114106398A CN202110000847.XA CN202110000847A CN114106398A CN 114106398 A CN114106398 A CN 114106398A CN 202110000847 A CN202110000847 A CN 202110000847A CN 114106398 A CN114106398 A CN 114106398A
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- 229920005989 resin Polymers 0.000 title claims abstract description 44
- 239000011347 resin Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000003921 oil Substances 0.000 claims abstract description 17
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003463 adsorbent Substances 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 231100000252 nontoxic Toxicity 0.000 claims abstract description 5
- 230000003000 nontoxic effect Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 31
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 26
- 229920002545 silicone oil Polymers 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 102000008186 Collagen Human genes 0.000 claims description 20
- 108010035532 Collagen Proteins 0.000 claims description 20
- 229920001436 collagen Polymers 0.000 claims description 20
- -1 methyl hydrogen Chemical compound 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000004005 microsphere Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- RRSXICBKOPODSP-UHFFFAOYSA-N 1,4-bis(chloromethoxy)butane Chemical group ClCOCCCCOCCl RRSXICBKOPODSP-UHFFFAOYSA-N 0.000 claims description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- VIEXQFHKRAHTQS-UHFFFAOYSA-N chloroselanyl selenohypochlorite Chemical compound Cl[Se][Se]Cl VIEXQFHKRAHTQS-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- 239000008213 purified water Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 13
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000012567 medical material Substances 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000008096 xylene Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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Abstract
The invention relates to the fields of medical materials, environmental protection, metallurgy and the like, and particularly discloses a preparation method of macroporous resin, which comprises the following steps: (1) preparing a water phase; (2) preparing an oil phase; (3) suspension polymerization: adding the water phase and the oil phase prepared in the step (1) and the step (2) into a three-neck flask for suspension polymerization; (4) cleaning and forming: repeatedly cleaning, removing redundant water phase, oil phase and pore-forming agent, and drying under vacuum and negative pressure to obtain a primary cross-linked macroporous resin adsorbent; (5) chloromethylation: adding chloromethylation agent, heating, adding catalyst, repeating the cleaning and other steps to obtain the secondary cross-linked macroporous resin. The invention adopts safe and nontoxic organic silicon solvent without pungent smell and difficult volatilization to replace traditional toxic organic solvent such as toluene, xylene and the like when synthesizing resin, thereby protecting the safety of experimenters, generating no waste liquid and gas, protecting the environment, being economical and convenient and being more beneficial to large-scale production.
Description
Technical Field
The invention relates to the fields of medical materials, environmental protection, metallurgy and the like, and particularly discloses a preparation method of macroporous resin.
Background
The polymer porous microsphere, also called macroporous resin, is a kind of organic polymer adsorbent with better adsorption property developed rapidly since the end of the last 70 th century, and is one of functional polymer materials. The macroporous resin has the characteristics of large surface area, high exchange speed, high mechanical strength, strong pollution resistance, good thermal stability and the like, and is widely applied to the aspects of daily production and life of people, including the fields of medical and biochemical industry, sewage and wastewater treatment, clinical identification and the like.
At present, most of macroporous resins are made into spherical particles with the diameter ranging from 0.04 mm to 1.2mm, and the particles are internally provided with adsorption sites and diffusion channels matched with the molecular size of a separation object, so that the adsorption performance and the loading capacity of the macroporous resins are usually high. The macroporous resin is prepared by taking styrene and acrylic ester as monomers, adding divinylbenzene as a cross-linking agent, taking methylbenzene and dimethylbenzene as pore-foaming agents, removing the pore-foaming agents after a polymer is formed, and leaving holes which are different in size and shape and are communicated with each other in the resin; the pore-forming technology of macroporous resin comprises the steps of pore-forming by polymerization, pore-forming by Friedel-Crafts crosslinking, pore-forming by emulsion, pore-forming by ultrafine powder and the like.
Because of the limitation of synthetic materials and processes, the macroporous resin generates a lot of pollution wastes in the production process, along with the enhancement of the awareness of environmental protection of human beings, the national attention on environmental protection is paid, and new requirements are also provided for the production process and the preparation method of the polymer material which is easy to generate pollution in the industry. Therefore, how to solve the problems of toxicity, easy volatilization, environmental pollution and the like of common pore-foaming agents such as toluene and the like, so that the synthesized resin is safer and more environment-friendly, has no toxic residues, and is suitable for large-scale production is the problem which needs to be solved by the technical personnel in the field.
Disclosure of Invention
Aiming at the situation, the invention provides a preparation method of macroporous resin, which is characterized in that when the resin is synthesized, the resin is prepared by adopting a safe, nontoxic, nonirritating and nonvolatile organic silicon solvent to replace the traditional toxic organic solvents such as toluene, xylene and the like through a suspension polymerization method, thereby protecting the safety of experimenters, generating no waste liquid and waste gas and protecting the environment.
The invention is realized by the following technical scheme, and the preparation method of the macroporous resin comprises the following steps:
(1) preparing a water phase: weighing collagen in a beaker, adding a proper amount of water, and stirring at a constant temperature to fully dissolve the collagen;
(2) preparing an oil phase: taking a certain amount of cross-linking agent and styrene according to the mass ratio of 1/0.1-1.5 for mixing pretreatment, taking 80% of the pretreated solution, adding methyl silicone oil pore-forming agent and benzoyl peroxide initiator, mixing and stirring at normal temperature until the solution turns slightly green;
(3) suspension polymerization: adding the water phase and the oil phase prepared in the step 1 and the step 2 into a three-neck flask, stirring for 10-120min at the rotation speed of 200-300rpm, gradually heating to 75 ℃ after the stirring is stopped and the reaction system is stabilized, reacting for 8h, and then heating to 85 ℃ for reacting for 3 h;
(4) cleaning and forming: cooling the solution obtained in the step (3) to 50 ℃, standing for layering, and then removing redundant water phase and oil phase; adding purified water, stirring at constant temperature, standing for layering, removing excessive water phase, and repeating the above operation for 3-4 times; cleaning with ethanol, stirring at constant temperature, standing for layering, removing excessive pore-forming agent, and repeating the above steps for 4-5 times; heating and drying the residual solution under a vacuum negative pressure state to obtain a primary cross-linked macroporous resin adsorbent;
(5) chloromethylation: weighing a certain amount of the once-crosslinked macroporous resin obtained in the step 4, adding a chloromethylation agent, stirring at room temperature, fully swelling, adding anhydrous ferric trichloride as a catalyst, and heating to 40-60 ℃ for reaction for 6-16 hours; after the reaction is finished, removing redundant solution after standing and layering, and adding absolute ethyl alcohol to clean for 4-5 times; naturally airing the obtained microspheres, adding the microspheres into a three-neck flask, adding excessive solvent which does not react with a chloromethylation reagent, fully swelling, stirring, heating, adding anhydrous selenium chloride as a catalyst, heating to 70-80 ℃, reacting for 10-24 hours, and finishing the reaction; washing with ethanol for 4-5 times, and naturally drying to obtain the final product, i.e. the secondary cross-linked macroporous resin.
Further, the collagen in step 1 is one of SDS, tween and PVA, the concentration of the collagen solution is 2 to 5wt%, and the collagen addition ratio (mass ratio) ranges from collagen/total monomer =1:0.05 to 0.1.
Further, the oil phase in step 2 is an organic silicon solvent, and the organic silicon solvent is one or more of methyl silicone oil, dimethyl silicone oil methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl vinyl silicone oil, methyl hydroxyl silicone oil, ethyl hydrogen-containing silicone oil, hydroxyl hydrogen-containing silicone oil and cyanogen-containing silicone oil.
Further, the step 2 of pretreating with 80% divinylbenzene comprises the following steps: adding excessive saturated sodium hydroxide solution into 80% divinylbenzene, mixing, demixing with separating funnel, collecting divinylbenzene, drying with anhydrous calcium chloride, and filtering to remove calcium chloride.
Further, the cross-linking agent in step 2 is one or more of styrene, divinylbenzene and acrylic acid.
Further, the initiator in the step 2 is one or more of benzoyl peroxide, ammonium persulfate, hydrogen peroxide, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide.
Further, the addition ratio (mass ratio) of the initiator/the total monomer in step 2 = 1/0.002-0.02.
Further, in the step 3, the temperature rise reaction process is that the temperature is raised to 70-80 ℃ at the speed of 2 ℃/30min for reaction for 6-20h, and then the temperature is raised to 80-90 ℃ for reaction for 2-4 h.
Further, in the step 4, the constant temperature is 40-60 ℃, the time is 20-80min, and the vacuum negative pressure drying temperature is 70-80 ℃.
Further, in step 5, the chloromethylating agent is 1, 4-dichloromethoxybutane, and the solvent which does not react with the chloromethylating agent is methyl silicone oil.
The invention has the following beneficial effects: (1) common toxic and volatile environment-polluting pore-foaming agents such as methylbenzene, nitrobenzene, dichloroethane, ethyl acetate and the like are replaced by safe, nontoxic and easily-obtained methyl silicone oil, so that the synthetic resin is safer and more environment-friendly and has no toxic residue; (2) the macroporous resin adsorbent with ideal particle size and pore diameter can be synthesized by adjusting the addition proportion, reaction temperature, rotating speed and the like of each reaction substance; (3) the preparation method is economical, convenient, safe and environment-friendly, and is convenient for large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a synthetic process diagram of a preparation method of macroporous resin.
Detailed Description
Example 1:
(1) preparing a water phase: 4g of collagen was weighed into a 500ml beaker (2 wt% collagen aqueous solution), 200ml of water was added, and the mixture was sufficiently dissolved with stirring at 50 ℃.
(2) Preparing an oil phase: taking a beaker, pretreating with 80% divinylbenzene for use, weighing 18.8g of divinylbenzene, 18.75g of styrene, 37.5g of methyl silicone oil and 0.375g of methyl ethyl ketone peroxide, mixing, stirring at room temperature for 60min, and waiting until the solution turns slightly green.
(3) Suspension polymerization: 187.5ml of the collagen solution prepared in the step (1) is added into a 500ml three-neck flask, and the position and the rotating speed of a stirring rod are adjusted. Stirring at normal temperature of 260rpm, stabilizing for 10min, adding 75ml of oil phase obtained in step (2), stirring at normal temperature of 260rpm, and stabilizing for 60 min. Then gradually heating to 75 ℃ (2 ℃/30 min) for reaction for 12h, and heating to 85 ℃ for reaction for 3 h.
(4) Cleaning and forming: after the reaction is finished, the temperature is reduced to 50 ℃. Removing excessive water phase and oil phase, adding purified water, stirring at 50 deg.C for 30min, repeating for 3-4 times to remove excessive collagen, cleaning microsphere with ethanol, stirring at 50 deg.C for 1 hr, repeating for 4-5 times to remove excessive silicone oil and gasoline. Then drying the mixture at the vacuum negative pressure of 80 ℃ to obtain the primary cross-linked macroporous resin adsorbent.
Example 2:
(1) preparing a water phase: 7.5g of collagen was weighed into a 500ml beaker (3 wt% collagen aqueous solution), and 250ml of water was added and sufficiently dissolved with stirring at 50 ℃.
(2) Preparing an oil phase: taking a beaker, pretreating with 80% divinylbenzene, weighing 18.8g of divinylbenzene, 18.75g of styrene, 7.5g of acrylic acid, 37.5g of methyl silicone oil and 0.45g of methyl ethyl ketone peroxide, mixing at room temperature, stirring for 60min, and waiting until the solution turns slightly green.
(3) Suspension polymerization: and (2) adding 220ml of the collagen solution prepared in the step (1) into a 500ml three-neck flask, and adjusting the position and the rotating speed of a stirring rod. Stirring at 300rpm at normal temperature for 10min, adding the oil phase 82.55ml obtained in step (2), stirring at 300rpm at normal temperature for 60 min. Then gradually heating to 75 ℃ (2 ℃/30 min) for reaction for 12h, and heating to 85 ℃ for reaction for 3 h.
(4) Cleaning and forming: after the reaction is finished, the temperature is reduced to 50 ℃. Removing excessive water phase and oil phase, adding purified water, stirring at 50 deg.C for 30min, repeating for 3-4 times to remove excessive collagen, cleaning microsphere with ethanol, stirring at 50 deg.C for 1 hr, repeating for 4-5 times to remove excessive silicone oil and gasoline. Then drying the mixture at the vacuum negative pressure of 80 ℃ to obtain the primary cross-linked macroporous resin adsorbent.
Example 3:
(1) 75g of the once crosslinked macroporous resin was weighed into a three-hole flask, 200ml of 1, 4-dichloromethoxybutane was added thereto, and the mixture was sufficiently stirred at room temperature for swelling for 4 hours. Heating to 50 ℃, adding 7.5g of anhydrous ferric trichloride, and carrying out chloromethylation reaction for 12 hours.
(2) After the reaction is finished, the excessive solution is sucked out, absolute ethyl alcohol is added for cleaning for 4-5 times, and 1, 4-dichloromethylbutane is washed clean.
(3) And (3) naturally drying the finished chloromethylated microspheres, and measuring the chlorine content of the chlorine spheres to be 12%.
(4) Adding 30g of chlorine ball into a three-neck flask, adding excessive methyl silicone oil, swelling for 4h, starting stirring, heating to 75 ℃, adding 3g of anhydrous selenium chloride, and reacting for 12 h. And (3) cleaning the methyl silicone oil with ethanol, and naturally airing to obtain the secondary cross-linked macroporous resin.
Example 4:
(1) 75g of the once crosslinked macroporous resin was weighed into a three-hole flask, 75ml of 1, 4-dichloromethoxybutane and 125ml of methylsilicone oil were added, and the mixture was stirred at room temperature and fully swollen for 4 hours. Heating to 50 ℃, adding 7.5g of anhydrous ferric trichloride, and carrying out chloromethylation reaction for 8 hours.
(2) The temperature of the system is raised to 75 ℃, 7.5g of anhydrous selenium chloride is added, and the reaction is continued for 12 hours.
(3) And (3) after the reaction is finished, cleaning the microspheres with absolute ethyl alcohol, and naturally airing to obtain the secondary cross-linked macroporous resin.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel and inventive features disclosed herein.
Claims (10)
1. The preparation method of the macroporous resin is characterized by comprising the following steps:
(1) preparing a water phase: weighing collagen in a beaker, adding a proper amount of water, and stirring at a constant temperature to fully dissolve the collagen;
(2) preparing an oil phase: taking a certain amount of cross-linking agent and styrene according to the mass ratio of 1/0.1-1.5 for mixing pretreatment, taking 80% of the pretreated solution, adding methyl silicone oil pore-forming agent and benzoyl peroxide initiator, mixing and stirring at normal temperature until the solution turns slightly green;
(3) suspension polymerization: adding the water phase and the oil phase prepared in the step 1 and the step 2 into a three-neck flask, stirring for 10-120min at the rotation speed of 200-300rpm, gradually heating to 75 ℃ after the stirring is stopped and the reaction system is stabilized, reacting for 8h, and then heating to 85 ℃ for reacting for 3 h;
(4) cleaning and forming: cooling the solution obtained in the step (3) to 50 ℃, standing for layering, and then removing redundant water phase and oil phase; adding purified water, stirring at constant temperature, standing for layering, removing excessive water phase, and repeating the above operation for 3-4 times; cleaning with ethanol, stirring at constant temperature, standing for layering, removing excessive pore-forming agent, and repeating the above steps for 4-5 times; heating and drying the residual solution under a vacuum negative pressure state to obtain a primary cross-linked macroporous resin adsorbent;
(5) chloromethylation: weighing a certain amount of the once-crosslinked macroporous resin obtained in the step 4, adding a chloromethylation agent, stirring at room temperature, fully swelling, adding anhydrous ferric trichloride as a catalyst, and heating to 40-60 ℃ for reaction for 6-16 hours; after the reaction is finished, removing redundant solution after standing and layering, and adding absolute ethyl alcohol to clean for 4-5 times; naturally airing the obtained microspheres, adding the microspheres into a three-neck flask, adding excessive solvent which does not react with a chloromethylation reagent, fully swelling, stirring, heating, adding anhydrous selenium chloride as a catalyst, heating to 70-80 ℃, reacting for 10-24 hours, and finishing the reaction; washing with ethanol for 4-5 times, and naturally drying to obtain the final product, i.e. the secondary cross-linked macroporous resin.
2. The method for preparing macroporous resin as claimed in claim 1, wherein the collagen of step 1 is one of SDS, tween and PVA, the concentration of the collagen solution is 2-5wt%, and the collagen addition ratio (mass ratio) is in the range of collagen/total monomer =1: 0.05-0.1.
3. The method for preparing macroporous resin as claimed in claim 1, wherein the oil phase in step 2 is an organic silicon solvent, and the organic silicon solvent is one or more of methyl silicone oil, dimethyl silicone oil, methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl vinyl silicone oil, methyl hydroxy silicone oil, ethyl hydrogen-containing silicone oil, hydroxy hydrogen-containing silicone oil and cyanogen-containing silicone oil.
4. The method for preparing macroporous resin as claimed in claim 1, wherein the 80% divinylbenzene pretreatment step of step 2: adding excessive saturated sodium hydroxide solution into 80% divinylbenzene, mixing, demixing with separating funnel, collecting divinylbenzene, drying with anhydrous calcium chloride, and filtering to remove calcium chloride.
5. The method for preparing macroporous resin as claimed in claim 1, wherein the crosslinking agent in step 2 is one or more of styrene, divinylbenzene and acrylic acid.
6. The method for preparing macroporous resin as claimed in claim 1, wherein the initiator in step 2 is one or more selected from benzoyl peroxide, ammonium persulfate, hydrogen peroxide, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide.
7. The method for preparing macroporous resin as claimed in claim 1, wherein the addition ratio (mass ratio) of the initiator/the total monomer in the step 2 is = 1/0.002-0.02.
8. The method for preparing resin according to claim 1, wherein the temperature-raising reaction process in step 3 is to raise the temperature to 70-80 ℃ at a rate of 2 ℃/30min for 6-20h, and then to raise the temperature to 80-90 ℃ for 2-4 h.
9. A novel safe and nontoxic method for preparing resin according to claim 1, wherein the constant temperature in step 4 is 40-60 ℃, the time is 20-80min, and the vacuum negative pressure drying temperature is 70-80 ℃.
10. The resin prepared by the novel safe and nontoxic method according to claim 1 is characterized in that: and 5, the chloromethylation agent is 1, 4-dichloromethoxybutane, and the solvent which does not react with the chloromethylation agent is methyl silicone oil.
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| CN114100589A (en) * | 2021-01-05 | 2022-03-01 | 河南省驼人医疗科技有限公司 | Method for modifying blood perfusion resin adsorbent for acute and chronic poisoning of medicine |
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