CN113321886A - Hydrophilic-hydrophobic polymer composite microsphere and preparation method thereof - Google Patents
Hydrophilic-hydrophobic polymer composite microsphere and preparation method thereof Download PDFInfo
- Publication number
- CN113321886A CN113321886A CN202110761254.5A CN202110761254A CN113321886A CN 113321886 A CN113321886 A CN 113321886A CN 202110761254 A CN202110761254 A CN 202110761254A CN 113321886 A CN113321886 A CN 113321886A
- Authority
- CN
- China
- Prior art keywords
- polymer
- hydrophilic
- cross
- hydrophobic
- linked
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Abstract
A hydrophilic-hydrophobic polymer composite microsphere and its preparing process are disclosed, the high-molecular polymer microsphere is used as a functional material and is widely used in medical and health field, chemical field and electronic display material. The invention provides a composite microsphere consisting of hydrophilic polymer and hydrophobic polymer, and a preparation method of the microsphere.
Description
Technical Field
The invention relates to the field of high molecular materials, in particular to a hydrophilic-hydrophobic polymer composite microsphere and a preparation method thereof.
Background
The high molecular polymer microsphere is used as a functional material and is widely applied to the fields of medicine and health, chemical engineering, electronic display materials and the like. The composite microspheres are formed by combining chemical substances with different components or structures, and the performance and application field of the high-molecular polymer microspheres are favorably expanded.
The Chinese invention patent CN106984290B discloses a preparation method of chitosan/sodium alginate magnetic composite microspheres capable of adsorbing heavy metal ions; chinese invention patent CN107715169A discloses a preparation method and a product of a sodium alginate drug-loaded composite embolic microsphere containing PLGA nano particles; the Chinese invention patent CN106881053A discloses an inverse opal polydopamine/polypyrrole composite microsphere; the Chinese invention patent CN107823700A discloses a preparation method of cellulose/chitosan composite microspheres for hemostasis; the Chinese invention patent CN108144590A discloses a method for preparing polyaniline @ polystyrene composite microspheres and application thereof as a Cr (VI) adsorbent; chinese invention patent CN108503880A discloses a method for preparing polyacrylamide-calcium alginate composite microspheres by reverse microemulsion polymerization; chinese invention patent CN108620004A discloses a starch/PVA composite microsphere and a preparation method thereof; the Chinese invention patent CN110935406A discloses a high-strength polysaccharide-nano-grade laponite composite microsphere and a preparation method thereof; chinese patent CN112480325AV discloses a phenolic resin-acrylamide composite microsphere and a preparation method and application thereof.
Disclosure of Invention
The invention provides a hydrophilic-hydrophobic polymer composite microsphere and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: a hydrophilic-hydrophobic polymer composite microsphere, hydrophilic (water absorbing) cross-linked polymer microsphere contains hydrophobic linear high molecular polymer 1-35% by mass.
As a further improvement of the invention: the hydrophilic crosslinked polymer microspheres are crosslinked acrylic acid polymers, or crosslinked hydroxyethyl methacrylate polymers, or crosslinked methacrylic acid polymers, or crosslinked 2-acrylamido-2-methylpropanesulfonic acid polymers, or crosslinked N, N-dimethylaminoethyl methacrylate polymers.
As a further improvement of the invention: the hydrophobic linear high molecular polymer is polymethyl methacrylate, polyethylene, polypropylene, EVA resin, polystyrene or a mixture of two or more of the two in any proportion.
A preparation method of a hydrophilic-hydrophobic polymer composite microsphere comprises the following steps:
1) dissolving a hydrophobic linear high molecular polymer in a proper organic solvent;
2) adding a polymerization reaction monomer, a cross-linking agent and a thermal initiator; heating to initiate precipitation polymerization;
3) the hydrophobic linear high molecular polymer is subjected to cross-linking polymerization reaction until microspheres are separated out from the solution;
4) heating and vacuumizing to remove the organic solvent.
As a further improvement of the invention: the preparation method also comprises the following steps:
(1) firstly, dissolving one or a mixture of a plurality of polymethyl methacrylate, polyethylene, polypropylene, EVA resin and polystyrene in any proportion in a proper organic solvent;
(2) the dissolution of the hydrophobic linear high molecular polymer is accelerated by methods such as heating and the like;
(3) adding a polymerization reaction monomer, a cross-linking agent and a thermal initiator into the solution, and heating to initiate precipitation polymerization reaction by adopting a precipitation polymerization method.
Xylene, methylene chloride, chloroform, carbon tetrachloride, acetone, heptane, n-hexane, cyclohexane, tetrahydrofuran, t-butanol, dichloroethane, dioxane, etc.
As a further improvement of the invention: the polymerization reaction monomer in the step (3) is acrylic acid, methacrylic acid, hydroxyethyl methacrylate, 2-acrylamide-2-methylpropanesulfonic acid, and N, N-dimethylaminoethyl methacrylate.
As a further improvement of the invention: the cross-linking agent in the step (3) is a bifunctional compound soluble in the organic solvent, and includes but is not limited to divinylbenzene, ethylene glycol dimethacrylate, pentaerythritol triallyl ether, pentaerythritol triacrylate, and the like.
As a further improvement of the invention: in the precipitation polymerization reaction in the step (3), the hydrophobic linear high molecular polymer is separated out from the solution along with the growth of the hydrophilic high molecular chain and the microspheres; after the precipitation polymerization is finished, heating and vacuumizing are performed to remove the organic solvent, and the hydrophilic-hydrophobic polymer composite microspheres are obtained.
Compared with the prior art, the invention has the beneficial effects that: a hydrophilic-hydrophobic composite microsphere, the said composite microsphere is that the hydrophilic (water-absorbing) polymer microsphere of cross-linking also contains the linear high molecular polymer of hydrophobicity of certain proportion; utilizing the characteristic that hydrophobic linear polymer such as polymethyl methacrylate, polyethylene, polypropylene, EVA resin, polystyrene and the like can be dissolved in organic solvent such as benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, acetone, heptane, n-hexane, cyclohexane, tetrahydrofuran, t-butanol, dichloroethane, dioxane and the like, these organic solvents are in turn suitable precipitation polymerization solvents for acrylic acid, methacrylic acid, hydroxyethyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, N-dimethylaminoethyl methacrylate and the like, therefore, under the condition of proper process, the hydrophobic linear high molecular polymer dissolved in the organic solvent can be separated out from the solution along with the growth of the hydrophilic high molecular chain and the microspheres to form the hydrophilic-hydrophobic polymer composite microspheres.
Drawings
FIG. 1 is a schematic structural diagram of a crosslinked polyacrylic acid microsphere of the present invention.
FIG. 2 is a schematic structural diagram of a crosslinked polyacrylic acid-polymethyl methacrylate composite microsphere of the present invention.
Detailed Description
The invention will now be further described with reference to the accompanying description and examples:
the first embodiment is as follows:
200g of xylene was heated to 80 ℃ and 1.80g of polymethyl methacrylate was added and dissolved by stirring. 40g of acrylic acid, 0.89g of pentaerythritol triallyl ether and 1.0g of azobisisobutyronitrile were added, and after stirring uniformly, the mixture was placed in a sealed glass bottle, and the bottle was heated in a water bath at 80 ℃ for about 30 minutes, and a white precipitate was observed. And continuously reacting for 60min, transferring the product into an oil bath kettle at 120 ℃, heating, vacuumizing, and removing xylene to obtain white to light yellow powdery crosslinked polyacrylic acid-polymethyl methacrylate composite microspheres. Polymethyl methacrylate is not dissolved in xylene, and the cross-linked polyacrylic acid microspheres are prepared by the same method. The difference between the two microspheres is observed by an electron microscope, and the particle sizes of the two microspheres are both about 200nm, the particles of the crosslinked polyacrylic acid microspheres are loose, and the crosslinked polyacrylic acid-polymethyl methacrylate composite microspheres are entangled with each other, as shown in fig. 1 and fig. 2.
The second embodiment:
the crosslinked polyacrylic acid microspheres prepared in example 1 and 1.0g of crosslinked polyacrylic acid-polymethyl methacrylate composite microspheres prepared in example 1 were taken, dispersed in 100g of water under stirring, 0.01M aqueous sodium hydroxide solution was added dropwise, the pH of the solution was adjusted to 7.5 ± 0.3, and stirred sufficiently and uniformly, and the viscosity of the crosslinked polyacrylic acid microsphere solution was 7254mPaS and the viscosity of the crosslinked polyacrylic acid-polymethyl methacrylate composite microsphere solution was 9078mPaS as measured by a digital display rotational viscometer.
The third embodiment is as follows:
dissolving 1.35g of polystyrene in 120g of carbon tetrachloride, adding 22g of N, N-dimethylaminoethyl methacrylate, 0.26g of divinylbenzene and 0.3g of azodiisobutyronitrile, uniformly stirring, sealing in a glass bottle, heating in a 70 ℃ water bath kettle, continuing to react for 60min after white precipitates are observed, transferring the product to a 80 ℃ water bath kettle, heating, vacuumizing, and removing carbon tetrachloride to obtain white to light yellow powdery crosslinked polymethacrylic acid-N, N-dimethylaminoethyl ester-polystyrene composite microspheres. Polystyrene is not dissolved in carbon tetrachloride, and the cross-linked poly (N, N-dimethylaminoethyl methacrylate) microspheres are prepared by the same method.
The fourth embodiment is as follows:
1.0g of the crosslinked poly (N, N-dimethylaminoethyl methacrylate) microspheres and the crosslinked poly (N, N-dimethylaminoethyl methacrylate) -polystyrene composite microspheres prepared in the example 1 are taken respectively, stirred and dispersed in 100g of water, 0.01M dilute hydrochloric acid is dripped, the pH value of the water solution is adjusted to be 7.0 +/-0.2, the mixture is fully and uniformly stirred, the viscosity of the crosslinked poly (N, N-dimethylaminoethyl methacrylate) microspheres water solution is measured by a digital display rotational viscometer and is 896mPaS, and the viscosity of the crosslinked poly (acrylic acid) -poly (methyl methacrylate) composite microspheres water solution is 1165 mPaS.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; these modifications and substitutions do not cause the essence of the corresponding technical solution to depart from the scope of the technical solution of the embodiments of the present invention, and are intended to be covered by the claims and the specification of the present invention.
Claims (4)
1. The hydrophilic-hydrophobic polymer composite microsphere is characterized in that the hydrophilic cross-linked polymer microsphere contains 1-35% of hydrophobic linear high molecular polymer by mass ratio.
2. The hydrophilic-hydrophobic polymer composite microsphere according to claim 1, wherein the hydrophilic cross-linked polymer microsphere is a cross-linked acrylic polymer, or a cross-linked hydroxyethyl methacrylate polymer, or a cross-linked methacrylic acid polymer, or a cross-linked 2-acrylamido-2-methylpropanesulfonic acid polymer, or a cross-linked N, N-dimethylaminoethyl methacrylate polymer.
3. The hydrophilic-hydrophobic polymer composite microsphere according to claim 1, wherein the hydrophobic linear high molecular polymer is polymethyl methacrylate, polyethylene, polypropylene, EVA resin, polystyrene or a mixture of two or more of them in any proportion.
4. The preparation method of the hydrophilic-hydrophobic polymer composite microsphere is characterized by comprising the following steps:
1) dissolving a hydrophobic linear high molecular polymer in a proper organic solvent;
2) adding a polymerization reaction monomer, a cross-linking agent and a thermal initiator; heating to initiate precipitation polymerization;
3) the hydrophobic linear high molecular polymer is subjected to cross-linking polymerization reaction until microspheres are separated out from the solution;
4) heating and vacuumizing to remove the organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110761254.5A CN113321886A (en) | 2021-07-06 | 2021-07-06 | Hydrophilic-hydrophobic polymer composite microsphere and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110761254.5A CN113321886A (en) | 2021-07-06 | 2021-07-06 | Hydrophilic-hydrophobic polymer composite microsphere and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113321886A true CN113321886A (en) | 2021-08-31 |
Family
ID=77425804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110761254.5A Pending CN113321886A (en) | 2021-07-06 | 2021-07-06 | Hydrophilic-hydrophobic polymer composite microsphere and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113321886A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005306942A (en) * | 2004-04-19 | 2005-11-04 | Kao Corp | Composite particle |
| CN101033268A (en) * | 2007-03-30 | 2007-09-12 | 北京科技大学 | Method of preparing polarity controllable polymer microsphere |
| US20120045651A1 (en) * | 2008-07-07 | 2012-02-23 | David Myung | Hydrophobic and Hydrophilic Interpenetrating Polymer Networks Derived from Hydrophobic Polymers and Methods of Preparing the Same |
| CN107919496A (en) * | 2017-11-23 | 2018-04-17 | 齐鲁工业大学 | Method for preparing quasi-single-ion solid polymer electrolyte with semi-interpenetrating network structure by using in-situ polymerization method |
| CN110404584A (en) * | 2019-07-25 | 2019-11-05 | 东南大学 | A kind of 4-methyl umbelliferone molecular engram nanofiber, preparation method and application |
| CN110511309A (en) * | 2019-09-06 | 2019-11-29 | 无锡迈科为生物科技有限公司 | A kind of preparation method of magnetic macromolecular microsphere |
-
2021
- 2021-07-06 CN CN202110761254.5A patent/CN113321886A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005306942A (en) * | 2004-04-19 | 2005-11-04 | Kao Corp | Composite particle |
| CN101033268A (en) * | 2007-03-30 | 2007-09-12 | 北京科技大学 | Method of preparing polarity controllable polymer microsphere |
| US20120045651A1 (en) * | 2008-07-07 | 2012-02-23 | David Myung | Hydrophobic and Hydrophilic Interpenetrating Polymer Networks Derived from Hydrophobic Polymers and Methods of Preparing the Same |
| CN107919496A (en) * | 2017-11-23 | 2018-04-17 | 齐鲁工业大学 | Method for preparing quasi-single-ion solid polymer electrolyte with semi-interpenetrating network structure by using in-situ polymerization method |
| CN110404584A (en) * | 2019-07-25 | 2019-11-05 | 东南大学 | A kind of 4-methyl umbelliferone molecular engram nanofiber, preparation method and application |
| CN110511309A (en) * | 2019-09-06 | 2019-11-29 | 无锡迈科为生物科技有限公司 | A kind of preparation method of magnetic macromolecular microsphere |
Non-Patent Citations (3)
| Title |
|---|
| CHEN CHEN ET AL: "Synthesis and self-assembly of amphiphilic polyphosphazene with controllable composition via two step thiol-ene click reaction", 《POLYMER》 * |
| 金莎 等: "回流沉淀聚合：单分散聚合物纳米水凝胶微球制备新技术", 《化学学报》 * |
| 金莎等: "回流沉淀聚合:单分散聚合物纳米水凝胶微球制备新技术", 《化学学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7189279B2 (en) | Cross-linked polymeric nanoparticles and metal nanoparticles derived therefrom | |
| Zheng et al. | Superadsorbent with three-dimensional networks: From bulk hydrogel to granular hydrogel | |
| US5777054A (en) | Process for producing an oil sorbent polymer and the product thereof | |
| CN104448161B (en) | Organic composite hydrogel cross-linked by modified gelatin nano-microsphere and preparation method of organic composite hydrogel | |
| Ibrahim et al. | Synthesis of poly (acrylamide-graft-chitosan) hydrogel: optimization of the grafting parameters and swelling studies | |
| US20050272876A1 (en) | Process for emulsion graft polymerization and products thereof | |
| CN104829777A (en) | Preparation method of micron-sized highly-crosslinked polymethyl methacrylate (PMMA) microspheres | |
| JPH07100746B2 (en) | Method for producing uniform macroporous polymer beads | |
| JPH06345819A (en) | Production of highly water absorbing resin | |
| CN110790856A (en) | Graphene oxide/polyacrylic acid composite hydrogel and preparation method thereof | |
| JPH05125127A (en) | Polymer granule having single inner pore | |
| CN113694248A (en) | Embolism microsphere based on soluble starch and preparation and application thereof | |
| CN113321886A (en) | Hydrophilic-hydrophobic polymer composite microsphere and preparation method thereof | |
| US4259223A (en) | Cross-linked polyvinyl pyridine coated glass particle catalyst support and aqueous composition or polyvinyl pyridine adducted microspheres | |
| Li et al. | In situ synthesis and self-reinforcement of polymeric composite hydrogel based on particulate macro-RAFT agents | |
| JPH03137105A (en) | Production of highly adsorptive copolymer | |
| CN105504139B (en) | Poly (methyl methacrylate-co-N-vinyl pyrrolidone) and synthetic method thereof | |
| CA2410034C (en) | Cross-linked polymeric nanoparticles and metal nanoparticles derived therefrom | |
| CN110028611B (en) | Monodisperse shell-core polystyrene microsphere and preparation method thereof | |
| CN108129599B (en) | Hollow polymer plastic microsphere with micro-channels on surface and preparation method and application thereof | |
| KR101776369B1 (en) | Polymer having high adsorption ability for metal ions and preparation method thereof | |
| KR101776370B1 (en) | Polymer capsule adsorbent having high adsorption ability for metal ions and capable of being reused, and preparation method thereof | |
| KR100420372B1 (en) | Synthesis of Nanocomposite Based on Amphiphilic Polyurethane Nonionomer. | |
| An et al. | Synthesis and characterization of salt-resistant super absorbent derived from maize bran | |
| Abd Ghapar et al. | Preparation and characterization of chitosan beads grafted with poly (methyl methacrylate) for controlled release study |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20230728 |
|
| AD01 | Patent right deemed abandoned |