CN101955571A - Method for preparing rosin-based polymer microspheres - Google Patents
Method for preparing rosin-based polymer microspheres Download PDFInfo
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- CN101955571A CN101955571A CN2010102761047A CN201010276104A CN101955571A CN 101955571 A CN101955571 A CN 101955571A CN 2010102761047 A CN2010102761047 A CN 2010102761047A CN 201010276104 A CN201010276104 A CN 201010276104A CN 101955571 A CN101955571 A CN 101955571A
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Abstract
The invention discloses a method for preparing rosin-based polymer microspheres, which adopts nontoxic, harmless and reproducible rosin with sufficient raw materials as a raw material, and comprises the following steps: firstly reacting with 2-hydroxyethyl methacrylate to obtain ester, and then taking the ester and styrene as a reaction monomer, divinylbenzene as a cross-linking monomer, and gelatin as a stabilizer for preparing the micron-size rosin-based polymer microspheres by suspension polymerization, wherein the particle size of the obtained microspheres is 80-250 micrometers. The invention fully utilizes the natural resource of rosin in China, and the obtained product can be used as a pharmaceutical carrier and also an adsorbent and a separating agent.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of preparation method of polymer microballoon, particularly a kind of method of utilizing rosin to prepare polymer microballoon.
Technical background
Rosin is a kind of abundant renewable natural industrial chemicals.In recent years, along with the shortage of crude oil and the lifting of price, the scientific research personnel begins to explore and can substitute oil and become the renewable resources of producing macromolecular material.Rosin becomes the important source material source of preparation macromolecular material with its distinctive The Nomenclature Composition and Structure of Complexes.The rosin constitutional features is to contain two two keys and a carboxyl on the hydrogenation phenanthrene ring.Utilize reaction active groups such as carboxyl in the rosin molecular structure, conjugated double bond can obtain deep processed products such as polymerized rosin, staybelite and various rosin esters by reactions such as polymerization, additions, and further modification obtain high added value fine chemicals and polymer novel material.
The polymer microballoon of cross-linking type has characteristics such as specific surface area is big, solvent resistance good, adsorptivity is strong, the surface reaction ability is strong, is widely used in fields such as catalyzer, polymeric sorbent, biological medicine, information and microelectronics.With the polymer microballoon of crosslinked polystyrene as skeleton, raw material is easy to get and low price, has become the functional polymer that is most widely used up to now.
The preparation method of polymer microballoon is varied, is that the preparation method of the polymer microballoon of raw material has letex polymerization, suspension polymerization, dispersion polymerization and precipitation polymerization etc. with the monomer.Its used monomer mainly contains: vinyl, styrenic, (methyl) esters of acrylic acid, (methyl) acrylamide monomers, and epoxies monomer and vinyl acetate esters monomer etc.If when polymerization, add the monomer of the bifunctional of copolymerization with it, then can obtain crosslinked polymer microballoon, improve the intensity and the stability of polymer microballoon greatly.Common polymer microballoon is to be that raw material, divinylbenzene are linking agent by vinylbenzene, obtains by suspension polymerization.Along with the shortage of disposable resources such as oil, replace petrochemicals with renewable resourcess such as rosin, have important application prospects.
Summary of the invention
It is that raw material replaces vinylbenzene to prepare the method for polymer microballoon with rosin that the purpose of invention provides a kind of.Specifically, adopting rosin Jia Jibingxisuanβ-Qiang Yizhi carboxylate and vinylbenzene is raw material, and Vinylstyrene is the method that cross-linking monomer prepares polymer microballoon.Microspherulite diameter is 80-250 μ m, can also can be used as sorbent material and separating agent and use as pharmaceutical carrier.
Summary of the invention: with nontoxic, raw material is sufficient, reproducible rosin is raw material, at first obtain carboxylate with the Jia Jibingxisuanβ-Qiang Yizhi reaction, again with vinylbenzene as reaction monomers, Vinylstyrene is a cross-linking monomer, adopts suspension polymerization to prepare micron order rosinyl polymer microballoon.
Concrete steps are as follows:
(1) be that the raw material application number is that the preparation method of 200710085381.8 patent of invention makes rosin and crylic acid hydroxy ester carboxylate with rosin, methacrylic acid-beta-hydroxy ethyl ester, abbreviate carboxylate as, (application number is that 200710085381.8 patent of invention name is called " utilizing rosin and crylic acid hydroxy ester to prepare the method for carboxylate ");
(2) in the reactor that condenser, thermometer, agitator are housed, add the deionized water of weight percent 70～80% and the stablizer gelatin that weight percent is 0.1-1%, cool to about 60 ℃ after being heated to 70～80 ℃ of dissolvings fully, as water;
(3) carboxylate that step (1) is made is mixed and made into monomer mixture with weight percent 4.6～8% with the vinylbenzene of weight percent 9.6～14.8%, the Vinylstyrene of weight percent 0.5～1%; Add the initiator Diisopropyl azodicarboxylate of weight percent 0.1～0.3% and the pore-creating agent toluene of weight percent 0～10% again, mix, as oil phase;
(4) step (3) gained oil phase is added step (2) gained aqueous phase, under 300-500r/min, stir and be warming up to 80 ℃ of reactions after 3 hours, be warming up to 90 ℃ of reactions again and finished in 2 hours; With the product distilled water wash, filter the back oven dry after the cooling, obtain faint yellow rosinyl polymer microballoon, particle diameter is at the 80-250 micron.
The present invention makes full use of China's rosin natural resource, and products therefrom can be used as pharmaceutical carrier, also can be used as sorbent material and separating agent and uses.
Embodiment
Embodiment 1:
(1) is that the raw material application number is that the preparation method of 200710085381.8 patent of invention makes rosin and crylic acid hydroxy ester carboxylate with rosin, methacrylic acid-beta-hydroxy ethyl ester, abbreviates carboxylate as.The carboxylate acid number is below 15mgKOH/g.
(2) in the reactor that condenser, thermometer, agitator are housed, add the deionized water of weight percent 76% and the stablizer gelatin of weight percent 0.6%, cool to about 60 ℃ after being heated to 70～80 ℃ of dissolvings fully, as water;
(3) carboxylate that step (1) is made is with weight percent 5.0%, be mixed and made into monomer mixture with the vinylbenzene of weight percent 12.7% and the Vinylstyrene of weight percent 1%; Add the initiator Diisopropyl azodicarboxylate of weight percent 0.2% and the pore-creating agent toluene of weight percent 4.7% again, mix, as oil phase;
(4) step (3) gained oil phase is added step (2) gained aqueous phase,, under 300r/min, stir and be warming up to 80 ℃ of reactions after 3 hours, be warming up to 90 ℃ of reactions again and finished in 2 hours; With the product distilled water wash, filter back drying in baking oven after the cooling, obtain faint yellow rosinyl polymer microballoon, median size is 80 microns.
Embodiment 2:
(1) is that the raw material application number is that the preparation method of 200710085381.8 patent of invention makes rosin and crylic acid hydroxy ester carboxylate with rosin, methacrylic acid-beta-hydroxy ethyl ester, abbreviates carboxylate as.The carboxylate acid number is below 15mgKOH/g.
(2) in the reactor that condenser, thermometer, agitator are housed, add the deionized water of weight percent 73% and the stablizer gelatin of weight percent 0.4%, cool to about 60 ℃ after being heated to 70～80 ℃ of dissolvings fully, as water;
(3) carboxylate that step (1) is made is with weight percent 4.9%, be mixed and made into monomer mixture with the vinylbenzene of weight percent 12.2% and the Vinylstyrene of weight percent 0.5%; Add the initiator Diisopropyl azodicarboxylate of weight percent 0.2% and the pore-creating agent toluene of weight percent 8.8% again, mix, as oil phase;
(4) step (3) gained oil phase is added step (2) gained aqueous phase, under 500r/min, stir and be warming up to 80 ℃ of reactions after 3 hours, be warming up to 90 ℃ of reactions again and finished in 2 hours; With the product distilled water wash, filter back drying in baking oven after the cooling, obtain faint yellow rosinyl polymer microballoon, median size is 117 microns.
Embodiment 3:
(1) is that the raw material application number is that the preparation method of 200710085381.8 patent of invention makes rosin and crylic acid hydroxy ester carboxylate with rosin, methacrylic acid-beta-hydroxy ethyl ester, abbreviates carboxylate as.The carboxylate acid number is below 15mgKOH/g.
(2) in the reactor that condenser, thermometer, agitator are housed, add the deionized water of weight percent 80% and the stablizer gelatin of weight percent 0.1%, cool to about 60 ℃ after being heated to 70～80 ℃ of dissolvings fully, as water;
(3) carboxylate that step (1) is made is mixed and made into monomer mixture with weight percent 5.6% with the vinylbenzene of weight percent 13.6% and the Vinylstyrene of weight percent 0.5%; The initiator Diisopropyl azodicarboxylate that adds weight percent 0.2% again is as oil phase.
(4) step (3) gained oil phase is added step (2) gained aqueous phase, under 300r/min, stir and be warming up to 80 ℃ of reactions after 3 hours, be warming up to 90 ℃ of reactions again and finished in 2 hours; With the product distilled water wash, filter back drying in baking oven after the cooling, obtain faint yellow rosinyl polymer microballoon, median size is 250 microns.
Claims (1)
1. method for preparing the rosinyl polymer microballoon is characterized in that concrete steps are:
(1) is that the raw material application number is that the preparation method of 200710085381.8 patent of invention makes rosin and crylic acid hydroxy ester carboxylate with rosin, methacrylic acid-beta-hydroxy ethyl ester, abbreviates carboxylate as;
(2) in the reactor that condenser, thermometer, agitator are housed, add the deionized water of weight percent 70～80% and the stablizer gelatin that weight percent is 0.1-1%, cool to about 60 ℃ after being heated to 70～80 ℃ of dissolvings fully, as water;
(3) carboxylate that step (1) is made is mixed and made into monomer mixture with weight percent 4.6～8% with the vinylbenzene of weight percent 9.6～14.8%, the Vinylstyrene of weight percent 0.5～1%; Add the initiator Diisopropyl azodicarboxylate of weight percent 0.1～0.3% and the pore-creating agent toluene of weight percent 0～10% again, mix, as oil phase;
(4) step (3) gained oil phase is added step (2) gained aqueous phase, under 300-500r/min, stir and be warming up to 80 ℃ of reactions after 3 hours, be warming up to 90 ℃ of reactions again and finished in 2 hours; With the product distilled water wash, filter the back oven dry after the cooling, obtain faint yellow rosinyl polymer microballoon, particle diameter is at the 80-250 micron.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102761047A CN101955571A (en) | 2010-09-07 | 2010-09-07 | Method for preparing rosin-based polymer microspheres |
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| CN2010102761047A CN101955571A (en) | 2010-09-07 | 2010-09-07 | Method for preparing rosin-based polymer microspheres |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675517A (en) * | 2012-05-23 | 2012-09-19 | 桂林理工大学 | Preparation method of rosinyl magnetic polymer microspheres |
| CN102863646A (en) * | 2012-10-16 | 2013-01-09 | 桂林理工大学 | Preparation method for rosin-based porous polymer microsphere |
| CN103073090A (en) * | 2013-02-17 | 2013-05-01 | 桂林理工大学 | Method for removing methylene blue in waste water by carboxylated rosin-based polymeric microspheres |
| CN106732416A (en) * | 2016-12-01 | 2017-05-31 | 桂林理工大学 | A kind of rosin modifies the preparation method and applications of stalk adsorbent |
| CN109225083A (en) * | 2018-08-14 | 2019-01-18 | 桂林理工大学 | A kind of preparation method of self-crosslinking abietyl polyaminoester microball |
-
2010
- 2010-09-07 CN CN2010102761047A patent/CN101955571A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675517A (en) * | 2012-05-23 | 2012-09-19 | 桂林理工大学 | Preparation method of rosinyl magnetic polymer microspheres |
| CN102863646A (en) * | 2012-10-16 | 2013-01-09 | 桂林理工大学 | Preparation method for rosin-based porous polymer microsphere |
| CN102863646B (en) * | 2012-10-16 | 2014-01-08 | 桂林理工大学 | Preparation method for rosin-based porous polymer microsphere |
| CN103073090A (en) * | 2013-02-17 | 2013-05-01 | 桂林理工大学 | Method for removing methylene blue in waste water by carboxylated rosin-based polymeric microspheres |
| CN106732416A (en) * | 2016-12-01 | 2017-05-31 | 桂林理工大学 | A kind of rosin modifies the preparation method and applications of stalk adsorbent |
| CN109225083A (en) * | 2018-08-14 | 2019-01-18 | 桂林理工大学 | A kind of preparation method of self-crosslinking abietyl polyaminoester microball |
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Application publication date: 20110126 |