CN104475164B - A kind of preparation method of the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of rhenium - Google Patents
A kind of preparation method of the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of rhenium Download PDFInfo
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- CN104475164B CN104475164B CN201410665613.7A CN201410665613A CN104475164B CN 104475164 B CN104475164 B CN 104475164B CN 201410665613 A CN201410665613 A CN 201410665613A CN 104475164 B CN104475164 B CN 104475164B
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Abstract
The preparation method that the present invention relates to the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of a kind of rhenium.Under agitation, polymethyl methacrylate solution is added dropwise in poly-vinyl alcohol solution, after dripping polymethyl methacrylate solution, add the rehenic acid ammonium of mixed liquor gross weight 0.01～0.3%, 0.5～2% dispersant, continuously stirred 0.5～8h, supersound process 10～30min under 100～500W, obtain uniform, stable emulsion；By uniform, stable emulsion swelling 24 hours in dichloroethanes, with concentrated sulphuric acid sulfonation 4 hours at 70～80 DEG C, washing microsphere, to neutral, obtains target product.The modified sulfonic acid type poly (methyl methacrylate) micro-sphere of rhenium prepared by application the inventive method has the active and better stability of better catalysis, particle diameter is substantially all at 10～100 microns, water content 47%～49%, the required process time is shorter, also has good activity after many secondary responses.
Description
Technical field
The invention belongs to materials synthesis field, the preparation method being specially the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of a kind of rhenium.
Background technology
Polymethyl methacrylate (PMMA) be acrylate apoplexy due to endogenous wind most important be also the most frequently used a kind of material, function admirable, of many uses, it has also become one of plastic product being used widely in each department of national economy.PMMA after polishing is widely used in making Medical vessel, the transparent cover of medical equipment (such as calorstat, control box etc.), observation mirror, operational tool etc..Owing to PMMA and tissue have the good compatibility, to human non-toxic, light transmission is good, stable chemical nature, it is readily processible to required form, therefore medically can produce artificial cornea, orthopaedics bonding fixing joint prosthese, bone cement, artificial tooth, justice neck, model powder, dental base acrylic resin powder, acrylic resin teeth and skeleton slow-release material etc. with PMMA.Show that polymethyl methacrylate is better than politef silica gel, the tissue bulking material in the past used through base apatite and polypropylene phthalein amine etc. without anaphylaxis, biocompatibility and chemical inertness in the clinical practice of orthopaedics, ophthalmology for many years.
The polymer microballoon of different-grain diameter, its performance and range of application are also different.The preparation method of polymer microballoon has chemical method and Physical.In prior art, the preparation method of PMMA microsphere has: emulsion polymerization (0.01～0.5 μm), emulsifier-free emulsion polymerization (0.2～0.8 μm), seeding polymerization (0.5～1 μm), dispersin polymerization (0.8～10 μm), seed swelling (1～l0 μm), suspension polymerisation (100～1000 μm).Particle size range is between 0.01～10 μm and 100～1000 μm.Particle diameter microsphere between 10～100 μm not easily pollutes owing to having, and should not block, and the feature of good stability and activity can be kept to be favored, and future also can be widely used in the field such as catalysis and material.
Summary of the invention
The preparation method that it is an object of the invention to provide the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of a kind of rhenium.
The present invention is achieved through the following technical solutions: the preparation method of the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of a kind of rhenium, comprises the following steps:
1) polymethyl methacrylate is dissolved in organic solvent, obtains the polymethyl methacrylate solution that mass percentage concentration is 0.5～2.0%；Described organic solvent is one or both mixing of dichloromethane, dichloroethanes, chloroform, oxolane, toluene or acetone.
2) dissolve polyvinyl alcohol in deionized water, obtain the poly-vinyl alcohol solution that mass percentage concentration is 1.0～2.5%；
3) under agitation, polymethyl methacrylate solution is added dropwise in poly-vinyl alcohol solution, after dripping polymethyl methacrylate solution, add the rehenic acid ammonium of mixed liquor gross weight 0.01～0.3%, the dispersant of 0.5～2%, continuously stirred 0.5～8h, supersound process 10～30min under 100～500W, obtain uniform, stable emulsion.Described dispersant is alkylphenol polyoxyethylene (op-10)；The volume ratio of polymethyl methacrylate solution and poly-vinyl alcohol solution is 1:1-3
4) in dichloroethanes, swelling, after 24 hours, obtains poly (methyl methacrylate) micro-sphere；
5) by solid-to-liquid ratio 1:5, poly (methyl methacrylate) micro-sphere being added concentrated sulphuric acid, sulfonation 3～4 hours at 70～80 DEG C, washing microsphere, to neutral, obtains target product.
The invention has the beneficial effects as follows: the present invention has the advantage that operating procedure is simple, implementation condition is gentle.The present invention regulates and controls the size of poly (methyl methacrylate) micro-sphere, particle size distribution by the ratio of the concentration of polymethyl methacrylate solution, polyvinyl alcohol concentration, organic facies and aqueous phase, ultrasonic power, ultrasonic time, adds rehenic acid ammonium and serves the dual function of strengthening and pore.The modified sulfonic acid type poly (methyl methacrylate) micro-sphere of gained rhenium of the present invention has excellent catalytic performance, has better dispersibility, and better activity, also can keep good activity after many secondary responses.
Accompanying drawing explanation
Fig. 1 is the optical microscope of modified sulfonic acid type polymethyl methacrylate (PMMA) microsphere of rhenium that embodiment 3 prepares.
Fig. 2 is the scanning electron microscope of modified sulfonic acid type polymethyl methacrylate (PMMA) microsphere of rhenium that embodiment 3 prepares.
Detailed description of the invention
The preparation method of the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of embodiment 1 rhenium
1) weigh the polymethyl methacrylate that relative molecular mass is 410000 to be dissolved in chloroform, be completely dissolved, obtain the polymethyl methacrylate solution that mass percentage concentration is 0.5%.
2) dissolve polyvinyl alcohol in deionized water, obtain the poly-vinyl alcohol solution that mass percentage concentration is 1%.
3) measuring polyvinyl alcohol (PVA) the aqueous solution 10mL of 1%, load in 500mL conical flask, by magnetic stirrer, mixing speed is 1200r/min.Under agitation, it is that 0.5% polymethyl methacrylate solution 10ml is added dropwise in poly-vinyl alcohol solution by mass percentage concentration, after dripping polymethyl methacrylate solution, add the rehenic acid ammonium of mixed liquor gross weight 0.01%, dispersant op-10 (alkylphenol polyoxyethylene) the at room temperature continuous uniform stirring 2h of 0.5%, supersound process 10min under 150W, obtains uniform, stable emulsion.
4) obtaining uniform, stable emulsion, in dichloroethanes, swelling 24 hours, obtain poly (methyl methacrylate) micro-sphere.
5) by solid-to-liquid ratio 1:5, poly (methyl methacrylate) micro-sphere being added concentrated sulphuric acid, sulfonation 3 hours at 70 DEG C, washing microsphere, to neutral, obtains target product.
6) particle diameter taken microsphere 100% between 10～100 microns is sieved by screen cloth.
The preparation method of the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of embodiment 2 rhenium
1) weigh the polymethyl methacrylate that relative molecular mass is 410000 to be dissolved in chloroform, be completely dissolved, obtain the polymethyl methacrylate solution that mass percentage concentration is 1%.
2) dissolve polyvinyl alcohol in deionized water, obtain the poly-vinyl alcohol solution that mass percentage concentration is 1.5%.
3) measuring polyvinyl alcohol (PVA) the aqueous solution 20mL of 1.5%, load in 500mL conical flask, by magnetic stirrer, mixing speed is 1400r/min.Under agitation, it is that 1% polymethyl methacrylate solution 10ml is added dropwise in poly-vinyl alcohol solution by mass percentage concentration, after dripping polymethyl methacrylate solution, add the rehenic acid ammonium of mixed liquor gross weight 0.1%, dispersant op-10 (alkylphenol polyoxyethylene) the at room temperature continuous uniform stirring 2.5h of 1%, supersound process 20min under 250W, obtains uniform, stable emulsion.
4) by obtaining uniform, stable emulsion swelling 24 hours in dichloroethanes, poly (methyl methacrylate) micro-sphere is obtained.
5) adding concentrated sulphuric acid, sulfonation 3.5 hours at 70 DEG C by solid-to-liquid ratio 1:5 poly (methyl methacrylate) micro-sphere, washing microsphere, to neutral, obtains target product.
6) particle diameter taken microsphere 100% between 10～100 microns is sieved by screen cloth.
The preparation method of the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of embodiment 3 rhenium
1) weigh the polymethyl methacrylate that relative molecular mass is 410000 to be dissolved in chloroform, be completely dissolved, obtain the polymethyl methacrylate solution that mass percentage concentration is 1.5%.
2) dissolve polyvinyl alcohol in deionized water, obtain the poly-vinyl alcohol solution that mass percentage concentration is 2%.
3) measuring polyvinyl alcohol (PVA) the aqueous solution 20mL of 2%, load in 500mL conical flask, by magnetic stirrer, mixing speed is 1600r/min.Under agitation, it is that 1.5% polymethyl methacrylate solution 10ml is added dropwise in poly-vinyl alcohol solution by mass percentage concentration, after dripping polymethyl methacrylate solution, add the rehenic acid ammonium of mixed liquor gross weight 0.3%, dispersant op-10 (alkylphenol polyoxyethylene) the at room temperature continuous uniform stirring 3h of 1.5%, supersound process 25min under 350W, obtains uniform, stable emulsion.
4) obtaining uniform, stable emulsion, in dichloroethanes, swelling 24 hours, obtain poly (methyl methacrylate) micro-sphere.
5) by solid-to-liquid ratio 1:5, poly (methyl methacrylate) micro-sphere being added concentrated sulphuric acid sulfonation 3.5 hours at 80 DEG C, washing microsphere, to neutral, obtains target product.
6) particle diameter taken microsphere 100% between 10～100 microns is sieved by screen cloth.
The optical microscope of modified sulfonic acid type polymethyl methacrylate (PMMA) microsphere of target product rhenium is as shown in Figure 1, scanning electron microscope is as shown in Figure 2, from Fig. 1 and Fig. 2, microspherulite diameter is substantially at 10～100 microns, show that Particle dispersity is fine, activity is also significantly high, high more a lot of than general polymethyl methacrylate (PMMA) microsphere activity.
The preparation method of the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of embodiment 4 rhenium
1) weigh the polymethyl methacrylate that relative molecular mass is 410000 to be dissolved in chloroform, be completely dissolved, obtain the polymethyl methacrylate solution that mass percentage concentration is 2%.
2) dissolve polyvinyl alcohol in deionized water, obtain the poly-vinyl alcohol solution that mass percentage concentration is 2.5%.
3) measuring polyvinyl alcohol (PVA) the aqueous solution 30mL of 2.5%, load in 500mL conical flask, by magnetic stirrer, mixing speed is 1800r/min.Under agitation, it is that 2% polymethyl methacrylate solution 10ml is added dropwise in poly-vinyl alcohol solution by mass percentage concentration, after dripping polymethyl methacrylate solution, add the rehenic acid ammonium of mixed liquor gross weight 0.25%, dispersant op-10 (alkylphenol polyoxyethylene) the at room temperature continuous uniform stirring 4h of 2%, supersound process 30min under 500W, obtains uniform, stable emulsion.
4) by obtaining uniform, stable emulsion swelling 24 hours in dichloroethanes, poly (methyl methacrylate) micro-sphere is obtained.
5) by solid-to-liquid ratio 1:5, poly (methyl methacrylate) micro-sphere being added concentrated sulphuric acid sulfonation 4 hours at 80 DEG C, washing microsphere, to neutral, obtains target product.
6) particle diameter taken microsphere 100% between 10～100 microns is sieved by screen cloth.
Claims (2)
1. the preparation method of the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of rhenium, it is characterised in that comprise the following steps:
1) polymethyl methacrylate is dissolved in organic solvent, obtains the polymethyl methacrylate solution that mass percentage concentration is 0.5～2.0%；
2) dissolve polyvinyl alcohol in deionized water, obtain the poly-vinyl alcohol solution that mass percentage concentration is 1.0～2.5%；
3) under agitation, polymethyl methacrylate solution is added dropwise in poly-vinyl alcohol solution, after dripping polymethyl methacrylate solution, add the rehenic acid ammonium of mixed liquor gross weight 0.01～0.3%, continuously stirred 0.5～the 8h of dispersant of 0.5～2%, then supersound process 10～30min under 100～500W, obtains uniform, stable emulsion；Described dispersant is alkylphenol polyoxyethylene；The volume ratio of polymethyl methacrylate solution and poly-vinyl alcohol solution is 1:1～3；
4), in dichloroethanes after swelling 24 hours, poly (methyl methacrylate) micro-sphere is obtained；
5) poly (methyl methacrylate) micro-sphere being added concentrated sulphuric acid, sulfonation 3～4 hours at 70～80 DEG C, washing microsphere, to neutral, obtains target product；The solid-to-liquid ratio of poly (methyl methacrylate) micro-sphere and concentrated sulphuric acid is 1:5.
2. the preparation method of the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of rhenium as claimed in claim 1, it is characterised in that: described organic solvent is one or both mixing of dichloromethane, dichloroethanes, chloroform, oxolane, toluene or acetone.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1702085A (en) * | 2005-05-19 | 2005-11-30 | 华南理工大学 | Process for preparing magnetic polymethyl methacrylate microsphere by two-step method |
| CN101787138A (en) * | 2010-01-26 | 2010-07-28 | 广东冠昊生物科技股份有限公司 | Preparation method of micron-sized polymethylmethacrylate microsphere |
| CN103554376A (en) * | 2013-10-22 | 2014-02-05 | 上海华明高技术（集团）有限公司 | Preparation method of monodisperse cross-linked polymethyl methacrylate microspheres |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1702085A (en) * | 2005-05-19 | 2005-11-30 | 华南理工大学 | Process for preparing magnetic polymethyl methacrylate microsphere by two-step method |
| CN101787138A (en) * | 2010-01-26 | 2010-07-28 | 广东冠昊生物科技股份有限公司 | Preparation method of micron-sized polymethylmethacrylate microsphere |
| CN103554376A (en) * | 2013-10-22 | 2014-02-05 | 上海华明高技术（集团）有限公司 | Preparation method of monodisperse cross-linked polymethyl methacrylate microspheres |
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Effective date of registration: 20190920 Address after: 116000 No. 7, 8-1, Taishan Street, Shahekou District, Dalian City, Liaoning Province Patentee after: Gao Linyu Address before: 110000, Liaoning, Shenyang, Shenbei New Area moral South Avenue No. 58 Patentee before: Liaoning University |
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Effective date of registration: 20230412 Address after: No. 1, Xiaopingdao Square, Ganjingzi District, Dalian City, Liaoning Province, 116000 Patentee after: Eric (Dalian) Safety Technology Group Co.,Ltd. Address before: 8-1, No. 7, Mount Taishan East Street, Shahekou District, Dalian City, Liaoning Province, 116000 Patentee before: Gao Linyu |