CN104341546B - A kind of preparation method of shelly oil absorbing polymer microsphere - Google Patents
A kind of preparation method of shelly oil absorbing polymer microsphere Download PDFInfo
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- CN104341546B CN104341546B CN201310316803.3A CN201310316803A CN104341546B CN 104341546 B CN104341546 B CN 104341546B CN 201310316803 A CN201310316803 A CN 201310316803A CN 104341546 B CN104341546 B CN 104341546B
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Abstract
The present invention is the preparation method of a kind of shelly oil absorbing polymer microsphere. It is to adopt suspension polymerization, first deionized water and dispersant are joined in the there-necked flask with agitating device, the mass ratio of deionized water and dispersant is 100:0.03��4.5, it is heated to 30��50 DEG C after dispersant dissolves, in there-necked flask, acrylate or methacrylate reaction monomers, the diacrylate crosslinking agents of glycol, radical polymerization initiator is added successively under the protection of high pure nitrogen, it is to slowly warm up to 60��80 DEG C, reacts and obtain oil absorbing polymer microsphere in 3��6 hours; Rear addition styrene and divinylbenzene, react 1��3 hour, generates high-crosslinking-degree surface structure outside microsphere; When stirring, reaction system is down to room temperature, oil suction microsphere is filtered, washing, sucking filtration, dry and just can obtain shelly oil absorbing polymer microsphere. Shelly oil absorbing polymer microsphere prepared by the present invention has the advantages that swelling rate is fast.
Description
Technical field
The present invention is the preparation method of a kind of shelly oil absorbing polymer microsphere, relates to technical field of petroleum industry.
Background technology
Day by day frequent along with offshore oil exploitation activity and oil transportation at sea, marine oil spill accident emerges in an endless stream. Oils is once after entering ocean, all can cause harm difficult to the appraisal, Oil spills to be referred to as the super killer of marine environment natural environment, aquaculture, shallow water seashore, harbour industry etc. The pollution of water body on road, also serious harm can be caused to environment, the impact that such as Song Hua River in 2005 is exploded by chemical plant, benzene class material enters river, flowing along with water body, pollutant downstream drift about, and cause that Heilungkiang, Song Hua River section is heavily contaminated, and two sides ecology, Aquatic product and DRINKING WATER are threatened. Simultaneously, the industrial wastewaters such as the industrial a large amount of electroplating wastewater of annual generation, wastewater from chemical industry, dyeing waste water, wherein contain substantial amounts of Organic substance, how quickly to separate from these industrial wastewaters from organic harmful toxic matter, be always up the difficult problem being not yet solved.
Polymer oil absorption material is a kind of high molecular polymer with three-dimensional netted chemical crosslinking structure, compared with traditional oil absorption material, polymer oil absorption material has the features such as absorption organism kinds is many, adsorbance big, guarantor's oil is effective, adsorption rate is fast, oil-water selectivity is high, recovery is convenient. The synthon of current high score subclass oil absorption material is mainly esters of acrylic acid and alpha-olefines, owing to the latter is expensive, therefore mostly adopts acrylic ester monomer to synthesize.Synthetic method mainly adopts suspension polymerisation and emulsion polymerization, and with esters of acrylic acid for raw material, oleosoluble radical initiators is that initiator carries out causing polymerization. Chinese patent CN1095727 discloses the synthetic method of a kind of oil absorption material, with acrylic acid, esters of acrylic acid material for monomer, with N, N-di-2-ethylhexylphosphine oxide acrylamide, EDIA class are cross-linking agent, with gelatin, polyvinyl alcohol, cellulose, inorganic salt powder for dispersant, calcium dodecyl benzene sulfonate is dispersion aids, is prepared for oil absorption material by free radical suspensioning polymerization. (Shandong Sunyu of Shandong Sunyu et al., Lu Jianmei, Nanjing Chemical Engineering College's journal, 1995,2,43-47) with acrylic acid-2-ethyl caproite and butyl methacrylate for monomer, atent solvent carries out suspension polymerisation, reaction terminate after with the solvent in methanol extraction particle thus being prepared for porous granule shape adsorbing material. These methods need porogen affiliated in specific means elimination preparation process, and preparation process is complicated, relatively costly, are unfavorable for the industry amplification of product and the popularization and application of product.
Summary of the invention
It is an object of the invention to invent that a kind of surface texture is different from nexine structure, improve oil absorption material performance, the preparation method improving the shelly oil absorbing polymer microsphere of oil absorption material swelling rate.
The shelly oil absorbing polymer microsphere of the present invention is divided into surface texture and nexine structure, and the synthetic ratio of shelly oil absorbing polymer microsphere interior layer material is: in weight 100%
The synthesizing formula of shelly oil absorbing polymer microsphere high-crosslinking-degree skin-material is: in weight 100%
Divinylbenzene accounts for 66.7��99%
Styrene accounts for 1��33.3%
The present invention is 100:0.1��5 for synthesizing the polymerization single polymerization monomer acrylate of interior layer material and skin-material or methacrylate and cinnamic weight ratio.
Described acrylate or methacrylate are carbon numbers be 4��18 straight chain fat or side chain fat;
Described cross-linking agent is the diacrylate of glycol, for instance diethylene glycol diacrylate, 1,3-PD diacrylate, 1,3 butylene glycol diacrylate, BDO diacrylate, 1,6-hexanediyl ester;
Described dispersant is polyvinyl alcohol, gelatin or modified cellulose class material, is one or more mixture.
Described initiator is common radical initiator, for instance azo dibutyl nitrile, azo diisobutyl nitrile, the different heptyl nitrile of azo two, azo-bis-iso-dimethyl, benzoyl peroxide, the benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide.
The preparation method of this shelly oil absorbing polymer microsphere, it is adopt suspension polymerization, first deionized water and dispersant are joined in the there-necked flask with agitating device, the mass ratio of deionized water and dispersant is 100:0.03��4.5, it is heated to 30��50 DEG C after dispersant dissolves, in there-necked flask, acrylate or methacrylate reaction monomers is added successively under the protection of high pure nitrogen, the diacrylate crosslinking agents of glycol, radical polymerization initiator, it is to slowly warm up to 60��80 DEG C, react and obtain oil absorbing polymer microsphere in 3��6 hours, monomer: cross-linking agent: the mass ratio of initiator is 100:0.01��3:0.05��4, being subsequently adding styrene and divinylbenzene, react 1��3 hour and can react generation one floor height degree of cross linking surface structure outside oil absorbing polymer microsphere, divinylbenzene and cinnamic mass ratio are 100:1��50,Then when stirring, reaction system is down to room temperature, finally oil suction microsphere is filtered, washing, sucking filtration, dry and just can obtain shelly oil absorbing polymer microsphere.
Concrete enforcement step is as follows:
1. adding aqueous dispersion in the there-necked flask with agitating device, under 30��50 DEG C of conditions, mix homogeneously is until dispersant is completely dissolved, and the mass ratio of water and dispersant is 100��1000:0.03��4.5;
2. under the protection of high pure nitrogen, in there-necked flask, add acrylate or methacrylate reaction monomers, the diacrylate crosslinking agents of glycol, radical polymerization initiator successively, monomer: cross-linking agent: the mass ratio of initiator is 100:0.01��3:0.05��4, slowly heat up 60��80 DEG C when steadily at the uniform velocity stirring, react 3��6 hours, oil absorbing polymer microsphere can be obtained;
3. styrene and divinylbenzene joining there-necked flask, reacts 1��3 hour, divinylbenzene and cinnamic mass ratio are 100:1��50, namely prepare the surface structure of a floor height degree of cross linking at oil absorbing polymer microsphere surface;
4. when stirring, reaction system is down to room temperature, finally polymerizing microballoons is filtered, washing, sucking filtration, the dry shelly oil absorbing polymer microsphere that just can obtain high-crosslinking-degree top layer.
The present invention is that production process is simple, course of reaction is easily controllable, adopt suspension polymerization to prepare shelly oil absorbing polymer microsphere for one, and prepared oil absorption material shows the feature that super-hydrophobicity, super-oleophilic and speed of oil absorption are fast.
Detailed description of the invention
Embodiment 1.
Weigh 600g deionized water and 1g polyvinyl alcohol dispersant joins in there-necked flask, to 45 DEG C, heating treats that polyvinyl alcohol is completely dissolved, in there-necked flask, 100g butyl methacrylate, 0.5g diethylene glycol diacrylate cross-linking agent, 0.6g benzoyl peroxide initiator is added successively under the protection of high pure nitrogen, it is to slowly warm up to 80 DEG C, reacts and within 4 hours, obtain oil absorbing polymer microsphere; Then in there-necked flask, add 1g styrene and 2g divinylbenzene, react 2 hours and can react generation one floor height degree of cross linking surface structure outside oil absorbing polymer microsphere; Then when stirring, reaction system is down to room temperature, finally oil suction microsphere is filtered, washing, sucking filtration, dry and just can obtain shelly oil absorbing polymer microsphere.
Embodiment 2.
Weigh 500g deionized water and 1g polyvinyl alcohol dispersant joins in there-necked flask, to 45 DEG C, heating treats that polyvinyl alcohol is completely dissolved, in there-necked flask, 100g butyl methacrylate, 3g1 is added successively under the protection of high pure nitrogen, 6-hexanediyl ester cross-linking agent, 3g benzoyl peroxide initiator, it is to slowly warm up to 80 DEG C, reacts and within 4 hours, obtain oil absorbing polymer microsphere; Then in there-necked flask, add 1g styrene and 5g divinylbenzene, react 2 hours and can react generation one floor height degree of cross linking surface structure outside oil absorbing polymer microsphere; Then when stirring, reaction system is down to room temperature, finally oil suction microsphere is filtered, washing, sucking filtration, dry and just can obtain shelly oil absorbing polymer microsphere.
Embodiment 3.
Weigh 800g deionized water and 2g polyvinyl alcohol dispersant joins in there-necked flask, to 45 DEG C, heating treats that polyvinyl alcohol is completely dissolved, in there-necked flask, 100g lauryl methacrylate, 0.5g1 is added successively under the protection of high pure nitrogen, 6-hexanediyl ester cross-linking agent, 0.6g benzoyl peroxide initiator, it is to slowly warm up to 80 DEG C, reacts and within 4 hours, obtain oil absorbing polymer microsphere;Then in there-necked flask, add 1g styrene and 2g divinylbenzene, react 2 hours and can react generation one floor height degree of cross linking surface structure outside oil absorbing polymer microsphere; Then when stirring, reaction system is down to room temperature, finally oil suction microsphere is filtered, washing, sucking filtration, dry and just can obtain shelly oil absorbing polymer microsphere.
Embodiment 4.
Weigh 600g deionized water and 1g polyvinyl alcohol dispersant joins in there-necked flask, to 45 DEG C, heating treats that polyvinyl alcohol is completely dissolved, in there-necked flask, 100g butyl methacrylate, 0.5g1 is added successively under the protection of high pure nitrogen, 6-hexanediyl ester cross-linking agent, 0.6g benzoyl peroxide initiator, it is to slowly warm up to 80 DEG C, reacts and within 4 hours, obtain oil absorbing polymer microsphere; Then in there-necked flask, add 2g styrene and 4g divinylbenzene, react 2 hours and can react generation one floor height degree of cross linking surface structure outside oil absorbing polymer microsphere; Then when stirring, reaction system is down to room temperature, finally oil suction microsphere is filtered, washing, sucking filtration, dry and just can obtain shelly oil absorbing polymer microsphere.
This example synthesis condition is wide in range, test through many experiments, above example all can prepare super-hydrophobic oil absorption material, its contact angle with water is all higher than 120 ��, to common liquid organic solvent such as gasoline, kerosene, benzene, toluene, Nitrobenzol, hexamethylene absorption multiplying power be all higher than 10, to common organic solvents all can reach in 1 minute absorption saturated.
Claims (1)
1. a preparation method for shelly oil absorbing polymer microsphere, shelly oil absorbing polymer microsphere is surface texture and nexine structure, and the synthetic ratio of shelly oil absorbing polymer microsphere interior layer material is: in weight 100%
The synthesizing formula of shelly oil absorbing polymer microsphere high-crosslinking-degree skin-material is: in weight 100%
Divinylbenzene accounts for 66.7��99%
Styrene accounts for 1��33.3%
It is 100:0.1��5 for synthesizing the polymerization single polymerization monomer acrylate of interior layer material and skin-material or methacrylate and cinnamic weight ratio;
The preparation method that it is characterized in that this shelly oil absorbing polymer microsphere, it is adopt suspension polymerization, first deionized water and dispersant are joined in the there-necked flask with agitating device, the mass ratio of deionized water and dispersant is 100:0.03��4.5, it is heated to 30��50 DEG C after dispersant dissolves, in there-necked flask, acrylate or methacrylate reaction monomers is added successively under the protection of high pure nitrogen, the diacrylate crosslinking agents of glycol, radical polymerization initiator, it is to slowly warm up to 60��80 DEG C, react and obtain oil absorbing polymer microsphere in 3��6 hours, monomer: cross-linking agent: the mass ratio of initiator is 100:0.01��3:0.05��4, being subsequently adding styrene and divinylbenzene, react 1��3 hour and can react generation one floor height degree of cross linking surface structure outside oil absorbing polymer microsphere, divinylbenzene and cinnamic mass ratio are 100:1��50, then when stirring, reaction system is down to room temperature, finally oil suction microsphere is filtered, washing, sucking filtration, dry and just can obtain shelly oil absorbing polymer microsphere.
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| CN104841386A (en) * | 2015-04-13 | 2015-08-19 | 浙江海洋学院 | Preparation method for composite high oil-absorption resin |
| CN104841388A (en) * | 2015-04-13 | 2015-08-19 | 浙江海洋学院 | Preparation method for resin adsorbent compounded with mussel shell powder |
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| CN105001377A (en) * | 2015-07-06 | 2015-10-28 | 安徽成方新材料科技有限公司 | Complex polyacrylate polymeric absorbent for rapidly absorbing oil and preparation method thereof |
| CN112076725A (en) * | 2019-06-12 | 2020-12-15 | 中国石油化工股份有限公司 | Modified mesoporous molecular sieve, and preparation method and application thereof |
| CN112076724B (en) * | 2019-06-12 | 2024-02-27 | 中国石油化工股份有限公司 | Supported mesoporous molecular sieve and preparation method and application thereof |
| CN112076726A (en) * | 2019-06-12 | 2020-12-15 | 中国石油化工股份有限公司 | Mesoporous molecular sieve loaded with ionic liquid and preparation method and application thereof |
| CN112592426A (en) * | 2020-12-16 | 2021-04-02 | 唐鹏飞 | Pore-forming preparation method of oil-absorbing resin |
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