CN1296402C - Process for preparing active nano attapulgite intermediate - Google Patents
Process for preparing active nano attapulgite intermediate Download PDFInfo
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- CN1296402C CN1296402C CNB2004100732487A CN200410073248A CN1296402C CN 1296402 C CN1296402 C CN 1296402C CN B2004100732487 A CNB2004100732487 A CN B2004100732487A CN 200410073248 A CN200410073248 A CN 200410073248A CN 1296402 C CN1296402 C CN 1296402C
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Abstract
The present invention relates to a preparation method of active nanometer concave-convex rod intermediate bodies. In the method, equimolar addition is carried out to toluene diisocyanate and acrylic acid-beta-ester; addition products carry out addition reaction with xylene solution systems of nanometer concave-convex rods for generating nanometer concave-convex rod active intermediate bodies combined with double bonds on the surfaces. Prepared nanometer particles have a small particle diameter, are uniformly distributed and have good dispersivity in non-polar solvents; the nanometer particles can be copolymerized with other double-bond monomers for forming compound systems combined by nanometer concave-convex rods/polymers through covalent bond force and can cause nanometer concave-convex rods and macromolecule chains are combined through covalent bonds; the nanometer particles strengthen the bonding force between nanometer concave-convex rods and polymers, cause the distribution of nanometer concave-convex rods to be uniform in polymers and are favorable to sufficiently exerting the nanometer properties of nanometer concave-convex rods.
Description
Technical field
The present invention relates to the field of chemical synthesis of polymer active intermediate.
Background technology
Nano level Attapulgite and mixture thereof are little owing to having size, specific surface area reaches characteristics such as quantum size effect and macro quanta tunnel effect greatly, make it light, electricity, magnetic and chemical aspect represented novel characteristic, the research of therefore relevant in recent years preparation, performance and the application to the Attapulgite nano material at home and abroad is subjected to paying close attention to widely always.Wherein active nano attapulgite is different from the nano-attapulgite/polymer composite body system of coupling dispersing method preparation, at present about the application of nano-attapulgite in polymer composite body system, main by organic coupler and nano-attapulgite surface with of bonding assembling formation supramolecular system covalently or non-covalently, and then be scattered in polymeric constituent and form compound system, combining mainly between the nano-attapulgite that in this compound system, organises and the polymkeric substance with the combination of secondary valence bond power, in conjunction with not firm, to disperse irregular be its deficiency.
Summary of the invention
The objective of the invention is to overcome exist in the nano-attapulgite utilisation technology in the past disperse irregular, in conjunction with not firm deficiency, provide can be by copolyreaction with nano-attapulgite and polymer with nano-attapulgite intermediates preparation covalent bonds, that have high reaction activity.
The present invention is the preparation of active nano attapulgite intermediate, and its synthetic route is as follows:
N=1～6 wherein, A is attapulgite based.
Concrete synthesis step is as follows:
Step 1: being equipped with that stirring, heating, dropping liquid are reinforced, in the reactor of temp measuring system, adding tolylene diisocyanate, open to stir also and heat up, drip equimolar methacrylic acid-beta-hydroxy ethyl ester simultaneously, controlled temperature obtains affixture in 60 ℃ of reaction 2h.
Step 2: be equipped with that stirring, heating, dropping liquid are reinforced, in the reactor of oily water separation and temp measuring system, adding dimethylbenzene, is heating up back and heat up in a steamer anhydrous taking out of to the system, beginning to lower the temperature; When temperature is lower than 65 ℃, add the nano-attapulgite powder, dibutyltin dilaurate catalyst of 270 ℃ of oven dry, an amount of powerful stirring of anthraquinone stopper, treat the system homodisperse after, above-mentioned affixture is slowly dripped, in 70 ℃ of stirring reaction 4h; Underpressure distillation, separating dimethyl benzene obtain the active nano attapulgite intermediate.
Nano-attapulgite and affixture are collectively referred to as reaction mass.Following per-cent all is weight percentage.
The ratio of nano-attapulgite is 30%～75% of a reaction mass.
Selecting dimethylbenzene for use is solvent, and ratio is 40% of total charging capacity.Total charging capacity is that reaction mass adds dimethylbenzene.
Selecting catalyzer for use is dibutyl tin laurate, and ratio is 0.5% of a reaction mass.
Selecting anthraquinone for use is stopper, and ratio is 1% of methacrylic acid-beta-hydroxy ethyl ester consumption.
Reaction system adopts underpressure distillation, and pressure is 380mmHg.
Adopt the active nano attapulgite of the inventive method preparation, can form nano-attapulgite/polymer composite body system with two key class monomer copolymerizations, make nano-attapulgite and macromolecular chain with covalent bonds, strengthened the bonding force between nano-attapulgite and the polymkeric substance, and make nano-attapulgite being more evenly distributed in polymkeric substance, more help giving full play to of nano-attapulgite nano-meter characteristic.
Description of drawings
Fig. 1 is the transmission electron micrograph of Attapulgite.Fig. 2 is the projection electron Photomicrograph of prepared nano active intermediate.Fig. 3,4 is respectively the infrared analysis spectrogram of Attapulgite and active nano attapulgite intermediate.
Embodiment
Embodiment 1: the 34.4g tolylene diisocyanate is dropped in the reactor, 25.6g methacrylic acid-β hydroxyl ethyl ester places the dropping liquid feeder, open and stir and intensification, begin to drip methacrylic acid-β hydroxyl ethyl ester, system temperature must not be higher than 60 ℃, behind reinforced the end, insulation 2h, discharging must add adult; 160g dimethylbenzene is added in the reactor, heat up back and heat up in a steamer moisture in the system of taking out of, 70 ℃ of temperature are adjusted in anhydrous back, the 180g nano-attapulgite powder, 1.2g dibutyl tin laurate, the 0.5g anthraquinone that add 270 ℃ of oven dry, the powerful stirring is uniformly dispersed system, and gradation adds the adult that adds that 60g makes previously, adds the back in 70 ℃ of insulation 4h, in the survey system-and NCO content is lower than 5% termination reaction, and decompression steams dimethylbenzene and gets the active nano attapulgite intermediate.This embodiment Attapulgite accounts for total mass 75.0%.
Embodiment 2: the 60.7g tolylene diisocyanate is dropped in the reactor, 51.3g methacrylic acid-β hydroxyl ethyl ester places the dropping liquid feeder, open and stir and intensification, begin to drip methyl methacrylic acid-beta-hydroxy ethyl ester, system temperature must not be higher than 60 ℃, behind reinforced the end, insulation 2h, discharging must add adult; 160g dimethylbenzene is added in the reactor, heat up back and heat up in a steamer moisture in the system of taking out of, 70 ℃ of temperature are adjusted in anhydrous back, the 120g nano-attapulgite powder, 1.2g dibutyl tin laurate, the 0.5g anthraquinone that add 270 ℃ of oven dry, the powerful stirring is uniformly dispersed system, gradation add make previously add adult 120g, add the back in 70 ℃ of insulation 4h, in the survey system-and NCO content is lower than 5% termination reaction, and decompression steams dimethylbenzene and gets the active nano attapulgite intermediate.This embodiment Attapulgite accounts for total mass 50.0%.
Embodiment 3: the 96.2g tolylene diisocyanate is dropped in the reactor, 71.8g methacrylic acid-beta-hydroxy ethyl ester places the dropping liquid feeder, open and stir and intensification, begin to drip methacrylic acid-beta-hydroxy ethyl ester, system temperature must not be higher than 60 ℃, behind reinforced the end, insulation 2h, discharging must add adult; 160g dimethylbenzene is added in the reactor, heat up back and heat up in a steamer moisture in the system of taking out of, 70 ℃ of temperature are adjusted in anhydrous back, the 72g nano-attapulgite powder, 1.2g dibutyl tin laurate, the 0.5g anthraquinone that add 270 ℃ of oven dry, the powerful stirring is uniformly dispersed system, and gradation adds the adult that adds that 168g makes previously, adds the back in 70 ℃ of insulation 4h, in the survey system-and NCO content is lower than 5% termination reaction, and decompression steams dimethylbenzene and gets the active nano attapulgite intermediate.This embodiment Attapulgite accounts for total mass 30.0%
Fig. 1 is the transmission electron micrograph of Attapulgite, and the diameter that can see Attapulgite is 15-25nm.Fig. 2 is the projection electron Photomicrograph of prepared nano active intermediate, and prepared as seen from the figure Attapulgite active intermediate good dispersion is nano level, and diameter is 30-40nm.Fig. 3,4 is respectively the infrared analysis spectrogram of Attapulgite and active nano attapulgite intermediate.Can see the obvious grafting of affixture of Attapulgite and TDI-HEMA by transmission electron microscope and infared spectrum.
Claims (6)
1, active nano attapulgite intermediates preparation is characterized in that synthetic route is as follows:
N=1～6 wherein, A is attapulgite based,
Step 1: being equipped with that stirring, heating, dropping liquid are reinforced, in the reactor of temp measuring system, adding tolylene diisocyanate, open to stir also and heat up, drip equimolar methacrylic acid-beta-hydroxy ethyl ester simultaneously, controlled temperature obtains affixture in 60 ℃ of reaction 2h;
Step 2: be equipped with that stirring, heating, dropping liquid are reinforced, in the reactor of oily water separation and temp measuring system, adding dimethylbenzene, is heating up back and heat up in a steamer anhydrous taking out of to the system, beginning to lower the temperature; When temperature is lower than 65 ℃, add the nano-attapulgite powder, dibutyltin dilaurate catalyst of 270 ℃ of oven dry, an amount of powerful stirring of anthraquinone stopper, treat the system homodisperse after, above-mentioned affixture is slowly dripped, in 70 ℃ of stirring reaction 4h; Underpressure distillation, separating dimethyl benzene obtain the active nano attapulgite intermediate.
2, active nano attapulgite intermediates preparation according to claim 1, the ratio that it is characterized in that nano-attapulgite is 30%～75% of a reaction mass weight percent.
3, active nano attapulgite intermediates preparation according to claim 1, it is characterized in that selecting for use dimethylbenzene is solvent, ratio is 40% of total charging capacity weight percent.
4, active nano attapulgite intermediates preparation according to claim 1, it is characterized in that selecting for use catalyzer is dibutyl tin laurate, ratio is 0.5% of a reaction mass weight percent.
5, active nano attapulgite intermediates preparation according to claim 1, it is characterized in that selecting for use anthraquinone is stopper, ratio is 1% of methacrylic acid-beta-hydroxy ethyl ester consumption weight percent.
6, active nano attapulgite intermediates preparation according to claim 1 is characterized in that reaction system adopts underpressure distillation, and pressure is 380mmHg.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100732487A CN1296402C (en) | 2004-10-27 | 2004-10-27 | Process for preparing active nano attapulgite intermediate |
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| CNB2004100732487A CN1296402C (en) | 2004-10-27 | 2004-10-27 | Process for preparing active nano attapulgite intermediate |
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| CN1296402C true CN1296402C (en) | 2007-01-24 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039193A (en) * | 1989-04-11 | 1990-01-31 | 四川建筑材料工业学院 | The semidry method acid heat activation of attapulgite clay |
| CN1255510A (en) * | 1998-11-26 | 2000-06-07 | 中国石油化工集团公司 | nm-class polyolefine-clay composition |
| CN1334289A (en) * | 2000-07-20 | 2002-02-06 | 中国石油化工股份有限公司 | Polypropylene composite material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039193A (en) * | 1989-04-11 | 1990-01-31 | 四川建筑材料工业学院 | The semidry method acid heat activation of attapulgite clay |
| CN1255510A (en) * | 1998-11-26 | 2000-06-07 | 中国石油化工集团公司 | nm-class polyolefine-clay composition |
| CN1334289A (en) * | 2000-07-20 | 2002-02-06 | 中国石油化工股份有限公司 | Polypropylene composite material |
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