CN105085776A - Preparation method of rare-earth fluorescent microspheres - Google Patents

Abstract

The invention relates to a preparation method of rare-earth fluorescent microspheres, belonging to the technical field of fluorescent substance preparation. The method comprises the following steps: carrying out pretreatment to obtain a monomer refined methyl methacrylate and an initiator refined azodiisobutyronitrile, preparing a rare-earth high-luminescent-intensity three-element coordination compound with polymerization activity by a coprecipitation process, copolymerizing the three-element coordination compound with methyl methacrylate to obtain a high-molecular-weight high-polymer rare-earth metal copolymer solid material which is the rare-earth fluorescent microspheres. The example proves that the rare-earth fluorescent microspheres can be used in the aspects of biological detection, fluorescent markers, special-type inks, medical immune detection and cell markers, can not injure the human body, and has stable and efficient luminous emissivity and longer fluorescent lifetime (by 30% or above).

Description

A kind of preparation method of rare-earth fluorescent microballoon

Technical field

The present invention relates to a kind of preparation method of rare-earth fluorescent microballoon, belong to fluorescent material preparing technical field.

Background technology

Fluorescent microsphere refers to diameter at nano level in micro-scaled range, and load has fluorescent substance, and stimulate the solia particle that can inspire fluorescence by outside energy, its profile can be arbitrary shape, and representative configuration is spherical.The carrier of fluorescent microsphere mostly is organic or inorganic polymer materials, and it has metastable morphological structure with exciting light behavior, less than pure fluorescent chemicals by the impact of ambient conditions as solvent, heat, electricity, magnetic etc.It is widely used in biomedical sector as a kind of novel solid support material, and the medicine orientation as biological chemistry and biomedical aspect is transported, Medical latex reagent, biomolecular labeling and spike, the mark of immunodetection, cell marking, accounting hybridization etc.

In daily life, along with fluorescent material is in the application of each artwork industry and toy industry, increasing businessman utilizes fluorescent material to change the performance of self product, but the plasticity-of general fluorescent material is poor, and do not reach industry standard, some clients be ignorant of often select expensive fluorescence product, think expensive good, but some simple characters of fluorescent material are not understood, fluorescence product all at present all unlike chemical composition can easily be decomposed, but at people's body accumulation, produce many objectionable impuritiess, greatly cut down body immunity, in addition, human body cell can also be made to occur that variability is inclined to, its toxicity is accumulated in liver or other vitals, potential carcinogenic factor can be become, cause blood system impaired.Moreover, the luminous intensity of current fluorescent material is very weak, the just few of brightness of general 2 hours, and the assay that said 10h, 20h are only theoretical, effect in reality is also not obvious.

Summary of the invention

The technical problem that the present invention mainly solves: poor for the product plasticity-at present made by general fluorescent material, and fluorescent material itself is containing a large amount of harmful material, human carcinoma's incidence can be improved, in addition, current fluorescent material luminous intensity is more weak, be difficult to maintain long-time luminous problem, provide a kind of preparation of rare-earth fluorescent microballoon, the method first obtains monomer refining methacylic acid methyl esters by pre-treatment and Diisopropyl azodicarboxylate refined by initiator, there is with coprecipitation method preparation the ternary complex of the rare earth high luminous intensity of polymerization activity, again itself and methyl methacrylate copolymer are obtained the polymer rare earth metal copolymer solids material that a class has high molecular, i.e. a kind of rare-earth fluorescent microballoon, not only plasticity-is strong, to human body without any harm, and fluorescent lifetime is permanent, fluorescent lifetime is made to improve more than 85%.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

(1) separating funnel that 100 ~ 200mL methyl methacrylate puts into 250mL is got, wash 3 ~ 5 times with the sodium hydroxide solution that mass concentration is 5%, each consumption 30 ~ 40mL is until colourless, again with deionized water rinsing to pH be after 7 ~ 8 with anhydrous sodium sulfate drying 5 ~ 7 days, obtain refining methacylic acid methyl esters;

(2) toward in 150mL Erlenmeyer flask, add 50 ~ 100mL dehydrated alcohol, put into water-bath and be heated to 50 ~ 55 DEG C, add 5 ~ 10g Diisopropyl azodicarboxylate again, shaking table vibration is all dissolved to it, fast filtering, filtrate is cooled to white crystal and separates out, with filtered on buchner funnel, the obtained refining Diisopropyl azodicarboxylate of vacuum drying oven drying is put in crystallization;

(3) in the 150mL there-necked flask that condensation reflux unit is housed, add 5 ~ 10mg europium sesquioxide, 1 ~ 2g α-methacrylic acid and 50 ~ 100mL water, heating in water bath to 80 ~ 90 DEG C, and pass into water of condensation, be placed on stirring reaction 2 ~ 3h on magnetic stirrer, mixing speed is 100 ~ 200r/min, obtained α-methacrylic acid europium complex solution;

(4) take 100 ~ 200mg phenanthroline and be dissolved in 50 ~ 100mL dehydrated alcohol, make phenanthroline alcoholic solution, by above-mentioned obtained complex solution warming-in-water to 60 ~ 70 DEG C, dropwise add phenanthroline alcoholic solution, bath temperature reaction 1 ~ 2h is kept to obtain suspension, put into pressure-reduction filter device, be decompressed to 800 ~ 900Pa, white solid is obtained after suction filtration, air dry oven is moved into again with after absolute ethanol washing 3 ~ 4 times, dry at 60 ~ 70 DEG C, obtain white powder, namely rare earth luminous title complex, for subsequent use;

(5) the above-mentioned obtained rare earth luminous title complex of 10 ~ 20g is got, 5 ~ 10mgN, N '-dimethyl methane amide and 50 ~ 100mL n-caprylic acid, put into sonic oscillation instrument supersound process 5 ~ 10min, ultrasonic frequency is 25 ~ 30kHz, get an Erlenmeyer flask again and put into thermostat water bath, bath temperature is 60 ~ 70 DEG C, pour the mixed solution after supersound process into Erlenmeyer flask, slowly be stirred to it to be become clearly by muddiness, continue to add 10 ~ 15mL ethanol, 50 ~ 60mg polyvinylpyrrolidone and 100 ~ 200mg Sodium dodecylbenzene sulfonate, bottleneck is sealed with film, 1 ~ 2h is stirred with homogenizer after raising bath temperature to 80 ~ 90 DEG C, mixing speed is 500 ~ 600r/min, activation dispersion agent,

(6) bath temperature to 50 ~ 60 DEG C are reduced, add 50 ~ 100g refining methacylic acid methyl esters and 10 ~ 15g refines Diisopropyl azodicarboxylate, 90 ~ 95 DEG C are warming up to after shaking table oscillatory reaction 3 ~ 4h under constant temperature, slaking reaction 1 ~ 2h, move into supercentrifuge, centrifugal 20 ~ 30min under the rotating speed of 9000 ~ 10000r/min, be separated and remove supernatant liquor, by throw out with after vacuum drier drying, obtain a kind of rare-earth fluorescent microballoon.

Application method of the present invention is: the rare-earth fluorescent microballoon made by the present invention can be used as biological detection, fluorescent mark, special ink and medical immunodetection, cell marking aspect, not only harmless, and have stable and luminosity factor efficiently, extend fluorescent lifetime, make fluorescent lifetime improve more than 30%.

The invention has the beneficial effects as follows:

(1) though immobilized on microballoon have fluorescence, to human body without any injury;

(2) rare-earth fluorescent microballoon has stable morphological structure and stablizes and efficient luminosity factor;

(3) illumination effect is remarkable, substantially increases fluorescent lifetime, makes fluorescent lifetime improve more than 30%.

Embodiment

First the separating funnel that 100 ~ 200mL methyl methacrylate puts into 250mL is got, wash 3 ~ 5 times with the sodium hydroxide solution that mass concentration is 5%, each consumption 30 ~ 40mL is until colourless, again with deionized water rinsing to pH be after 7 ~ 8 with anhydrous sodium sulfate drying 5 ~ 7 days, obtain refining methacylic acid methyl esters;

Then toward in 150mL Erlenmeyer flask, add 50 ~ 100mL dehydrated alcohol, put into water-bath and be heated to 50 ~ 55 DEG C, add 5 ~ 10g Diisopropyl azodicarboxylate again, shaking table vibration is all dissolved to it, fast filtering, filtrate is cooled to white crystal and separates out, with filtered on buchner funnel, the obtained refining Diisopropyl azodicarboxylate of vacuum drying oven drying is put in crystallization; Subsequently in the 150mL there-necked flask that condensation reflux unit is housed, add 5 ~ 10mg europium sesquioxide, 1 ~ 2g α-methacrylic acid and 50 ~ 100mL water, heating in water bath to 80 ~ 90 DEG C, and pass into water of condensation, be placed on stirring reaction 2 ~ 3h on magnetic stirrer, mixing speed is 100 ~ 200r/min, obtained α-methacrylic acid europium complex solution; Next take 100 ~ 200mg phenanthroline and be dissolved in 50 ~ 100mL dehydrated alcohol, make phenanthroline alcoholic solution, by above-mentioned obtained complex solution warming-in-water to 60 ~ 70 DEG C, dropwise add phenanthroline alcoholic solution, bath temperature reaction 1 ~ 2h is kept to obtain suspension, put into pressure-reduction filter device, be decompressed to 800 ~ 900Pa, white solid is obtained after suction filtration, air dry oven is moved into again with after absolute ethanol washing 3 ~ 4 times, dry at 60 ~ 70 DEG C, obtain white powder, namely rare earth luminous title complex, for subsequent use;

Get the above-mentioned obtained rare earth luminous title complex of 10 ~ 20g again, 5 ~ 10mgN, N '-dimethyl methane amide and 50 ~ 100mL n-caprylic acid, put into sonic oscillation instrument supersound process 5 ~ 10min, ultrasonic frequency is 25 ~ 30kHz, get an Erlenmeyer flask again and put into thermostat water bath, bath temperature is 60 ~ 70 DEG C, pour the mixed solution after supersound process into Erlenmeyer flask, slowly be stirred to it to be become clearly by muddiness, continue to add 10 ~ 15mL ethanol, 50 ~ 60mg polyvinylpyrrolidone and 100 ~ 200mg Sodium dodecylbenzene sulfonate, bottleneck is sealed with film, 1 ~ 2h is stirred with homogenizer after raising bath temperature to 80 ~ 90 DEG C, mixing speed is 500 ~ 600r/min, activation dispersion agent, finally reduce bath temperature to 50 ~ 60 DEG C, add 50 ~ 100g refining methacylic acid methyl esters and 10 ~ 15g refines Diisopropyl azodicarboxylate, 90 ~ 95 DEG C are warming up to after shaking table oscillatory reaction 3 ~ 4h under constant temperature, slaking reaction 1 ~ 2h, move into supercentrifuge, centrifugal 20 ~ 30min under the rotating speed of 9000 ~ 10000r/min, be separated and remove supernatant liquor, by throw out with after vacuum drier drying, obtain a kind of rare-earth fluorescent microballoon.

Example 1

First the separating funnel that 100mL methyl methacrylate puts into 250mL is got, 3 times are washed with the sodium hydroxide solution that mass concentration is 5%, each consumption 30mL until colourless, then with deionized water rinsing to pH be after 7 with anhydrous sodium sulfate drying 5 days, obtain refining methacylic acid methyl esters, then toward in 150mL Erlenmeyer flask, add 50mL dehydrated alcohol, put into water-bath and be heated to 50 DEG C, add 5g Diisopropyl azodicarboxylate again, shaking table vibration is all dissolved to it, fast filtering, filtrate is cooled to white crystal and separates out, with filtered on buchner funnel, the obtained refining Diisopropyl azodicarboxylate of vacuum drying oven drying is put in crystallization, subsequently in the 150mL there-necked flask that condensation reflux unit is housed, add 5mg europium sesquioxide, 1g α-methacrylic acid and 50mL water, heating in water bath to 80 DEG C, and pass into water of condensation, be placed on stirring reaction 2h on magnetic stirrer, mixing speed is 100r/min, obtained α-methacrylic acid europium complex solution, next take 100mg phenanthroline and be dissolved in 50mL dehydrated alcohol, make phenanthroline alcoholic solution, by above-mentioned obtained complex solution warming-in-water to 60 DEG C, dropwise add phenanthroline alcoholic solution, keep bath temperature reaction 1h to obtain suspension, put into pressure-reduction filter device, be decompressed to 800Pa, white solid is obtained after suction filtration, air dry oven is moved into again with after absolute ethanol washing 3 times, dry at 60 DEG C, obtain white powder, namely rare earth luminous title complex, for subsequent use, get the above-mentioned obtained rare earth luminous title complex of 10g again, 5mgN, N '-dimethyl methane amide and 50mL n-caprylic acid, put into sonic oscillation instrument supersound process 5min, ultrasonic frequency is 25kHz, get an Erlenmeyer flask again and put into thermostat water bath, bath temperature is 60 DEG C, pour the mixed solution after supersound process into Erlenmeyer flask, slowly be stirred to it to be become clearly by muddiness, continue to add 10mL ethanol, 50mg polyvinylpyrrolidone and 100mg Sodium dodecylbenzene sulfonate, bottleneck is sealed with film, 1h is stirred with homogenizer after raising bath temperature to 80 DEG C, mixing speed is 500r/min, activation dispersion agent, finally reduce bath temperature to 50 DEG C, add 50g refining methacylic acid methyl esters and 10g refines Diisopropyl azodicarboxylate, 90 DEG C are warming up to after shaking table oscillatory reaction 3h under constant temperature, slaking reaction 1h, move into supercentrifuge, centrifugal 20min under the rotating speed of 9000r/min, be separated and remove supernatant liquor, by throw out with after vacuum drier drying, obtain a kind of rare-earth fluorescent microballoon.

This example operation is simple, rare-earth fluorescent microballoon made by the present invention can be used as the fluorescent mark coating on motorway, not only for human body, environment without any impact, and have stable and luminosity factor efficiently, extend fluorescent lifetime, make fluorescent lifetime improve 30%.

Example 2

First the separating funnel that 150mL methyl methacrylate puts into 250mL is got, 4 times are washed with the sodium hydroxide solution that mass concentration is 5%, each consumption 35mL until colourless, then with deionized water rinsing to pH be after 7.5 with anhydrous sodium sulfate drying 6 days, obtain refining methacylic acid methyl esters, then toward in 150mL Erlenmeyer flask, add 80mL dehydrated alcohol, put into water-bath and be heated to 53 DEG C, add 7g Diisopropyl azodicarboxylate again, shaking table vibration is all dissolved to it, fast filtering, filtrate is cooled to white crystal and separates out, with filtered on buchner funnel, the obtained refining Diisopropyl azodicarboxylate of vacuum drying oven drying is put in crystallization, subsequently in the 150mL there-necked flask that condensation reflux unit is housed, add 8mg europium sesquioxide, 1.2g α-methacrylic acid and 80mL water, heating in water bath to 85 DEG C, and pass into water of condensation, be placed on stirring reaction 2.5h on magnetic stirrer, mixing speed is 150r/min, obtained α-methacrylic acid europium complex solution, next take 150mg phenanthroline and be dissolved in 80mL dehydrated alcohol, make phenanthroline alcoholic solution, by above-mentioned obtained complex solution warming-in-water to 65 DEG C, dropwise add phenanthroline alcoholic solution, keep bath temperature reaction 1.5h to obtain suspension, put into pressure-reduction filter device, be decompressed to 850Pa, white solid is obtained after suction filtration, air dry oven is moved into again with after absolute ethanol washing 3.5 times, dry at 65 DEG C, obtain white powder, namely rare earth luminous title complex, for subsequent use, get the above-mentioned obtained rare earth luminous title complex of 15g again, 7mgN, N '-dimethyl methane amide and 80mL n-caprylic acid, put into sonic oscillation instrument supersound process 8min, ultrasonic frequency is 28kHz, get an Erlenmeyer flask again and put into thermostat water bath, bath temperature is 65 DEG C, pour the mixed solution after supersound process into Erlenmeyer flask, slowly be stirred to it to be become clearly by muddiness, continue to add 13mL ethanol, 55mg polyvinylpyrrolidone and 150mg Sodium dodecylbenzene sulfonate, bottleneck is sealed with film, 1.5h is stirred with homogenizer after raising bath temperature to 85 DEG C, mixing speed is 550r/min, activation dispersion agent, finally reduce bath temperature to 550 DEG C, add 80g refining methacylic acid methyl esters and 13g refines Diisopropyl azodicarboxylate, 93 DEG C are warming up to after shaking table oscillatory reaction 3.5h under constant temperature, slaking reaction 1.5h, move into supercentrifuge, centrifugal 25min under the rotating speed of 9000 ~ 10000r/min, be separated and remove supernatant liquor, by throw out with after vacuum drier drying, obtain a kind of rare-earth fluorescent microballoon.

This example operation is simple, rare-earth fluorescent microballoon made by the present invention can be used as medical science noctilucence mark, not only for human body, environment without any impact, and have stable and luminosity factor efficiently, extend fluorescent lifetime, make fluorescent lifetime improve 33%.

Example 3

First the separating funnel that 200mL methyl methacrylate puts into 250mL is got, 5 times are washed with the sodium hydroxide solution that mass concentration is 5%, each consumption 40mL until colourless, then with deionized water rinsing to pH be after 8 with anhydrous sodium sulfate drying 7 days, obtain refining methacylic acid methyl esters, then toward in 150mL Erlenmeyer flask, add 100mL dehydrated alcohol, put into water-bath and be heated to 55 DEG C, add 10g Diisopropyl azodicarboxylate again, shaking table vibration is all dissolved to it, fast filtering, filtrate is cooled to white crystal and separates out, with filtered on buchner funnel, the obtained refining Diisopropyl azodicarboxylate of vacuum drying oven drying is put in crystallization, subsequently in the 150mL there-necked flask that condensation reflux unit is housed, add 10mg europium sesquioxide, 2g α-methacrylic acid and 100mL water, heating in water bath to 90 DEG C, and pass into water of condensation, be placed on stirring reaction 3h on magnetic stirrer, mixing speed is 200r/min, obtained α-methacrylic acid europium complex solution, next take 200mg phenanthroline and be dissolved in 100mL dehydrated alcohol, make phenanthroline alcoholic solution, by above-mentioned obtained complex solution warming-in-water to 70 DEG C, dropwise add phenanthroline alcoholic solution, keep bath temperature reaction 2h to obtain suspension, put into pressure-reduction filter device, be decompressed to 900Pa, white solid is obtained after suction filtration, air dry oven is moved into again with after absolute ethanol washing 4 times, dry at 70 DEG C, obtain white powder, namely rare earth luminous title complex, for subsequent use, get the above-mentioned obtained rare earth luminous title complex of 20g again, 10mgN, N '-dimethyl methane amide and 100mL n-caprylic acid, put into sonic oscillation instrument supersound process 10min, ultrasonic frequency is 30kHz, get an Erlenmeyer flask again and put into thermostat water bath, bath temperature is 70 DEG C, pour the mixed solution after supersound process into Erlenmeyer flask, slowly be stirred to it to be become clearly by muddiness, continue to add 15mL ethanol, 60mg polyvinylpyrrolidone and 200mg Sodium dodecylbenzene sulfonate, bottleneck is sealed with film, 1 ~ 2h is stirred with homogenizer after raising bath temperature to 90 DEG C, mixing speed is 600r/min, activation dispersion agent, finally reduce bath temperature to 60 DEG C, add 100g refining methacylic acid methyl esters and 15g refines Diisopropyl azodicarboxylate, 95 DEG C are warming up to after shaking table oscillatory reaction 4h under constant temperature, slaking reaction 2h, move into supercentrifuge, centrifugal 30min under the rotating speed of 10000r/min, be separated and remove supernatant liquor, by throw out with after vacuum drier drying, obtain a kind of rare-earth fluorescent microballoon.

This example operation is simple, rare-earth fluorescent microballoon made by the present invention can be used as fluorescent mark pen and ink raw material, not only for human body, environment without any impact, and have stable and luminosity factor efficiently, extend fluorescent lifetime, make fluorescent lifetime improve 35%.

Claims (1)

1. a preparation method for rare-earth fluorescent microballoon, is characterized in that concrete preparation process is:

(1) separating funnel that 100 ~ 200mL methyl methacrylate puts into 250mL is got, wash 3 ~ 5 times with the sodium hydroxide solution that mass concentration is 5%, each consumption 30 ~ 40mL is until colourless, again with deionized water rinsing to pH be after 7 ~ 8 with anhydrous sodium sulfate drying 5 ~ 7 days, obtain refining methacylic acid methyl esters;

(2) toward in 150mL Erlenmeyer flask, add 50 ~ 100mL dehydrated alcohol, put into water-bath and be heated to 50 ~ 55 DEG C, add 5 ~ 10g Diisopropyl azodicarboxylate again, shaking table vibration is all dissolved to it, fast filtering, filtrate is cooled to white crystal and separates out, with filtered on buchner funnel, the obtained refining Diisopropyl azodicarboxylate of vacuum drying oven drying is put in crystallization;

(3) in the 150mL there-necked flask that condensation reflux unit is housed, add 5 ~ 10mg europium sesquioxide, 1 ~ 2g α-methacrylic acid and 50 ~ 100mL water, heating in water bath to 80 ~ 90 DEG C, and pass into water of condensation, be placed on stirring reaction 2 ~ 3h on magnetic stirrer, mixing speed is 100 ~ 200r/min, obtained α-methacrylic acid europium complex solution;

(4) take 100 ~ 200mg phenanthroline and be dissolved in 50 ~ 100mL dehydrated alcohol, make phenanthroline alcoholic solution, by above-mentioned obtained complex solution warming-in-water to 60 ~ 70 DEG C, dropwise add phenanthroline alcoholic solution, bath temperature reaction 1 ~ 2h is kept to obtain suspension, put into pressure-reduction filter device, be decompressed to 800 ~ 900Pa, white solid is obtained after suction filtration, air dry oven is moved into again with after absolute ethanol washing 3 ~ 4 times, dry at 60 ~ 70 DEG C, obtain white powder, namely rare earth luminous title complex, for subsequent use;

(5) the above-mentioned obtained rare earth luminous title complex of 10 ~ 20g is got, 5 ~ 10mgN, N '-dimethyl methane amide and 50 ~ 100mL n-caprylic acid, put into sonic oscillation instrument supersound process 5 ~ 10min, ultrasonic frequency is 25 ~ 30kHz, get an Erlenmeyer flask again and put into thermostat water bath, bath temperature is 60 ~ 70 DEG C, pour the mixed solution after supersound process into Erlenmeyer flask, slowly be stirred to it to be become clearly by muddiness, continue to add 10 ~ 15mL ethanol, 50 ~ 60mg polyvinylpyrrolidone and 100 ~ 200mg Sodium dodecylbenzene sulfonate, bottleneck is sealed with film, 1 ~ 2h is stirred with homogenizer after raising bath temperature to 80 ~ 90 DEG C, mixing speed is 500 ~ 600r/min, activation dispersion agent,

(6) bath temperature to 50 ~ 60 DEG C are reduced, add 50 ~ 100g refining methacylic acid methyl esters and 10 ~ 15g refines Diisopropyl azodicarboxylate, 90 ~ 95 DEG C are warming up to after shaking table oscillatory reaction 3 ~ 4h under constant temperature, slaking reaction 1 ~ 2h, move into supercentrifuge, centrifugal 20 ~ 30min under the rotating speed of 9000 ~ 10000r/min, be separated and remove supernatant liquor, by throw out with after vacuum drier drying, obtain a kind of rare-earth fluorescent microballoon.