CN102174131B - Rubber with fluorescence response to pH value and preparation method thereof - Google Patents
Rubber with fluorescence response to pH value and preparation method thereof Download PDFInfo
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- CN102174131B CN102174131B CN201110039396A CN201110039396A CN102174131B CN 102174131 B CN102174131 B CN 102174131B CN 201110039396 A CN201110039396 A CN 201110039396A CN 201110039396 A CN201110039396 A CN 201110039396A CN 102174131 B CN102174131 B CN 102174131B
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- rhodamine
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Abstract
The invention relates to rubber with fluorescence response to a pH value and a preparation method thereof. The method comprises the following steps of: measuring acetyl chloride, adding into rhodamine B-containing alcohol solution dropwise, preserving heat for reaction, evaporating to remove the alcohol solution under reduced pressure, and washing by using ethyl acetate to obtain rhodamine B ester; dissolving the rhodamine B ester in hot methanol, adding ethylenediamine, performing refluxing reaction, cooling to room temperature, removing the methanol, adding an organic solvent 1 and water, and washing and drying an organic layer to obtain ethylenediamine substituted rhodamine B; and weighing chlorosulfonated polyethylene rubber, swelling in an organic solvent 2, adding the ethylenediamine substituted rhodamine B, reacting, filtering off a solid, washing, and drying to obtain the rubber with the fluorescence response to the pH value. The rubber prepared by the method is functional rubber with the fluorescence response to the pH value, and can detect and analyze the pH value of a biological system, a chemical reaction system, industrial wastewater, a river, a lake or an ocean.
Description
Technical field
The present invention relates to a kind ofly has rubber of fluorescence response and preparation method thereof to the pH value; Be particularly related to the chlorosulfonated polyethylene rubber of side chain graft rhodamine (Rhodamine) fluorescence molecule, the pH value that is used for living things system, chemical reaction system, trade effluent, river, lake or ocean detects, analyzes.
Background technology
The pollution of natural water, the carrying out of chemical reaction or completion, many important physiological processes of cell and organoid etc. are all closely related with the pH value.At present, many methods can be used for detecting these methods of pH and comprise electrochemistry, nuclear-magnetism, absorption spectrum and fluorescence spectrum method.The method of the most generally measuring the pH value is to use glass electrode.But owing to exist electrochemistry to disturb, defective such as possible physical abuse and be inappropriate for the water body of some chemical reaction, serious pollution and the pH of living microbe detects.In addition, glass electrode also is inappropriate for the measurement of extreme pH.
Fluorescent spectrometry is because its nondestructive, high sensitivity and specificity, and widely available optical dye has more meliority than additive method when measuring pH.The rhodamine fluorochrome has high molar absorption coefficient and high-fluorescence quantum yield, and its absorption spectrum is at visible region, and emmission spectrum is near red light district (500～680 nm).The rhodamine fluorochrome that has polar group changes the pH value mostly has fluorescence response, and through can satisfy the needs of different working conditionss (for example: maximum absorption wavelength, maximum emission wavelength, quantum yield etc.) to the modification of parent.The rhodamine fluorochrome has obtained using widely as the pH fluorescent probe.
For the ease of push away band and use occurred in recent ten years multiple with the pH probe of pH probe stationary on carrier.Its curing mainly is to adopt absorption, covalent bonding and three kinds of modes of embedding.Organic carrier commonly used through covalent linkage parcel pH indicator has usually: polymkeric substance (methacrylic ester (PMPMA), agar gel, hydrogel and plastic pvc.But because the limitation of physics, chemistry and the mechanical property thereof of these carriers makes its purposes receive certain restriction.
Summary of the invention
One of the object of the invention provides a kind ofly has the rubber of fluorescence response to the pH value, has chemical structure as follows:
Logical formula I
(CSM) represents chlorosulfonated polyethylene rubber, R in the logical formula I
1, R
2, R
3And R
4Be respectively H or C
1-C
6Alkane.
Two of the object of the invention provides a kind of preparation method who the pH value is had the rubber of fluorescence response; This method is to be carrier with the chlorosulfonated polyethylene rubber, rhodamine B is propped up through quadrol form a kind of rubber that the pH value is had fluorescence response on the side chain that is loaded in chlorosuphonated-polyethylene.
For realizing that the technical scheme that the object of the invention adopts is:
1, the esterification of rhodamine B
Measuring 125mL～150mL Acetyl Chloride 98Min. and be added dropwise in the 500mL anhydrous alcohol solution that contains 10g～13g rhodamine B, under the protection of rare gas element, is between 35 ℃～50 ℃ in temperature of reaction, insulation reaction 2～3.5 hours.The pure bullion that gets of pressure reducing and steaming; Dissolving crude product with ETHYLE ACETATE washing 3 ~ 5 times, removes water under reduced pressure in water, obtains the rhodamine B of esterification.
Reaction equation is following:
R in the formula
1, R
2, R
3And R
4Be respectively H or C
1-C
6Alkane.
The alcohol that reacts used is ethanol, propyl alcohol, propyl carbinol, Pentyl alcohol or n-hexyl alcohol.
2, quadrol replaces the preparation of rhodamine
The rhodamine B of getting 10g～12g esterification is dissolved in the methyl alcohol of 30 ℃～45 ℃ of 200mL～220mL, adds 30mL～35mL quadrol simultaneously, back flow reaction 1～2 hour.Be cooled to room temperature, remove methyl alcohol under reduced pressure; Add 1000mL organic solvent 1 and 2000mL water again, collected organic layer is with water washing 1 ~ 2 time.Organic phase is used anhydrous sodium sulfate drying, removes organic solvent under reduced pressure and gets quadrol replacement rhodamine B.
The described organic solvent 1 of this step is chloroform, methylene dichloride, benzene, toluene, ETHYLE ACETATE, ether or pimelinketone.
Reaction equation is following:
3, the preparation of the chlorosulfonated polyethylene rubber of side chain graft rhodamine fluorescence molecule
Take by weighing chloride mass percent and be chlorosulfonated polyethylene rubber 100g～150g of 23% ~ 47%, swelling stirs and is warming up to 50～60 ℃ in 200mL～350mL organic solvent 2; Add quadrol and replace rhodamine B 5g～15g, reacted 10～14 hours, leach solid; Solid is added in a certain amount of ether, and stirring at normal temperature 1 hour leaches solid once more; Use washed several times with water, dry, make the chlorosulfonated polyethylene rubber of side chain graft rhodamine fluorescence molecule.
This rubber can present different fluorescence in the aqueous solution in 1 ~ 14pH value scope, be a kind of functional rubber that the pH value is had fluorescence response.
The described organic solvent 2 of this step is tetracol phenixin, chloroform, methylene dichloride, benzene, toluene, ether or DMSO 99.8MIN..
Reaction equation is following:
The chlorosulfonated polyethylene rubber of side chain graft rhodamine fluorescence molecule of the present invention; Produce required starting material and be the commercial goods; Wide material sources, cheap, the compound method of employing or production technology also belong to classical organic synthesis or high molecular weight reactive.Each step products yield is high, and technology is simple, and production cost is low.
Present different electriferous states in the aqueous solution of the chlorosulfonated polyethylene rubber of side chain graft rhodamine fluorescence molecule of the present invention in 1 ~ 14pH value scope; Thereby produce different fluorescence; Be a kind of the pH value to be had the functional rubber of fluorescence response, can under multiple environment, the pH value to living things system, chemical reaction system, trade effluent, river, lake or ocean detect, analyze.
Functional rubber of the present invention has anti-ozone, UV resistant, and acid and alkali-resistance and a series of performances such as heat-resisting, easy machine-shaping is: spherical, column, sheet, cotton-shaped, fibrous or spumescence, suitability is wide.
Embodiment
Embodiment 1
1, the preparation of rhodamine ester
Measuring the 125mL Acetyl Chloride 98Min. slowly is added drop-wise in the anhydrous ethanol solvent that 500mL contains the 10g rhodamine B, at N
2Protection down, 50 ℃ of insulation reaction 2 hours.Pressure reducing and steaming ethanol gets bullion.Dissolving crude product in 1000mL water, ETHYLE ACETATE washing (3 * 500mL), remove water under reduced pressure, rhodamine B ethyl ester 10.6g, productive rate 90%.
2, quadrol replaces the preparation of rhodamine
10g rhodamine B ethyl ester is dissolved in 30 ℃ of methyl alcohol of 200mL, adds the 30mL quadrol.Reaction mixture reflux 1 hour is cooled to room temperature, and methanol solvate is removed in decompression.Add 1000mLCCl
4, 2000mL water, collected organic layer is with water washing 2 times.Organic phase is used anhydrous sodium sulfate drying, and removal of solvent under reduced pressure gets quadrol and replaces rhodamine B 6.8g, productive rate 70%.
1H?NMR(400MHz,?CDCl
3)?δ:1.16(t,?J=7.2Hz,?3H×4,?CH
2 CH 3 )；2.42(t,?J=6.4Hz,?2H,?CH
2CH
2),?3.19(t,?J=6.4Hz,?2H,?CH
2CH
2),?3.33(q,?J=7.2Hz,?2H×4,?
CH 2 CH
3),?6.26(d,?J=2.8Hz,?1H,?C
13H
6O),?6.28(d,?J=2.4Hz,?1H,?C
13H
6O),?6.37(d,?J=2.8Hz,?2H,?C
13H
6O),?6.42(s,?1H,?C
13H
6O),?6.44(s,?1H,?C
13H
6O),?7.09(dd,?J=2.8,?5.6Hz,?1H,?C
6H
4),?7.44(dd,?J=2.8,?5.6Hz,?2H,?C
6H
4),?7.90(dd,?J=3.2,?5.6Hz,?1H,?C
6H
4)。
3, the preparation of the chlorosulfonated polyethylene rubber of side chain graft rhodamine fluorescence molecule
Take by weighing commercially available chlorinity and be 23% chlorosulfonated polyethylene rubber grain 100g, add in the 200mL chloroform.Stirring is warming up to 50 ℃, adds quadrol and replaces rhodamine B 5.0g reaction 10 hours.Leach micelle, drop in the 300mL ether, stirring at normal temperature 1 hour leaches micelle once more, washes 3 times, dries, and makes the chlorosulfonated polyethylene rubber 104.3g of side chain graft rhodamine fluorescence molecule.
Embodiment 2
1, the preparation of rhodamine ester
Measuring the 145mL Acetyl Chloride 98Min. slowly is added drop-wise in the anhydrous butanols solvent that 500mL contains the 13g rhodamine B, at N
2Protection down, 35 ℃ of insulation reaction 3 hours.The pressure reducing and steaming butanols gets bullion.Dissolving crude product in 1000mL water, ETHYLE ACETATE washing (3 * 500mL), remove water under reduced pressure, rhodamine B butyl ester 12.6g, productive rate 86.3%.
2, quadrol replaces the preparation of rhodamine
12g rhodamine B butyl ester is dissolved in 45 ℃ of methyl alcohol of 230mL, adds the 35mL quadrol.Reaction mixture reflux 2 hours is cooled to room temperature, and methanol solvate is removed in decompression.Add 1000mL ETHYLE ACETATE, 2000mL water, collected organic layer is with water washing 2 times.Organic phase is used anhydrous sodium sulfate drying, and removal of solvent under reduced pressure gets quadrol and replaces rhodamine B 7.5g, productive rate 70.5%.
1H?NMR(400MHz,?CDCl
3)?δ:1.16(t,?J=7.2Hz,?3H×4,?CH
2 CH 3 )；2.42(t,?J=6.4Hz,?2H,?CH
2CH
2),?3.19(t,?J=6.4Hz,?2H,?CH
2CH
2),?3.33(q,?J=7.2Hz,?2H×4,?
CH 2 CH
3),?6.26(d,?J=2.8Hz,?1H,?C
13H
6O),?6.28(d,?J=2.4Hz,?1H,?C
13H
6O),?6.37(d,?J=2.8Hz,?2H,?C
13H
6O),?6.42(s,?1H,?C
13H
6O),?6.44(s,?1H,?C
13H
6O),?7.09(dd,?J=2.8,?5.6Hz,?1H,?C
6H
4),?7.44(dd,?J=2.8,?5.6Hz,?2H,?C
6H
4),?7.90(dd,?J=3.2,?5.6Hz,?1H,?C
6H
4)。
3, the preparation of the chlorosulfonated polyethylene rubber of side chain graft rhodamine fluorescence molecule
Take by weighing commercially available chlorinity and be 35% chlorosulfonated polyethylene rubber grain 120g, add in the 300mL tetracol phenixin.Stirring is warming up to 60 ℃, adds quadrol and replaces rhodamine B 7.5g reaction 12 hours.Leach micelle, drop in the 300mL ether, stirring at normal temperature 1 hour leaches micelle once more, washes 3 times, dries, and makes the chlorosulfonated polyethylene rubber 114.3g of side chain graft rhodamine fluorescence molecule.
Embodiment 3
1, the preparation of rhodamine ester
Measuring the 140mL Acetyl Chloride 98Min. slowly is added drop-wise in the anhydrous amylalcohol solvent that 500mL contains the 12g rhodamine B, at N
2Protection down, 45 ℃ of insulation reaction 2.5 hours.The pressure reducing and steaming amylalcohol gets bullion.Dissolving crude product in 1000mL water, ETHYLE ACETATE washing (3 * 500mL), remove water under reduced pressure, rhodamine B pentyl ester 12.6g, productive rate 91.3%.
2, quadrol replaces the preparation of rhodamine
11g rhodamine B pentyl ester is dissolved in 45 ℃ of methyl alcohol of 200mL, adds the 33mL quadrol.Reaction mixture reflux 1.5 hours is cooled to room temperature, and methanol solvate is removed in decompression.Add the 1000mL pimelinketone, 2000mL water, collected organic layer is with water washing 2 times.Organic phase is used anhydrous sodium sulfate drying, and removal of solvent under reduced pressure gets quadrol and replaces rhodamine B 6.8g, productive rate 70.3%.
1H?NMR(400MHz,?CDCl
3)?δ:1.16(t,?J=7.2Hz,?3H×4,?CH
2 CH 3 )；2.42(t,?J=6.4Hz,?2H,?CH
2CH
2),?3.19(t,?J=6.4Hz,?2H,?CH
2CH
2),?3.33(q,?J=7.2Hz,?2H×4,?
CH 2 CH
3),?6.26(d,?J=2.8Hz,?1H,?C
13H
6O),?6.28(d,?J=2.4Hz,?1H,?C
13H
6O),?6.37(d,?J=2.8Hz,?2H,?C
13H
6O),?6.42(s,?1H,?C
13H
6O),?6.44(s,?1H,?C
13H
6O),?7.09(dd,?J=2.8,?5.6Hz,?1H,?C
6H
4),?7.44(dd,?J=2.8,?5.6Hz,?2H,?C
6H
4),?7.90(dd,?J=3.2,?5.6Hz,?1H,?C
6H
4)。
3, the preparation of the chlorosulfonated polyethylene rubber of side chain graft rhodamine fluorescence molecule
Take by weighing commercially available chlorinity and be 47% chlorosulfonated polyethylene rubber grain 150g, add in the 350mL tetracol phenixin.Stirring is warming up to 55 ℃, adds quadrol and replaces rhodamine B 6.5g reaction 14 hours.Leach micelle, drop in the 300mL toluene, stirring at normal temperature 1 hour leaches micelle once more, washes 3 times, dries, and makes the chlorosulfonated polyethylene rubber 110.2g of side chain graft rhodamine fluorescence molecule.
Embodiment 4
The preparation of the chlorosuphonated-polyethylene film of side chain graft rhodamine fluorescence molecule
The preparation process of the preparation of the preparation of rhodamine ester, quadrol replacement rhodamine, the chlorosuphonated-polyethylene rubber of side chain graft rhodamine fluorescence molecule is with embodiment 1.
Take by weighing the chlorosulfonated polyethylene rubber grain 100g of the side chain graft rhodamine fluorescence molecule of instance 1 gained, be dispersed in the methyl-sulphoxide of 1000mL, stir and be warming up to 80 ℃, dissolve fully until micelle.Solution is coated on the clean glass surface, uses 2000mL distilled water wash coating.Stripping film after 1 day, deionized water wash several, drying, the chlorosuphonated-polyethylene film of the side chain graft rhodamine fluorescence molecule of the specific thicknesses that can make and area.Through control coating condition, the aperture of thin-film material can be controlled at the nano level scope.
Embodiment 5
The preparation of the cotton-shaped material of chlorosuphonated-polyethylene of side chain graft rhodamine fluorescence molecule
The preparation process of the preparation of the preparation of rhodamine ester, quadrol replacement rhodamine, the chlorosuphonated-polyethylene rubber of side chain graft rhodamine fluorescence molecule is with embodiment 1.
Take by weighing the chlorosulfonated polyethylene rubber grain 100g of the side chain graft rhodamine fluorescence molecule of instance 1 gained, be dispersed in the methyl-sulphoxide of 1000mL, stir and be warming up to 90 ℃, dissolve fully until micelle.Add 50mL acetone, stir, in the 1000mL zero(ppm) water that quick impouring is 80 ℃, after the cooling, the pressurization suction filtration removes and desolvates, and filter cake is with distilled water wash several, drying, the cotton-shaped material of chlorosuphonated-polyethylene of the side chain graft rhodamine fluorescence molecule that can make.
Claims (9)
1. one kind has the rubber of fluorescence response to the pH value, has chemical structure as follows:
Logical formula I
(CSM) represents chlorosulfonated polyethylene rubber, R in the logical formula I
1, R
2, R
3And R
4Be respectively H or C
1-C
6Alkane.
2.
As claimed in claim 1 A kind of have the preparation method of the rubber of fluorescence response to the pH value, it is characterized in that may further comprise the steps:
(1) measure 125mL～150mL Acetyl Chloride 98Min. and dropwise be added in the 500mL absolute alcohol that contains 10g～13g rhodamine B,
Under 35 ℃～50 ℃, carry out Insulation reaction, pressure reducing and steaming ethanol gets bullion, and dissolving crude product with the ETHYLE ACETATE washing, removes water under reduced pressure in water, obtains the rhodamine B of esterification;
The rhodamine B of (2) getting 10g～12g esterification is dissolved in the methyl alcohol of 30 ℃～45 ℃ of 200mL～220mL, adds 30mL～35mL quadrol simultaneously, and back flow reaction 1～2 hour is cooled to room temperature, removes methyl alcohol under reduced pressure; Add 1000mL organic solvent 1 and 2000mL water again, collected organic layer, with water washing 1-2 time, organic phase is used anhydrous sodium sulfate drying, removes organic solvent under reduced pressure and gets quadrol replacement rhodamine B;
(3) taking by weighing chloride mass percent is chlorosulfonated polyethylene rubber 100g～150g of 23% ~ 47%, and swelling stirs and heats up in 200mL～350mL organic solvent 2; Add quadrol and replace rhodamine B 5g～15g, leach solid after the reaction, drop in the ether; Stirring at normal temperature 1 hour leaches solid, washed several times with water once more; Dry, make the chlorosulfonated polyethylene rubber of side chain graft rhodamine fluorescence molecule.
3. according to claim 2 a kind ofly have the preparation method of the rubber of fluorescence response to the pH value, it is characterized in that described alcohol is ethanol, propyl alcohol, propyl carbinol, Pentyl alcohol or n-hexyl alcohol.
4. according to claim 2 a kind ofly have the preparation method of the rubber of fluorescence response to the pH value, it is characterized in that described insulation reaction, and the reaction times is 2～3.5 hours.
5. according to claim 2 a kind ofly have the preparation method of the rubber of fluorescence response to the pH value, it is characterized in that described hot methanol, and its temperature is 30 ℃～45 ℃.
6. according to claim 2 a kind ofly have the preparation method of the rubber of fluorescence response to the pH value, it is characterized in that described chlorosulfonated polyethylene rubber swelling is in organic solvent 2 after, stirring the temperature that heats up is 50～60 ℃.
7. according to claim 2 a kind ofly have the preparation method of the rubber of fluorescence response to the pH value, and it is characterized in that adding the reaction times that quadrol replaces behind the rhodamine B is 10～14 hours.
8. according to claim 2 a kind ofly have the preparation method of the rubber of fluorescence response to the pH value, it is characterized in that described organic solvent 1 is chloroform, methylene dichloride, benzene, toluene, ETHYLE ACETATE, ether or pimelinketone.
9. according to claim 2 a kind ofly have the preparation method of the rubber of fluorescence response to the pH value, it is characterized in that described organic solvent 2 is tetracol phenixin, chloroform, methylene dichloride, benzene, toluene, ether or DMSO 99.8MIN..
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| CN102174131B true CN102174131B (en) | 2012-10-17 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183657A (en) * | 2011-12-31 | 2013-07-03 | 中国科学院成都有机化学有限公司 | Synthesis method of rhodamine esterification derivative |
| CN102590208A (en) * | 2012-01-19 | 2012-07-18 | 上海交通大学 | Preparation method for biological scale-based in-situ optical pH value detector |
| CN104017569B (en) * | 2014-05-23 | 2017-01-11 | 苏州科技学院 | Rhodamine-containing lactam group micromolecule pH fluorescent probe and synthetic method |
| CN103992791B (en) * | 2014-06-06 | 2016-08-24 | 福建师范大学 | A kind of rhodamine base pH value fluorescent probe in the linear response of faintly acid scope and preparation method thereof |
| CN106279552A (en) * | 2015-06-09 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of fluorescence rubber particle and preparation method thereof |
| CN104910301A (en) * | 2015-07-07 | 2015-09-16 | 南京工业大学 | Polystyrene microsphere having fluorescent response to potential of hydrogen (pH) value and preparation method thereof |
| CN110183554B (en) * | 2019-04-19 | 2021-07-09 | 苏州大学 | Perchloroethylene derivative and application thereof |
| CN110256614B (en) * | 2019-04-19 | 2021-12-10 | 苏州大学 | Fluorescent perchloroethylene macromolecule and application thereof |
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| CN101173099A (en) * | 2007-10-24 | 2008-05-07 | 东莞市盛达橡塑制品有限公司 | Fluorescence rubber material and production method for product adopting the material |
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| CN101173099A (en) * | 2007-10-24 | 2008-05-07 | 东莞市盛达橡塑制品有限公司 | Fluorescence rubber material and production method for product adopting the material |
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