CN102093290A - Fluorescent monomer and fluorescent acrylic acid polymer and preparation method of fluorescent monomer and fluorescent acrylic acid polymer - Google Patents
Fluorescent monomer and fluorescent acrylic acid polymer and preparation method of fluorescent monomer and fluorescent acrylic acid polymer Download PDFInfo
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Abstract
The invention provides a fluorescent monomer and a fluorescent acrylic acid polymer and a preparation method of the fluorescent monomer and the fluorescent acrylic acid polymer. The monomer and polymer are respectively shown in formulas (I) and (2), wherein m is 1 or 2, n is 10-120, R1 is H or -CH3, R2 is -CH3, -CH2CH3,-CH2CH2CH3 or -CH2CH2(OH)CH3. The preparation method is as follows: reacting 4-bromine-1,8-naphthalic anhydride with n-propylamine so as to obtain N-propyl-4-bromine-1,8-naphthalimide; reacting the N-propyl-4-bromine-1,8-naphthalimide with ethanolamine so as to obtain N-propyl-4-(2-ethoxyamino)-1,8-naphthalimide; reacting the N-propyl-4-(2-ethoxyamino)-1,8-naphthalimide with PBr3 so as to obtain N-propyl-4-(2-bromomethylamino)-1,8-naphthalimide, and dropwise adding unsaturated compound dimethylaminoethyl methacrylate so that the fluorescent monomer is obtained; and condensing the fluorescent monomer with at least one crylic acid monomer. The fluorescent polymer can be used as a special scale inhibitor for a sea water circulating cooling or sea water desalinization system, and has a good scale dispersion property and a good fluorescent trace characteristic.
Description
Technical field
The invention belongs to field of fine chemical, relate to a kind of water soluble fluorescence monomer and fluorescent tracing type dirt dispersion agent and technology of preparing thereof, particularly a kind of fluorescent monomer that is applicable to seawater circulation cooling or seawater desalination system and fluorescence acrylic polymers dirt dispersion agent and preparation method thereof.
Background technology
The dosing control of water treatment agent relies on on-the-spot water quality monitoring (WQM) usually, and as the criterion that judges whether dosing, this has caused the hysteresis of response to a certain extent with Analysis Results of Water Quality coupling system benefit, draining situation.For this reason, in system, add the spike type medicament contain fluorophore, adopt detection technique of fluorescence to measure that the concentration of medicament is to realize a kind of effective means of on-line monitoring in the water.In engineering practice, fluorescent tracer technique has obtained application in the fresh water water treatment system, respond well.Correlative study wherein comprises:
(1) invented a kind of method of utilizing polymer modification prepared in reaction fluorescent tracing scale inhibitor among the CN1229091A.This polymkeric substance is synthetic to be contained the polymkeric substance of phosphate, hydroxyalkyl base, carboxylic acid and sulfonic acid group and fluorescence organic acid salt join airtight vessel in heating and be warmed up to 90 ℃-200 ℃ and change the acid amides reaction and make.Yet commentaries on classics acid amides reaction needed reaches under the certain condition at temperature, pressure just can carry out, thereby has limited this The Application of Technology.
(2) CN 1781857A and CN 1939945A with naphthalimide as the fluorescence precursor structure, obtained containing the unsaturated monomer of double bond structure by series reaction, afterwards again with polyreactions such as P contained compound, maleic anhydride, vinylformic acid, prepared the fluorescent tracing dirt dispersion agent.CN 101475266A, and carries out radical polymerization with equisetic acid or its salt and makes the aqueous solution that solid content is 20-50wt% as the fluorescence parent with pyrene sulfonic acid, by the scale inhibition experiment lime carbonate scale inhibition performance is reached 76.3%.
Above-mentioned correlative study does not relate to the application in seawater.Utilizing seawater to replace fresh water to use as industrial cooling water or desalination back, can save a large amount of Freshwater resources, is the important development direction that present seawater resources utilize.The water soluble fluorescence monomer that exploitation is suitable then with other suitable monomer polymerization, obtains being applicable to that the polymkeric substance water treatment agent of seawater circulation cooling or seawater desalination system is the key that realizes online detection, improves automatic management.
Summary of the invention
The technical problem to be solved in the present invention is, provides a kind of and be applicable to seawater circulation cooling or seawater desalination system, has acrylic polymers of scale inhibition and dispersion performance and green fluorescence spike feature and preparation method thereof.
In order to solve the problems of the technologies described above, the invention provides following technical scheme:
(1) a kind of fluorescent monomer, N-(2-(methacryloxy) ethyl)-N, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) the ethyl brometo de amonio, its structural formula (1) is as follows:
(2) preparation method of the described fluorescent monomer of scheme (1), it may further comprise the steps:
(i) adopt 4-bromo-1,8-naphthalene acid anhydride (A1) and Tri N-Propyl Amine are that raw material makes N-n-propyl-4-bromo-1, and 8-naphthalimide (A2) makes N-n-propyl-4-(2-hydroxyethylamino)-1,8-naphthalimide (A3) with the thanomin reaction again;
(ii) with the N-n-propyl-4-(2-hydroxyethylamino)-1 that obtains, 8-naphthalimide (A3) is dissolved in the solvent (preferred solvent is a carboxylicesters, more preferably adopts ethyl acetate as solvent), the following and PBr of normal temperature condition
3Reaction, product obtains N-n-propyl-4-(2-bromotrifluoromethane amino)-1,8-naphthalimide (A4) through neutralization (preferably neutralizing with sodium bicarbonate aqueous solution), extraction (preferably using dichloromethane extraction); This product is dissolved in solvent (preferably uses the ketone material as solvent, more preferably use acetone as solvent) in, slowly drip the unsaturated compound dimethylaminoethyl methacrylate, heating, separate out fluorescent monomer N-(2-(methacryloxy) ethyl)-N with two keys, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) ethyl brometo de amonio (A5).
Wherein, in each reactions steps, Tri N-Propyl Amine, thanomin and PBr
3Each raw material consumption excessive a little, A1, A2 and A3 are reacted completely is purpose to reach; The amount of substance of A4 and dimethylaminoethyl methacrylate is than preferably in 1: 10～1: 1 scope.In addition, the preparation fluorescent monomer step (ii) in, described heating is meant that temperature is controlled in the 20-60 ℃ of scope.
The prepared fluorescent monomer maximum emission wavelength of the present invention is 524nm, is arranged in the green wavelength region 490～580nm of visible spectrum, presents green fluorescence.In the complicated test environment of seawater, its working concentration and fluorescent emission intensity are good linear relationship, and linearly dependent coefficient reaches 0.99981, are limited to 10 μ g/L under detecting.
Green fluorescence monomer of the present invention can aggregate into the polymkeric substance with green fluorescence characteristic with acrylic monomer, as the seawater dirt dispersion agent.
In addition, the present invention also provides following technical scheme:
(3) a kind of fluorescence acrylic polymers, its structural formula (2) is as follows:
Wherein, m is 1 or 2; N is the integer of 10-120;
R
1For H or-CH
3
R
2For-CH
3,-CH
2CH
3,-CH
2CH
2CH
3Or-CH
2CH
2(OH) CH
3
The present invention also provides following technical scheme:
(4) a kind of fluorescence acrylic polymers, it prepares by following method:
(i) utilize 4-bromo-1,8-naphthalene acid anhydride and Tri N-Propyl Amine (A1) make N-n-propyl-4-bromo-1 for raw material, and 8-naphthalimide (A2) makes N-n-propyl-4-(2-hydroxyethylamino)-1,8-naphthalimide (A3) with the thanomin reaction again;
(ii) with the N-n-propyl-4-(2-hydroxyethylamino)-1 that obtains, 8-naphthalimide (A3) is dissolved in the solvent (preferably adopt carboxylicesters as solvent, more preferably adopt ethyl acetate as solvent), the following and PBr of normal temperature condition
3Reaction, product obtains N-n-propyl-4-(2-bromotrifluoromethane amino)-1,8-naphthalimide (A4) through neutralization (preferably neutralizing with sodium bicarbonate aqueous solution), extraction (preferably using dichloromethane extraction); This product is dissolved in solvent (preferably uses the ketone material as solvent, more preferably use acetone as solvent) in, slowly drip the unsaturated compound dimethylaminoethyl methacrylate, heating (preferred temperature is 20-60 ℃), separate out fluorescent monomer N-(2-(methacryloxy) ethyl)-N with two keys, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) ethyl brometo de amonio (A5);
(iii) with initiator (being preferably persulphate) initiator system, utilize step (2) institute's synthetic fluorescent monomer and at least a acrylic monomer (be preferably be selected from (methyl) vinylformic acid, methyl acrylate, methyl acrylate, ethyl propenoate, the Propylene glycol monoacrylate at least a) to carry out polyreaction, temperature is controlled at 60 ℃～100 ℃ (preferred 70～90 ℃, more preferably 80～90 ℃); Wherein, the raw materials quality ratio of described fluorescent monomer and acrylic monomer is in 0.1%～10% scope.
(5) according to the described polymkeric substance of scheme (4), its number-average molecular weight is 1000～20000, is preferably 2500～17000, more preferably 2500～6500.
In addition, preferably the weight-average molecular weight of this polymkeric substance is 10000～60000, is preferably 15000～56000; More preferably 25000～35000.
The resulting fluorescence acrylic polymers of the present invention, in fluorescence spectrometry, maximum emission wavelength is 519nm, is arranged in the green wavelength region 490～580nm of visible spectrum, presents green fluorescence.
Wherein, in each reactions steps of preferred above-mentioned preparation fluorescence acrylic polymers, Tri N-Propyl Amine, thanomin and PBr
3Each raw material consumption excessive a little, be purpose so that A1, A2 and A3 are reacted completely; And preferred, the amount of substance of A4 and dimethylaminoethyl methacrylate is than preferably in 1: 10～1: 1 scope.
Wherein, preferred initiator amount is 5%～20% (quality) of monomer total amount, more preferably 5%～15% (quality).
Wherein, preferred described initiator adopts the dropping mode to add; Also behind preferred reaction 0.5～2h, continue back flow reaction 2～5h.
The present invention also provides following technical scheme:
(6) a kind of preparation method of fluorescence acrylic polymers, it comprises the steps:
(i) utilize 4-bromo-1,8-naphthalene acid anhydride (A1) and Tri N-Propyl Amine are that raw material makes N-n-propyl-4-bromo-1, and 8-naphthalimide (A2) makes N-n-propyl-4-(2-hydroxyethylamino)-1,8-naphthalimide (A3) with the thanomin reaction again;
(ii) with the N-n-propyl-4-(2-hydroxyethylamino)-1 that obtains, 8-naphthalimide (A3) is dissolved in solvent and (preferably adopts esters solvent, more preferably adopt ethyl acetate as solvent) in, following and the PBr3 reaction of normal temperature condition, product is through neutralization (preferably neutralizing with sodium bicarbonate aqueous solution), extraction (preferably using dichloromethane extraction), obtain N-n-propyl-4-(2-bromotrifluoromethane amino)-1,8-naphthalimide (A4); This product is dissolved in solvent (preferably uses letones as solvent, more preferably use acetone as solvent) in, slowly drip the unsaturated compound dimethylaminoethyl methacrylate, heating, separate out fluorescent monomer N-(2-(methacryloxy) ethyl)-N with two keys, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) ethyl brometo de amonio (A5);
(iii) with initiator (being preferably persulphate) initiator system, utilize step (2) institute's synthetic fluorescent monomer and at least a acrylic monomer (be preferably be selected from (methyl) vinylformic acid, methyl acrylate, methyl acrylate, ethyl propenoate, the Propylene glycol monoacrylate at least a) to carry out polyreaction, temperature is controlled at 60 ℃～100 ℃ (preferred 70～90 ℃, more preferably 80～90 ℃); Wherein, the raw materials quality ratio of described fluorescent monomer and acrylic monomer is in 0.1%～10% scope.
(7) preparation method of the described polymkeric substance of scheme (6), wherein, described initiator adopts the dropping mode to add; Behind preferred reaction 0.5～2h, continue back flow reaction 2～5h.
(8) preparation method of the described polymkeric substance of scheme (6), wherein, N-n-propyl-4-(2-bromotrifluoromethane amino)-1, the amount of 8-naphthalimide and dimethylaminoethyl methacrylate is than in 1: 10～1: 1 scope.
(9) preparation method of the described polymkeric substance of scheme (6), wherein, the preparation fluorescent monomer step (ii) in, described heating is meant that temperature is controlled in the 20-60 ℃ of scope.
(10) preparation method of the described polymkeric substance of scheme (6), wherein, initiator amount is 5%～15% (quality) of monomer total amount, preferred 5%～15% (quality).
Wherein, in each reactions steps of preferred above-mentioned preparation fluorescence acrylic polymers, Tri N-Propyl Amine, thanomin and PBr
3Each raw material consumption excessive a little, be purpose so that A1, A2 and A3 are reacted completely.
The resulting fluorescence acrylic polymers of above-mentioned preparation method structural formula (2) is:
Wherein, m is 1 or 2; N is the integer of 10-120;
R1 be H or-CH
3
R
2For-CH
3,-CH
2CH
3,-CH
2CH
2CH
3Or-CH
2CH
2(OH) CH
3
Fluorescence acrylic polymers of the present invention, its number-average molecular weight is 1000～20000, is preferably 2500～17000, more preferably 2500～6500.In addition, preferably the weight-average molecular weight of this polymkeric substance is 10000～60000, is preferably 15000～56000; More preferably 25000～35000.
The fluorescence acrylic polymers that the present invention is prepared, in fluorescence spectrometry, maximum emission wavelength is 519nm, is arranged in the green wavelength region 490～580nm of visible spectrum, presents green fluorescence.Fluorescence acrylic polymers of the present invention is the polymer water treatment agent with scale inhibition and dispersion performance and green fluorescence spike feature, be applicable to seawater circulation cooling or seawater desalination system, this polymkeric substance can guarantee the linear relationship of polymer concentration and fluorescence intensity in the complicated test environment of seawater, linearly dependent coefficient reaches 0.99976, is limited to 1mg/L under detecting.
Compared with prior art, the present invention has following remarkable advantage: (1) synthetic green fluorescence acrylic polymers reaction conditions gentleness, be applicable to seawater circulation cooling or seawater desalination system, maximum emission wavelength is in visible region and strong green fluorescence is arranged, and fluorescence intensity and polymer concentration are linear.Therefore, in seawater utilization (seawater circulation cooling or sea water desaltination) process, can change accurate, timely, its content of rapid determination, realize online dosing and quantitatively control by fluorescence intensity; (2) product has good inhibition calcium carbonate scale performance, is 2.0 at cycles of concentration, high contents of calcium and magnesium ion content and keeping in the concentrated seawater environment of Balance of nature pH value, and onset concentration only is 2mg/L; (3) in 2.0 times of concentrated seawater systems, the product using dosage of 10mg/L can be stablized 4mg/L phosphoric acid salt and 2mg/L zine ion, shows that this polymkeric substance seawater dirt dispersion agent can be the compound use of corrosion inhibitor of sea water with phosphorus zinc, and plays the satisfactory stability effect; (4) this polymkeric substance seawater dirt dispersion agent has good dissemination to ferric oxide, the using dosage of 6mg/L can be stabilized in the ferric oxide more than 80% (the about 5mg/L of iron ion content in the seawater) in the seawater, is the special-purpose dirt dispersion agent of seawater of high comprehensive performance.
Description of drawings
Fig. 1 is green fluorescence monomer N-of the present invention (2-(methacryloxy) ethyl)-N, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) fluorescence excitation spectrum and the emmission spectrum figure of ethyl brometo de amonio.
Fig. 2 A is green fluorescence monomer N-of the present invention (2-(methacryloxy) ethyl)-N, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) graph of relation of ethyl brometo de amonio working concentration and fluorescence intensity; Fig. 2 B is the linear regression graphic representation of this fluorescent monomer working concentration and fluorescent emission intensity.
Fig. 3 is the fluorescence excitation spectrum and the emmission spectrum figure of green fluorescence acrylic polymers of the present invention.
Fig. 4 A is a green fluorescence acrylic polymers of the present invention as the graph of relation of seawater dirt dispersion agent working concentration and fluorescent emission intensity in briny environment; Fig. 4 B is the linear regression graphic representation of this fluorescence acrylic polymers and fluorescent emission intensity.
Fig. 5 is the static seawater tosca experimental result picture of green fluorescence acrylic polymers of the present invention as the seawater dirt dispersion agent.
Fig. 6 is a green fluorescence acrylic polymers of the present invention as the working concentration of seawater dirt dispersion agent to phosphate-stabilized magnitude relation graphic representation.
Fig. 7 is a green fluorescence acrylic polymers of the present invention as the working concentration of seawater dirt dispersion agent to zinc salt stable quantity graph of relation.
Fig. 8 is a green fluorescence acrylic polymers of the present invention as the working concentration of seawater dirt dispersion agent to dispersing iron oxide Effect on Performance graph of a relation.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but be not used for limiting protection scope of the present invention.
Green fluorescence monomer N-(2-(methacryloxy) ethyl)-N, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) preparation of ethyl brometo de amonio
Preparation feedback formula (3) is as follows:
With 13.8g (0.05mol) 4-bromo-1,8-naphthalene acid anhydride (A1), 3.0g (0.05mol) Tri N-Propyl Amine and 65ml ethanol are incorporated with in the glass reactor of magnetic agitation, reflux condensing tube, 78 ℃ of heating reflux reaction 3h, along with the carrying out of reaction, raw material (A1) experience amidation process is constantly dissolved and is obtained product.Be spin-dried for solvent after reaction finishes and make white solid N-n-propyl-4-bromo-1,8-naphthalimide (A2) 14.4g, productive rate 90.5%.Subsequently with 9.5g (0.03mol) compd A 2 and another reactant thanomin 2.4g (0.04mol) and 50ml reaction solvent ethylene glycol monomethyl ether, reflux under magnetic agitation and 125 ℃ of reflux condensation mode conditions, be spin-dried for solvent after reaction finishes and make yellow solid N-n-propyl-4-(2-hydroxyethylamino)-1,8-naphthalimide 7.4g (A3), productive rate 82.4%.This 6.0g (0.02mol) A3 is dissolved in the 60ml ethyl acetate, and normal temperature slowly drips 10.8g (0.04mol) PBr
3, stir 3h, reaction finishes the back with 80ml saturated sodium bicarbonate aqueous solution neutralization reaction system, 3 * 50ml (extracting each consumption 50ml three times) dichloromethane extraction.Because hydroxyl is replaced by bromine, (methyl alcohol-ethyl acetate is as developping agent, and ratio is 1: 1, v/v) contrasts reactant and product, and A4 polarity obviously diminishes by the efficient thin layer silica gel chromatography of the HF254 of Qingdao Marine Chemical Co., Ltd. in the reaction.Be spin-dried for extraction liquid and make yellow solid N-n-propyl-4-(2-bromotrifluoromethane amino)-1,8-naphthalimide (A4) 4.6g, tight rate 64.2%.3.6g (0.01mol) A4 is dissolved in the 45ml acetone, add 0.4g (0.003mol) stopper p methoxy phenol, slowly drip 4.7g (0.03mol) dimethylaminoethyl methacrylate, be heated to 50 ℃ of reaction 6h, filter, 100ml petroleum ether filter residue, vacuum-drying, make 3.6g and have water miscible green quaternary ammonium salt fluorescent monomer N-(2-(methacryloxy) ethyl)-N, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) ethyl brometo de amonio (A5) amino), tight rate 68.9%.
Resulting green product A5 is adopted Finnigan LCQ spectrometer analysis, the molecular ion peak of compound (ESI, m/z as can be seen
+) be 438.32, because product is a salt compounds, in solution, dissociate into X
+Br
-, N-(2-(methacryloxy) ethyl)-N, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) ethyl brometo de amonio relative molecular mass is 517.9, Br
-Relative molecular mass is 79.9, i.e. X
+Relative molecular mass be 438.Therefore show that target product A5 generates.
In addition, adopt thermoelectric Buddhist nun's high-tensile strength Nicolet 6700 infrared spectrometers of the U.S. (KBr compressing tablet) that tight product A5 is carried out infrared spectrum characterization, by seeing 1639.60cm on the infrared spectrogram
-1, 1555.59cm
-1, 1454.90cm
-1Naphthalene nucleus skeletal vibration, 1726.04cm
-1Teritary amide C=O stretching vibration, 1639.60cm
-1The C=C stretching vibration, 2988.95cm
-1Methyl on the C-H stretching vibration, 1160.26cm
-1, 1160.26cm
-1Ester group C-O stretching vibration, 1351.11cm
-1Be the C-N stretching vibration, thereby the checking product is target product.
N-n-propyl-4-(2-bromotrifluoromethane amino)-1, the ratio between 8-naphthalimide (A4) and the dimethylaminoethyl methacrylate (DM) is to the influence experiment of fluorescent monomer productive rate
Except N-n-propyl-4-(2-bromotrifluoromethane amino)-1, the ratio of amount of substance is changed into beyond the ratio as shown in table 1 between 8-naphthalimide (A4) and the dimethylaminoethyl methacrylate (DM), other operations are all identical with embodiment 1, the ratio of amount of substance of investigating A4 and DM is to the influence of fluorescent monomer productive rate, and experimental result sees Table 1.
Table 1
| A4∶DM | Fluorescent monomer productive rate (%) |
| 1∶10 | 76.4 |
| 1∶6 | 75.3 |
| 1∶4 | 71.2 |
| 1: 3 (embodiment 1) | 68.9 |
| 1∶1 | 58.1 |
By above-mentioned experimental result as can be seen: N-n-propyl-4-(2-bromotrifluoromethane amino)-1, the amount of 8-naphthalimide and dimethylaminoethyl methacrylate than productive rate in 1: 10～1: 1 scope greater than 50%, and with ratio between two to reduce be that the consumption of A4 reduces and increases.
Embodiment 3
The monomeric fluorescence spectrum test of green fluorescence
Take by weighing N-(2-(methacryloxy) ethyl)-N, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) to be dissolved in salinity be in 35 the natural sea-water, to be configured to 100 μ g/L to the ethyl brometo de amonio.Fixedly the F7000 of Hitachi fluorescence spectrophotometer slit width 10nm scans excitation spectrum and emmission spectrum figure respectively.The excitation spectrum of fluorescent monomer solution and emmission spectrum figure see accompanying drawing 1, the maximum excitation wavelength and the maximum emission wavelength that obtain are respectively 430nm and 524nm, maximum emission wavelength is positioned at visible spectrum green range (490～580nm), and have very strong fluorescence intensity.
Fixedly excitation wavelength 430nm and slit width 10nm, measure the fluorescence intensity of fluorescent monomer sea water solution under 524nm of 10,20,40,60,80,100 μ g/L, the test result of concrete fluorescence intensity is seen accompanying drawing 2A, in addition, adopt method of least squares to obtain the working concentration of this monomer solution and the linear regression graphic representation of fluorescent emission intensity (Fig. 2 B); By Fig. 2 B as can be seen, the working concentration of this monomer solution and fluorescent emission intensity are good linear relationship, and linearly dependent coefficient reaches 0.99981, are limited to 10 μ g/L under detecting.
The preparation of polymer A 6-1
Preparation feedback formula (4) is as follows:
Take by weighing above-mentioned fluorescent monomer A5 0.45g (8.7 * 10
-4Mol) be dissolved in the 30mL deionized water, and it is miscible with 45g (0.64mol) vinylformic acid, input is equipped with in reflux condensing tube, constant pressure funnel, thermometer and the churned mechanically four-hole boiling flask, and in nitrogen atmosphere, be stirred and heated to 90 ℃, under this temperature, slowly drip the 75mL potassium persulfate solution that is dissolved with 6.8g with constant speed.After dropwising with 1h, continue back flow reaction 4h, cooling, solution colour deepens gradually in the reaction process, and product is a yellow-green colour mucus, and through the Tongji University's dynamo-electric NDJ-79 of factory type rotary viscosity design determining, viscosity is 130mPas.Promptly obtain green fluorescence acrylic polymers crude product A6-1.
Adopt U.S. VISCOTEK company's T DA 302 type gel chromatographs, gel chromatographic columns is TEKGMPW
XL, measuring temperature is 30 ℃, and moving phase adopts 0.3mol/L NaCl, and flow velocity is 1mL/min.The number-average molecular weight Mn=2881 that records, weight-average molecular weight Mw=25486.
Add suitable quantity of water in the synthetic crude product, regulate pH to 7～8 with NaOH, add absolute ethyl alcohol and stirring, separate out thick substances, inclining supernatant liquid, with the absolute ethanol washing precipitate, is positioned in the vacuum drying oven, obtains the purified polymer solid after the drying.Adopt thermoelectric Buddhist nun's high-tensile strength Nicolet 6700 infrared spectrometers of the U.S. (KBr compressing tablet) that A6-1 is carried out infrared spectrum characterization, remove 1639.60cm
-1, 1555.59cm
-1, 1454.90cm
-1The place has outside the naphthalene nucleus skeletal vibration, at 3433.87cm
-1Have strong and bands of a spectrum broad-the OH stretching vibration peak, at 1403.64cm
-1The stretching vibration of carboxyl C=O is arranged, and illustrating has fluorescent monomer and all functional groups that have of vinylformic acid on the polymkeric substance.
The preparation of A6-2
Repeat the operation of embodiment 4, except following difference is arranged: use fluorescent monomer 0.23g, initiator amount to be 2.3g, preparation A6-2.The viscosity of resulting green fluorescence acrylic polymers A6-2 is 240mPas, the number-average molecular weight Mn=5171 that records, weight-average molecular weight Mw=34726.
Repeat the operation of embodiment 4, change temperature, initiator amount, fluorescent monomer content obtain following a series of polymkeric substance, gather and list in table 2:
Table 2
By seeing in the table 2: remove A6-5 and be outside the thickness micelle not soluble in water, other products all are water-soluble transparent liquids preferably.Therefore, temperature of reaction should be controlled at that 60 ℃～100 ℃ (preferred 70～90 ℃, more preferably 80～90 ℃), green fluorescence monomer consumption and Acrylic Acid Monomer consumption mass ratios are 0.1%～10%, the persulfate initiator consumption is 5%～15% of a monomer total amount.
Embodiment 7
The fluorescence spectrum test of green fluorescence acrylic polymers
With salinity is that 35 natural sea-water preparation mass concentration is the A6-1 green fluorescence acrylic polymers seawater dirt dispersion agent aqueous solution of 10mg/L, fixedly the F7000 of Hitachi fluorescence spectrophotometer slit width 10nm scans excitation spectrum and emmission spectrum figure respectively, the results are shown in accompanying drawing 3, its maximum excitation wavelength and maximum emission wavelength are 397nm and 519nm, maximum emission wavelength is positioned at visible spectrum green range (490～580nm), and have stronger fluorescence intensity.
Fixedly excitation wavelength 397nm and slit width 10nm measure 1,2,4,6,8, the fluorescence intensity of 10mg/L green fluorescence acrylic polymers product A 6-1 sea water solution under 519nm, and concrete test result is seen accompanying drawing 4A; In addition, adopt method of least squares to obtain the working concentration of this A6-1 product solution and the linear regression graphic representation of fluorescent emission intensity (Fig. 4 B); By Fig. 4 B as can be seen, its working concentration and fluorescent emission intensity are good linear relationship, and linearly dependent coefficient reaches 0.99976, are limited to 1mg/L under detecting.
Adopt the performance of seawater tosca experimental evaluation green fluorescence acrylic polymers
Test conditions is as follows: the seawater (ca that test water adopts Tanggu purifying sea water factory to provide
2+477.89mg/L, methyl orange alkalinity 122.58mg/L, pH=7.89, electricity lead 4534.53 * 10
4μ S/cm), medicament adopts above-mentioned polymer A 6-1 and A6-2, and using dosage is followed successively by 0,0.5,1,2,4,6,8mg/L, and cycles of concentration is 2.0 times, 80 ℃ of controlled temperature, test period 24h.Test solution concentration of chlorion and basicity before and after the determination test after cooling, constant volume and filtration is calculated Δ A (chlorion cycles of concentration with the difference between the cycles of concentration of methyl orange alkalinity calculating).Test result is seen Fig. 5.
As seen from the figure, when A6-1 and A6-2 using dosage during greater than 2mg/L, Δ A begins less than 0.2, shows that the onset concentration that two medicaments that according to said method record suppress toscas is 2mg/L.
Embodiment 9
Adopt seawater zinc phosphate sedimentation experiment to estimate the performance of green fluorescence acrylic polymers
Test conditions is as follows: the seawater (ca that test water adopts Tanggu purifying sea water factory to provide
2+477.89mg/L, methyl orange alkalinity 122.58mg/L, pH=7.89, electricity lead 4534.53 * 10
4μ S/cm), add 2.5mg/L Zn in the seawater
2+With 2.5mg/L PO
4 3-, medicament adopts above-mentioned polymer A 6-1 and A6-2, and using dosage is followed successively by 0,5,10,15,20mg/L, and cycles of concentration is 2.0 times, 80 ℃ of controlled temperature, test period 24h.Test solution is measured Zn after cooling, constant volume and filtration
2+And PO
4 3-Concentration.Test result is seen Fig. 6 and Fig. 7.
As seen from the figure: polymer A 6-1, A6-2 have obvious restraining effect at the using dosage of 10mg/L～20mg/L scope to the zinc phosphate dirt as the seawater dirt dispersion agent, can stablize 4mg/L phosphoric acid salt and 2mg/L zine ion.
Adopt the performance of seawater dispersing iron oxide experimental evaluation green fluorescence acrylic polymers
Test conditions is as follows: the seawater (ca that test water adopts Tanggu purifying sea water factory to provide
2+477.89mg/L, methyl orange alkalinity 122.58mg/L, pH=7.89, electricity lead 4534.53 * 10
4μ S/cm), add 5mg/L Fe in the seawater
2+, medicament adopts above-mentioned polymer A 6-1 and A6-2, and using dosage is followed successively by 0,2,4,6,8,10,15,20mg/L, 1.0 times of cycles of concentration controls, 50 ℃ of holding temperatures, total testing time 5h, the test post analysis is measured the total iron content of clear liquor.
Test result is seen Fig. 8, and the result shows that this base polymer seawater dirt dispersion agent can be stabilized in the ferric oxide more than 80% in the seawater at the using dosage of 6mg/L.
Can illustrate by the foregoing description, the performance that has excellent inhibition calcium carbonate scale, phosphoric acid salt crust, zinc dirt by the prepared fluorescence acrylic polymers of method of the present invention, and ferric oxide there is excellent dispersion properties, so can be used as dirty processing of chemistry that the special-purpose dirt dispersion agent of seawater is used for seawater circulation cooling or seawater desalination system, its green fluorescence spike feature can realize the online dosing of these systems and quantitatively control.
Claims (10)
1. fluorescent monomer, N-(2-(methacryloxy) ethyl)-N, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) the ethyl brometo de amonio, its structural formula (1) is as follows:
2. the preparation method of the described fluorescent monomer of claim 1, it may further comprise the steps:
(1) adopt 4-bromo-1,8-naphthalene acid anhydride and Tri N-Propyl Amine are that raw material makes N-n-propyl-4-bromo-1, and the 8-naphthalimide makes N-n-propyl-4-(2-hydroxyethylamino)-1,8-naphthalimide with the thanomin reaction again;
(2) with the N-n-propyl-4-(2-hydroxyethylamino)-1 that obtains, the 8-naphthalimide is dissolved in the solvent, the following and PBr of normal temperature condition
3Reaction, product obtains N-n-propyl-4-(2-bromotrifluoromethane amino)-1, the 8-naphthalimide through neutralization, extraction; This product is dissolved in the solvent, slowly drip the unsaturated compound dimethylaminoethyl methacrylate, fluorescent monomer N-(2-(methacryloxy) the ethyl)-N with two keys is separated out in heating, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) the ethyl brometo de amonio.
3. fluorescence acrylic polymers, its structural formula (2) is as follows:
Wherein, m is 1 or 2; N is the integer of 10-120;
R
1For H or-CH
3
R
2For-CH
3,-CH
2CH
3,-CH
2CH
2CH
3Or-CH
2CH
2(OH) CH
3
4. fluorescence acrylic polymers, it prepares by following method:
(1) utilize 4-bromo-1,8-naphthalene acid anhydride and Tri N-Propyl Amine are that raw material makes N-n-propyl-4-bromo-1, and the 8-naphthalimide makes N-n-propyl-4-(2-hydroxyethylamino)-1,8-naphthalimide with the thanomin reaction again;
(2) with the N-n-propyl-4-(2-hydroxyethylamino)-1 that obtains, the 8-naphthalimide is dissolved in the solvent, the following and PBr of normal temperature condition
3Reaction, product obtains N-n-propyl-4-(2-bromotrifluoromethane amino)-1, the 8-naphthalimide through neutralization, extraction; This product is dissolved in the solvent, slowly drip the unsaturated compound dimethylaminoethyl methacrylate, fluorescent monomer N-(2-(methacryloxy) the ethyl)-N with two keys is separated out in heating, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) the ethyl brometo de amonio;
(3) with initiator (being preferably persulphate) initiator system, utilize step (2) institute's synthetic fluorescent monomer and at least a acrylic monomer (be preferably be selected from (methyl) vinylformic acid, methyl acrylate, methyl acrylate, ethyl propenoate, the Propylene glycol monoacrylate at least a) to carry out polyreaction, temperature is controlled at 60 ℃～100 ℃, wherein, the raw materials quality ratio of described fluorescent monomer and acrylic monomer is in 0.1%～10% scope.
5. polymkeric substance according to claim 4, its number-average molecular weight is 1000～20000, is preferably 2500～17000, more preferably 2500～6500.
6. the preparation method of a fluorescence acrylic polymers, it comprises the steps:
(1) utilize 4-bromo-1,8-naphthalene acid anhydride and Tri N-Propyl Amine are that raw material makes N-n-propyl-4-bromo-1, and the 8-naphthalimide makes N-n-propyl-4-(2-hydroxyethylamino)-1,8-naphthalimide with the thanomin reaction again;
(2) with the N-n-propyl-4-(2-hydroxyethylamino)-1 that obtains, the 8-naphthalimide is dissolved in the solvent, the following and PBr of normal temperature condition
3Reaction, product obtains N-n-propyl-4-(2-bromotrifluoromethane amino)-1, the 8-naphthalimide through neutralization, extraction; This product is dissolved in the solvent, slowly drip the unsaturated compound dimethylaminoethyl methacrylate, fluorescent monomer N-(2-(methacryloxy) the ethyl)-N with two keys is separated out in heating, N-dimethyl-2-((N '-n-propyl-4, the 5-naphthalimide) amino) the ethyl brometo de amonio;
(3) with initiator (being preferably persulphate) initiator system, utilize step (2) institute's synthetic fluorescent monomer and at least a acrylic monomer (be preferably be selected from (methyl) vinylformic acid, methyl acrylate, methyl acrylate, ethyl propenoate, the Propylene glycol monoacrylate at least a) to carry out polyreaction, temperature is controlled at 60 ℃～100 ℃; Wherein, the raw materials quality ratio of described fluorescent monomer and acrylic monomer is in 0.1%～10% scope.
7. the preparation method of the preparation method of fluorescent monomer according to claim 2, the described polymkeric substance of claim 4 or the described polymkeric substance of claim 6, wherein, N-n-propyl-4-(2-bromotrifluoromethane amino)-1, the amount of 8-naphthalimide and dimethylaminoethyl methacrylate is than in 1: 10～1: 1 scope.
8. the preparation method of the preparation method of fluorescent monomer according to claim 2, the described polymkeric substance of claim 4 or the described polymkeric substance of claim 6, it is characterized in that: in the step (2) of preparation fluorescent monomer, described heating is meant that temperature is controlled at 20～60 ℃.
9. the preparation method of polymkeric substance according to claim 4 or the described polymkeric substance of claim 6, wherein, described initiator adopts the dropping mode to add; Behind preferred reaction 0.5～2h, continue back flow reaction 2～5h.
10. the preparation method of polymkeric substance according to claim 4 or the described polymkeric substance of claim 6 is characterized in that: initiator amount is 5%～20% (quality) of monomer total amount, preferred 5%～15% (quality).
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