CN1125090C - Polymer containing tracer group and synthetic method thereof - Google Patents
Polymer containing tracer group and synthetic method thereof Download PDFInfo
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- CN1125090C CN1125090C CN 99100444 CN99100444A CN1125090C CN 1125090 C CN1125090 C CN 1125090C CN 99100444 CN99100444 CN 99100444 CN 99100444 A CN99100444 A CN 99100444A CN 1125090 C CN1125090 C CN 1125090C
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- group
- amino
- sulfonic acid
- polymkeric substance
- naphthalene
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Abstract
The present invention relates to the technical fields of an industrial water treatment medicament and the preparation thereof. The present invention provides a water treatment medicament having a novel structure, a tracing function and a scale dispersion function. The polymer is prepared by that the synthesized polymer containing a phosphonic acid group, a carboxyl alkyl ester group, a carboxyl group and a sulfonic group, and fluorescent organic acid salt are added into a sealed container to be uniformly mixed and heated to 90 to 200 DEG C; the temperature is kept, and the materials are continuously stirred for 0.5 to 8 to carry out acid amide conversion reaction. The concentration of the product in water can be rapidly and accurately measured by fluorescent monitoring. Simultaneously, when various metal salt scale coexist, the present invention can ensure. A scale effect The synthetic technological method is simple and reliable and is easy to carry out industrialization control.
Description
The present invention relates to Treatment of Industrial Water medicament and manufacturing technology thereof.Exactly, relate to a kind of multipolymer and synthetic method thereof that has the novel texture of spike and scale inhibition dissemination concurrently; Be the resistance dispersion agent and the synthetic method thereof of tracer-containing.
The traditional analysis means of water treatment agent substantially all is that medicament is directly analyzed in the industrial circulating cooling water, and is generally all more loaded down with trivial details, and contained polymkeric substance is not still had accurate measuring method.Recent years, utilize the water treatment agent in the Measurement and analysis industrial circulating water fast of combining of Treatment of Industrial Water medicament and tracer agent.Existing patent major part all adopts the organism that will contain fluorescence and Treatment of Industrial Water with mixed with polymers together, joins in the industrial cycle water system, comes the content of monitoring polymer by the concentration of measurement fluorescent substance.As U.S. Pat 4783314, promptly be that water treatment agents such as 2-naphthene sulfonic acid (2-NSA) and polypropylene acid thing polyacrylamide are mixed, in the adding system, monitor by the mensuration fluorescence intensity.The flat 3-185341 of Japanese Patent then be with
Mix with polymer phase with water treatment, monitor by ultraviolet spectrometry.Though having satisfied, these patents analyze simple and efficient requirement, the problem of the direct measurement polymer content of failing fundamentally to solve.Japanese patent laid-open 5-163591 uses in the polymkeric substance in water treatment by chemical reaction, directly introduce the compound that shows fluorescence, therefore can measure the concentration of polymkeric substance itself easy, apace, but its used fluorescence compound is oil loving tagged compound monomer, in the water-soluble poly zoarium that the manufacturing water treatment is used, must in organic solvent, carry out carrying out the technology that solvent distills in the polymerization process, like this engineering not only numerous and diverse and also from the environment aspect, the aspect takes precautions against calamities, saving the resource aspect and consider, is not good method.
Purpose of the present invention proposes a kind of water treatment agent that has spike and scale inhibition dissemination concurrently with novel texture dirt dispersion agent and the synthetic method thereof of tracer-containing one by one exactly.Its concentration in the industrial cycle water system can be passed through the fluorescence monitoring rapid test, when multiple metal salt crust coexists, can guarantee scale inhibition effect simultaneously.The invention allows for synthetic method simple, reliable, that be easy to control.
The polymkeric substance that contains tracer group that the present invention proposes has the structure that following general structural formula (I) is expressed:
In the formula:
R is
R
2, R
4Be H or methyl; R
3Be C
nH
2n, n is 0 or the positive integer of 1-10; R
6Be hydroxyethyl (C
2H
4OH) or hydroxypropyl (C
3H
6OH); R
6Be methylene radical (CH
2-) or phenyl
Or 2-methyl-2 amide group-propyl group
Or main chain directly with-SO
3Z links to each other; R
8Be methyl or amide group or H; Z is H or sodium Metal 99.5 ion; M, b, L are positive integer; M is generally 1-60, is preferably 4-8; B is generally 1-22, is preferably 6-12; L is generally 0-10, is preferably 1-7.
F
1And F
2One is H or methyl (CH
3) or ethyl (C
2H
6), and another is the aromatic ring that contains 1-3 sulfonic acid group.
In the infrared spectrum of this polymkeric substance, at 3390cm
-1, 1700cm
-1, 1570cm
-1, 1450cm
-1, 1400cm
-1, 1130cm
-1, 1045cm
-1, and 1620cm
-1, 1500cm
-1About have absorption peak, be respectively-OH,
The charateristic avsorption band of carboxylate salt, sulfonate and organic phosphonate and aromatic ring.
In addition, its
31In the nmr spectrum of P, chemical shift has 1 peak at 46 σ places, shows to contain the C-P key in the structure, has phosphonyl group.
It is 1.02-1.10 that this polymkeric substance has relative viscosity, and optimal relative viscosity is 1.04-1.08.
The weight average molecular weight range of this polymkeric substance is 800-50000, and best weight average molecular weight range is 2200-4800.
The synthetic method of the polymkeric substance of the tracer-containing group of said structure, it is spike organic acid salt with structure shown in the polymkeric substance of structure shown in the commercially available formula that contains multiple functional group (II) and the formula (III), join in the airtight container, mix, heat to 90-2000 ℃, keep temperature, constantly stirred 0.5-8 hour, carry out the acid amides conversion reaction, promptly obtain product of the present invention.
The polymkeric substance of above-mentioned multiple functional group has following general structure (II):
In the formula: R
7For-OH or-NH
2
R
1, R
2, R
3, R
4, R
5, R, m, b explain that the multiple functional group of the above-mentioned polymkeric substance of cotype (I) is a phosphonate group, hydroxyalkyl base, carboxyl and sulfonic acid group etc.
Structural polymer shown in the formula (II) can be that phosphine carboxylic multipolymer, phosphinic sulfoacid, polycarboxylic acid multipolymer and oligopolymer etc. contain the phosphine polymkeric substance.
In the formula: F
1, F
2Can be H or methyl (CH
3) or ethyl (C
2H
6), but have at least one to contain tracer group.
Above-mentioned F
1, F
2Preferably H or methyl (CH
3) or ethyl (C
2H
6), and another is the aromatic ring that contains 1-3 sulfonic acid group.
Above-mentioned spike organic acid salt is to contain 1-3 sulfonic group and amino aromatic ring, comprise 1-methylamino-naphthalene-4-sulfonate, 1-ethylamino-naphthalene-4-sulfonate, 1-methylamino-naphthalene-5-sulfonate, 1-methylamino-naphthalene-7-sulfonate, 1-methylamino-naphthalene-8-sulfonate, 1-ethylamino-naphthalene-8-sulfonate, 2-amino-1-naphthalene sulfonic aicd, 1-amino-6-naphthene sulfonic acid, 1-amino-7-naphthene sulfonic acid, 2-amino-5-naphthene sulfonic acid, 1-amino-4,8-two naphthene sulfonic acid, 1-amino-3.8-two naphthene sulfonic acid, 1-amino-3.6.8-three naphthene sulfonic acid, 1-amino-4.6.8-three naphthene sulfonic acid etc.
The inventive method, organic acid (salt) shown in the polymkeric substance cotype (III) shown in the formula (II) reacts by the acid amides conversion, introduced tracer group on the molecular chain that contains phosphonate group, carboxyl, hydroxyalkyl base and sulfonic group polymkeric substance shown in the formula (II), its reaction formula can be expressed as follows formula (VI):
In the formula: R
1, R
2, R
4, R
5, R
6, R, m, b, z, F
1, F
2Explain cotype (I);
R
7For-OH or-NH
2
Synthetic method of the present invention, the consumption of the above-mentioned polymkeric substance that contains multiple functional group (II) is that solid content is the aqueous solution of 15%-90% (weight) in reaction solution, the scope of being more suitable for is 25%-47%.
The weight average molecular weight range of the above-mentioned polymkeric substance that contains multiple functional group (II) is 800-50000, and good weight average molecular weight range is 2000-10000, and optimal weight average molecular weight range is 2200--4800.
Synthetic method of the present invention, above-mentioned spike organic acid salt component (III) is when synthetic has contained the polymer reaction of multiple functional group, and consumption is the 0.01%-5% (weight) of polymer loading, and the scope of application is 0.05%-2% (weight).
Synthetic method of the present invention places encloses container with reaction solution, and temperature is controlled between 90 ℃-200 ℃, and the scope that is more suitable for is at 90 ℃-150 ℃.
It is 0.5-8 hour that synthetic method of the present invention, reaction solution place the reacting by heating time of encloses container, and the scope that is more suitable for was at 2-5 hour.
The present invention contains the polymkeric substance of tracer group, compares with the product of foreign patent report, have the low characteristics of molecular weight, thereby product improves greatly as the performance that water treatment agent hinders multiple incrustation scale.Product of the present invention has unique monitoring property, and concentration analysis shows that along with the variation of polymer concentration, its fluorescence intensity also changes pari passu, is a kind of dirt dispersion agent that can accurately be measured content.Simultaneous test proves that this product had both had the multiple dirty performance of good comprehensive dispersion, can supervise examination again apace and measure, and has reduced artificial test job in a large number, so show the multi-functional outstanding feature of potion.The process synthetic method of product of the present invention is simple, reliable, be easy to industrialization control.
Further specify the present invention in conjunction with following embodiment, but the present invention is not limited to following embodiment.
Embodiment 1
1.5g2-amino-1-naphthalene sulfonic aicd is joined 350g to be contained in the aqueous solution of 90g phosphine polymers of carboxylic acid, stir, this mixed solution is joined in the autoclave of 500ml, heating up is heated to 140 ℃ of temperature, kept this temperature 4 hours, be cooled to room temperature then, reaction solution is taken out, obtain brown solution, yield is 99%, solid content is 25.4%, and relative viscosity is 1.052, and weight-average molecular weight is 2200-3500.This liquid through gel chromatography separation, is carried out the fluorescent scanning analysis to collected each component and knows, 90% in 2-amino-1-naphthalene sulfonic aicd has been synthesized on the polymkeric substance.This product excitation wavelength and emission wavelength (representing with ex/em) are 309nm/402nm.
This product is mixed with the solution of different concns, and its fluorescence intensity sees Table (I):
Table (I)
Product concentration (ppm) | 1 | 2 | 5 | 10 | 20 |
Fluorescence intensity | 5 | 10.1 | 25.8 | 50.9 | 99.4 |
Embodiment 2
1.5g 2-amino-5-naphthene sulfonic acid is joined 350g to be contained in the aqueous solution of 100g phosphinic sulfoacid carboxylic acid multicomponent copolymer, stir, this mixed solution is joined in the autoclave of 500ml, heating up is heated to 140 ℃ of temperature, kept this temperature 5 hours, cool then, reaction solution is taken out, obtain brown solution, yield is 99%, solid content is 28.2%, and relative viscosity is 1.054, and weight-average molecular weight is 2600--3400.
Embodiment 3
1g2-amino-1-naphthalene sulfonic aicd is joined 350g contains in the aqueous solution of 150g oligopolymer, stir, below each step operation and condition with embodiment 1, obtain brown solution at last, product yield is 99%, solid content is 42.8%, relative viscosity is 1.068.
Embodiment 4
This reacts each condition and operation steps with embodiment 1, and wherein 2-amino-1-naphthalene sulfonic aicd replaces with 1g amino-7-naphthene sulfonic acid, obtains brown solution, and product yield is 99%.
Embodiment 5
This reacts each condition and operation steps with embodiment 1, and wherein 2-amino-1-naphthalene sulfonic aicd replaces with 1-amino-6-naphthene sulfonic acid, obtains brown solution, and product yield is 99%.
Embodiment 6
2g2-amino-1 naphthene sulfonic acid is joined 350g to be contained in the aqueous solution of 40g phosphine polymers of carboxylic acid; stir; this mixed solution is joined in the autoclave of 500ml; logical nitrogen protection heats up and is heated to 90 ℃ of temperature, keeps this temperature 8 hours; cool then; reaction solution is taken out, obtain brown solutions, yield is 99%.
Embodiment 7
1.5g1-amino-7-naphthene sulfonic acid is joined 320g contain in the aqueous solution of 150g phosphine polymers of carboxylic acid, stir.This mixed solution is joined in the autoclave of 500ml, logical nitrogen, and make that pressure reaches 6 normal atmosphere in the still, and heat up and be heated to 150 ℃, kept this temperature 2 hours, be cooled to room temperature then, reaction solution is taken out, obtain brown solution, yield is 99%.
Embodiment 8
This reacts each condition and operation steps with embodiment 2, and wherein 2-amino-5-naphthene sulfonic acid replaces with 1-amino-7-naphthene sulfonic acid, obtains brown solution, and product yield is 99%.
Embodiment 9
1.35g1-amino-4.8-two naphthene sulfonic acid are joined 350g contain in the aqueous solution of 27g oligopolymer, stir.This mixed solution is joined in the autoclave of 500ml, logical nitrogen, and make in the still pressure reach 6 big chlorine to press, heat up and be heated to 120 ℃, kept this temperature 5 hours, be cooled to room temperature then, reaction solution is taken out, obtain the brown product.
Embodiment 10
This reacts each condition and operation steps with embodiment 2, and wherein 2-amino-5-naphthene sulfonic acid replaces with 1-methylamino-naphthalene-8 sulfonate, obtains the brown product.
Embodiment 11
This reacts each condition and the same examples of implementation of operation steps, and wherein 2-amino-1-naphthalene sulfonic aicd replaces with 1-ethylamino-naphthalene-4-sulfonate, obtains the brown product.
Embodiment 12
Scale inhibition and dispersion performance test condition and result: 1. test conditions (1) lime carbonate scale inhibition performance test condition:
Ca
+ 2(with CaCO
3Meter) 80 ℃ of 600ppm PH=9 6 hours
Dirt dispersion agent add-on 4ppm; (2) calcium phosphate scale inhibition performance test condition:
Ca
+ 2(with CaCO
3Meter) 250ppm PO
4 3-80 ℃ of 6ppm PH=9
6 hours
Dirt dispersion agent add-on 4ppm; (3) iron dirt rate test condition:
Fe
+ 280 ℃ of 9ppm PH=9 6 hours
Dirt dispersion agent add-on 2ppm; (4) zinc dirt test condition:
Zn
+ 27.8ppm 80 ℃ of PH=9 6 hours
Dirt dispersion agent add-on 4ppm; 2. test result sees Table (2):
Table (2)
The sample title | Scale inhibition performance % | |||
Lime carbonate | Calcium phosphate | The iron dirt | The zinc dirt | |
Example 1 | 75 | 85 | 99 | 88 |
Example 7 | 85 | 86 | 98 | - |
Example 8 | 76 | 84 | 99 | 88 |
External sample | 60 | 72 | 90 | 80 |
Claims (8)
1. polymkeric substance that contains tracer group is characterized in that having following general structural formula (I):
In the formula:
R
1For
Or H; R is
Or
R
2, R
4Be H or methyl; R
3Be C
nH
2n, n is 0 or the positive integer of 1-10; R
5Be hydroxyethyl (C
2H
4OH) or hydroxypropyl (C
3H
6OH); R
6Be methylene radical (CH
2-) or phenyl
Or 2-methyl-2 amide group-propyl group
Or main chain directly with-SO
3Z links to each other; R
8Be methyl or amide group or H;
Z is H or sodium Metal 99.5 ion;
M is 1-60, and b is 1-22, and L is the positive integer of 0-10, when L=0 then R=0 be binary polymer.
At F
1And F
2In, one of them is H or methyl (CH
3) or ethyl (C
2H
6), another then is the aromatic ring that contains 1-3 sulfonic acid group
2. one kind is synthesized the method for general structure polymkeric substance according to claim 1, and it is characterized in that: will have general structure (II) is:
In the formula: R
7For-OH or (NH
2)
R
1, R
2, R
3, R
4, R
5R, m, b explains the phosphonate group that contains with claim 1, polymkeric substance and general structure (III) that phosphine carboxylic multipolymer, phosphinic sulfoacid multipolymer, polycarboxylic acid multipolymer and the oligopolymers etc. of hydroxyalkyl base, carboxyl and the multiple functional group of sulfonic group and weight average molecular weight range are 800-50000 are:
In the formula: F
1, F
2Can be H or methyl (CH
3) or ethyl (C
2H
6), but wherein have at least
A spike organic acid salt thing that contains the aromatic ring of tracer group and 1-3 sulfonic acid group, comprising 1-methylamino-naphthalene-4-sulfonate, 1-ethylamino-naphthalene-4-sulfonate, 1-methylamino-naphthalene-5-sulfonate, 1-methylamino-naphthalene-7-sulfonate, 1-methylamino-naphthalene-8-sulfonate, 1-ethylamino-naphthalene-8-sulfonate, 2-amino-1-naphthalene sulfonic aicd, 1-amino-6-naphthene sulfonic acid, 1-amino-7-naphthene sulfonic acid, 2-amino-5-naphthene sulfonic acid, 1-amino-4,8-two naphthene sulfonic acid, 1-amino-3.8-two naphthene sulfonic acid, 1-amino-3.6.8-three naphthene sulfonic acid, 1-amino-4.6.8-three naphthene sulfonic acid etc., carry out the acid amides conversion reaction: with more function group polymkeric substance (II) solid content is the aqueous solution of 15%-90% weight, with consumption is the spike organic acid thing (III) of (II) polymer loading 0.01%-5% weight, joins in the airtight container, mixes under the condition, be heated to 90 ℃-200 ℃, be incubated 0.5-8 hour then, reaction is finished, and promptly gets product of the present invention.
3. synthetic method as claimed in claim 2, it is further characterized in that: the weight average molecular weight range of more function group polymkeric substance (II) is 2000-10000.
4. synthetic method as claimed in claim 2, it is further characterized in that: the solid content of more function group polymkeric substance (II) is a 25%-47% weight.
5. synthetic method as claimed in claim 2, it is further characterized in that: the amount ranges of spike organic acid salt (III) is 0.05%-2%.
6. synthetic method as claimed in claim 2, it is further characterized in that: the insulation reaction temperature range is 90 ℃-150 ℃.
7. synthetic method as claimed in claim 2, it is further characterized in that: the insulation reaction time range is 2-5 hour.
8. synthetic method as claimed in claim 2, it is further characterized in that: it is 2200-4800 that the weight-average molecular weight of more function group polymkeric substance (II) is more suitable for scope.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 99100444 CN1125090C (en) | 1999-01-29 | 1999-01-29 | Polymer containing tracer group and synthetic method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 99100444 CN1125090C (en) | 1999-01-29 | 1999-01-29 | Polymer containing tracer group and synthetic method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1229091A CN1229091A (en) | 1999-09-22 |
CN1125090C true CN1125090C (en) | 2003-10-22 |
Family
ID=5270000
Family Applications (1)
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CN 99100444 Expired - Lifetime CN1125090C (en) | 1999-01-29 | 1999-01-29 | Polymer containing tracer group and synthetic method thereof |
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CN (1) | CN1125090C (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100410287C (en) * | 2005-09-30 | 2008-08-13 | 南京理工大学 | Phosphine-based Marpropy multipolymer containing fluorescent base-group and its production |
WO2008090854A1 (en) * | 2007-01-24 | 2008-07-31 | Kurita Water Industries Ltd. | Method for the treatment with reverse osmosis membrane |
CN102533256A (en) * | 2012-02-21 | 2012-07-04 | 上海瑞靖环境技术发展有限公司 | Fluorescence labeling tracer and preparation method thereof |
-
1999
- 1999-01-29 CN CN 99100444 patent/CN1125090C/en not_active Expired - Lifetime
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