CN103242476B - A kind of preparation method with the acrylic polymers of fluorescent characteristic - Google Patents
A kind of preparation method with the acrylic polymers of fluorescent characteristic Download PDFInfo
- Publication number
- CN103242476B CN103242476B CN201310170744.3A CN201310170744A CN103242476B CN 103242476 B CN103242476 B CN 103242476B CN 201310170744 A CN201310170744 A CN 201310170744A CN 103242476 B CN103242476 B CN 103242476B
- Authority
- CN
- China
- Prior art keywords
- preparation
- solvent
- acrylic polymers
- fluorescent characteristic
- disulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of preparation method with the acrylic polymers of fluorescent characteristic, the method comprises: by monomer 2-allyloxy naphthalene-6,8-disulfonic acid potassium and monomeric acrylic mix in reaction vessel with solvent, initiator ammonium persulfate, under the condition of normal pressure passing into rare gas element, control temperature 80-120 DEG C, reacts after 4-8 hour and obtains; Described solvent is selected from dimethyl formamide, alcohol ethers; 2-allyloxy naphthalene-6,8-disulfonic acid potassium: vinylformic acid: solvent: the mass ratio of initiator is 0.1 ~ 0.2%:1:50% ~ 80%:0.01% ~ 0.06%; The described viscosity-average molecular weight with the acrylic polymers of fluorescent characteristic is 3000-6000, and its fluorescence maximum excitation wavelength is λ ex=239nm, and maximum emission wavelength is λ em=355nm.The acrylic polymers of fluorescent characteristic that what the inventive method obtained have has the features such as fluorescent stability is good, immunity from interference is strong, scale-inhibiting properties is excellent, and the antiscaling dispersion and the fluorescence that can be used for industrial refrigeration cycle water treatment system detect automatically.
Description
Technical field
The invention belongs to technology on circulating cooling water treatment field, be specifically related to a kind of preparation method with the acrylic polymers of fluorescent characteristic.
Background technology
Usually phosphorus line formulation is adopted in industrial circulating water; that is in each antiscaling dispersion or corrosion inhibition formula all containing organophosphorus chemistry medicament; as hydroxy ethylene diphosphonic acid (HEDP); Amino Trimethylene Phosphonic Acid (ATMP); 2-phosphinylidyne butane-1.2.4-tri hydroxy acid (PBTC), ethylenediamine tetramethylene phosphonic acid (EDTMP) etc.Engineering technical personnel adopt the blue spectrophotometry of phosphorus molybdenum to regulate chemical feeding quantity, to control water quality to measure phosphorus content in recirculated water.Current most domestic producer still adopts this traditional analytical procedure to test, due to comparatively loaded down with trivial details and delayed to the analysis of total phosphorus in phosphorus line formulation, at present to trace polymer again without accurate testing method, cause medicament accurately and timely not add thus have impact on the treatment effect of medicament.
In addition, along with Water Treatment Chemicals environmental pollution is more and more subject to people's attention, people start to recognize that inorganic phosphorus, organophosphate hydrolysis etc. can cause body eutrophication, cause bacterium algae amount reproduction, form the environmental pollution phenomenons such as red tide, so low-phosphorous or without phosphorus formula starts to be subject to people's attention, but low-phosphorous formula adopts phosphorus molybdenum, and blue spectrophotometry test can cause sensitivity and accuracy greatly to reduce, and without phosphorus formula is difficult to measure especially.
The trace analysis appeared as in industrial circulating cooling water process with the acrylic polymers of fluorescent characteristic provides one novel method fast and accurately, owing to containing fluorophor in its molecular structure, its concentration in water can be obtained rapidly and accurately by fluoroscopic examination, thus achieves system detection and control automatically accurately.Engineering technical personnel by the drug concentration of mensuration very rapidly and in acquisition system easily to fluorescent characteristic material, thus can evaluate water treatment system and process accurately.Doing so avoids and cause the unfavorable factors such as corrosion and scaling because the detection of water Chinese medicine is inaccurate, ensure that good treatment effect.But there is the deficiency that comprehensive dispersion scale-inhibiting properties is poor, fluorescent stability is poor, immunity from interference is weak in the acrylic polymers with fluorescent characteristic existed at present.
Summary of the invention
Technical problem to be solved by this invention overcomes the problems referred to above of the prior art, there is provided a kind of there is excellent comprehensive dispersion scale-inhibiting properties, fluorescent stability is good, immunity from interference is strong, and manufacturing cost is lower, effects of energy saving and emission reduction is good, improve water treatment cycles of concentration and the preparation method with the acrylic polymers of fluorescence property without phosphatization corrosion-mitigation scale-inhibition net effect.
A kind of preparation method with the acrylic polymers of fluorescent characteristic of present method, it is characterized in that, the method comprises: by monomer 2-allyloxy naphthalene-6,8-disulfonic acid potassium and monomeric acrylic mix in reaction vessel with solvent, initiator, under the condition of normal pressure passing into rare gas element, obtain after control temperature 80-120 DEG C, polyreaction 4-8 hour;
Wherein, described solvent is selected from dimethyl formamide, alcohol ethers, and described initiator is ammonium persulphate; 2-allyloxy naphthalene-6,8-disulfonic acid potassium: vinylformic acid: solvent: the mass ratio of initiator is 1.0 ~ 2.0%:1:50% ~ 80%:0.01% ~ 0.06%;
The described viscosity-average molecular weight with the acrylic polymers of fluorescent characteristic is 3000-6000, and its fluorescence maximum excitation wavelength is λ ex=239nm, and maximum emission wavelength is λ em=355nm;
Described monomer 2-allyloxy naphthalene-6, the preparation method of 8-disulfonic acid potassium is: by beta naphthal-6, after 8-disulfonic acid potassium is dissolved in dimethylsulfoxide solvent, at the uniform velocity add propenyl chloride, wherein the mol ratio of beta naphthal-6,8-disulfonic acid potassium and propenyl chloride is 1:1.1 ~ 1:1.3, and water bath heating temperature controls at 40 ~ 50 DEG C, after heat-retaining condition reaction in 6 ~ 8 hours terminates, underpressure distillation is fallen solvent and is obtained.
In technique scheme, described 2-allyloxy naphthalene-6,8-disulfonic acid potassium and acrylic acid mass ratio are preferably 1.5%.
Described initiator preferably also comprises S-WAT, and described initiator and acrylic acid mass ratio are preferably 0.04% ~ 0.05%.
Described alcohol ether solvent is preferably selected from one or more in ethylene glycol monomethyl ether, butyl glycol ether and butyl, and described solvent and acrylic acid mass ratio are preferably 60% ~ 70%.
Described rare gas element is preferably nitrogen.
Described polymeric reaction temperature is preferably 90 ~ 100 DEG C.
Described polymerization reaction time is preferably 6 ~ 7 hours.
Compared with prior art, its beneficial effect is as follows for the inventive method:
It is good that the acrylic polymers of fluorescent characteristic that prepared by the inventive method have has fluorescent stability, and immunity from interference is strong, the features such as scale-inhibiting properties is excellent.The acrylic polymers of fluorescent characteristic that prepared by the method have is mainly used in the antiscaling dispersion of industrial refrigeration cycle water treatment system in petrochemical industry, power plant, iron and steel enterprise and fluorescence detects automatically, can realize monitoring recirculated water Chinese medicine concentration rapidly, greatly reduce made work amount, and have that manufacturing cost is lower, effects of energy saving and emission reduction good, improve water treatment cycles of concentration and without phosphatization corrosion-mitigation scale-inhibition net effect.
Accompanying drawing explanation
Fig. 1 be prepared by the inventive method there is the acrylic polymers concentration of fluorescent characteristic and the graph of a relation of fluorescence intensity.
Embodiment
Further illustrate the present invention in conjunction with following embodiment, but the present invention is not limited to following embodiment.
The preparation of fluorescent monomer 2-allyloxy naphthalene-6,8-disulfonic acid potassium
The beta naphthal-6 of 19.3g is added in the four-hole boiling flask that agitator, prolong and thermometer are housed, 8-disulfonic acid potassium and solvent methyl-sulphoxide 40g, start agitator and slowly heating, make beta naphthal-6,8-disulfonic acid sylvite dissolves gradually, then be at the uniform velocity added drop-wise in reaction flask by the propenyl chloride of 4.6g, bath temperature controls at 45 DEG C, heat-retaining condition 7 hours, after reaction terminates, solvent is fallen in underpressure distillation, finally obtains pale yellow powder shape solid 2-allyloxy naphthalene-6,8-disulfonic acid potassium.The raw material related in above-mentioned preparation process is commercial goods.
There is the synthesis of the acrylic polymers of fluorescent characteristic
Monomer 2-allyloxy naphthalene-6,8-disulfonic acid potassium in following examples 1-3 prepares by above-mentioned fluorescent monomer preparation method, and other raw materials are commercial goods.
Embodiment 1
1.0 grams of 2-allyloxy naphthalene-6,8-disulfonic acid potassiums and 50.0 grams of vinylformic acid are dissolved in 25 grams of dimethyl formamides, the ammonium persulphate of 20 grams of deionized water dissolvings 15.0 milligrams and the S-WAT of 7.5 milligrams; 72 grams of deionized waters add and are equipped with in the 250ml four-hole bottle of agitator, prolong and thermometer, stir, and logical nitrogen, controlling temperature of reaction is 90 DEG C, is incubated and obtains a kind of acrylic polymers with fluorescent characteristic after 4 hours.After measured, its fluorescence maximum excitation wavelength X ex=239nm, maximum emission wavelength is λ em=355nm.
Embodiment 2
0.75 gram of 2-allyloxy naphthalene-6,8-disulfonic acid potassium and 50.0 grams of vinylformic acid are dissolved in 35 grams of ethylene glycol monomethyl ether; The ammonium persulphate of 20 grams of deionized water dissolvings 15.0 milligrams and the S-WAT of 7.5 milligrams; 62 grams of deionized waters add and are equipped with in the 250ml four-hole bottle of agitator, prolong and thermometer, stir, and logical nitrogen, controlling temperature of reaction is 100 DEG C, is incubated and obtains a kind of acrylic polymers with fluorescent characteristic after 6 hours.After measured, its fluorescence maximum excitation wavelength X ex=239nm, maximum emission wavelength is λ em=355nm.
Embodiment 3
0.5 gram of 2-allyloxy naphthalene-6,8-disulfonic acid potassium and 50.0 grams of vinylformic acid are dissolved in 40 grams of butyl; The ammonium persulphate of 20 grams of deionized water dissolvings 15.0 milligrams and the S-WAT of 7.5 milligrams; 57 grams of deionized waters add and are equipped with in the 250ml four-hole bottle of agitator, prolong and thermometer, stir, and logical nitrogen, controlling temperature of reaction is 120 DEG C, is incubated and obtains a kind of acrylic polymers with fluorescent characteristic after 8 hours.After measured, its fluorescence maximum excitation wavelength X ex=239nm, maximum emission wavelength is λ em=355nm.
Fluorescence property is evaluated
Use Hitachi F-7000 spectrophotofluorometer to carry out 3-D scanning to the acrylic polymers with fluorescent characteristic prepared by embodiment 1-3, can obtain the maximum excitation wavelength X ex=239nm of this polymkeric substance, maximum emission wavelength is λ em=355nm.
Adopt maximum excitation wavelength X ex=239nm, maximum emission wavelength is λ em=355nm.What obtain in testing example 1 has the acrylic polymers concentration of fluorescent characteristic and the relation of fluorescence intensity, and test data is as shown in table 1, has the graph of a relation of the acrylic polymers concentration of fluorescent characteristic and fluorescence intensity as shown in Figure 1.
Table 1 has the acrylic polymers concentration of fluorescent characteristic and the relation of fluorescence intensity
| Concentration (ppm) | 0(is blank) | 0.5 | 1.0 | 2.0 | 3.0 |
| Fluorescence intensity | 3.55 | 3.25 | 6.13 | 9.61 | 13.5 |
| Concentration (ppm) | 4.0 | 5.0 | 6.0 | 8.0 | 10.0 |
| Fluorescence intensity | 17.4 | 21.1 | 24.5 | 31.7 | 39.2 |
Note: test condition is for exciting slit and launching slit 5nm, and voltage is 400V.
From table 1 and Fig. 1, the acrylic polymers with fluorescent characteristic concentration be within the scope of 0 ~ 10ppm fluorescence intensity and concentration linear, its minimum detecting is limited to 0.5ppm.
Scale-inhibiting properties is tested
The resistance CaCO with the acrylic polymers of fluorescent characteristic that polyacrylic acid and the inventive method are prepared
3dirt performance is evaluated, with reference to the mensuration>=carry out resistance CaCO of GB/T 6632-96≤water conditioner scale-inhibiting properties
3dirt assessment of performance.
Test conditions: [Ca
2+]=250mg/L, [HCO
3 -]=250mg/L(is all with CaCO
3meter), pH=9.0, water temperature 80 DEG C, 10hr, inhibitor concentration is 5ppm.
Polyacrylic acid and there is the acrylic polymers of fluorescent characteristic to CaCO
3the concrete data of restraining effect of dirt are as follows:
Table 2: polyacrylic acid contrasts with the acrylic polymers scale-inhibiting properties with fluorescent characteristic
| Name of product | Calcium carbonate scale inhibition performance (%) |
| Polyacrylic acid | 83.2 |
| Embodiment 1 has the acrylic polymers of fluorescent characteristic | 82.5 |
| Embodiment 2 has the acrylic polymers of fluorescent characteristic | 82.9 |
| Embodiment 3 has the acrylic polymers of fluorescent characteristic | 83.1 |
The acrylic polymers as seen by table 2 with fluorescent characteristic still remains polyacrylic excellent scale-inhibiting properties, does not affect the scale inhibition effect of water treatment.
Resistance to chlorine is tested
Test condition:
Maximum excitation wavelength 239nm and maximum emission wavelength 355nm testing example 2 is adopted to have the acrylic polymers of fluorescent characteristic, test concentrations is 10ppm, excite slit to be 5nm with transmitting slit, voltage is 400V, the trichloroisocyanuric acid that oxidizing substance selects water treatment system conventional.
Table 3 trichloroisocyanuric acid is on the impact with the acrylic polymers fluorescence intensity of fluorescent characteristic of 10ppm
As shown in Table 3: in water, the concentration of trichloroisocyanuric acid is within the scope of 0-10ppm, and fluorescence intensity is basicly stable, variation range, within 5%, meets onsite application requirement.
And most fluorescent chemicals is deposited in case at oxidizing substance, there is generation quenching of fluorescence.Normally cannot use in industrial circulation water treatment system.
The impact of water intermediate ion
Calcium ion concn (in calcium carbonate mg/L) has the acrylic polymers fluorescence intensity of fluorescent characteristic impact on embodiment 1 is as shown in table 4.
Table 4 calcium ion is on the impact with the acrylic polymers fluorescence intensity of fluorescent characteristic of 10ppm
| Calcium ion concn ppm | 1 day | 2 days | 3 days | 4 days |
| 0(is blank) | 54.7 | 54.5 | 53.7 | 53.3 |
| 100 | 54.6 | 54.4 | 54.2 | 54.2 |
| 200 | 54.5 | 54.1 | 54.0 | 54.0 |
| 300 | 54.3 | 54.0 | 53.7 | 53.1 |
| 400 | 53.9 | 53.7 | 53.4 | 53.0 |
| 600 | 53.8 | 53.5 | 53.0 | 52.4 |
As shown in Table 4: in water, calcium ion concn is within the scope of 0-600ppm, the acrylic polymers fluorescence intensity that embodiment 1 has fluorescent characteristic is basicly stable, and variation range is within 5%.
Magnesium ion concentration (in calcium carbonate mg/L) has the acrylic polymers fluorescence intensity of fluorescent characteristic impact on embodiment 1 is as shown in table 5.
Table 5 magnesium ion is on the impact with the acrylic polymers fluorescence intensity of fluorescent characteristic of 10ppm
| Magnesium ion concentration ppm | 1 day | 2 days | 3 days | 4 days |
| 0(is blank) | 54.6 | 54.4 | 53.7 | 53.4 |
| 50 | 54.4 | 54.3 | 53.7 | 53.2 |
| 100 | 54.2 | 53.8 | 53.6 | 53.1 |
| 200 | 54.1 | 53.9 | 53.7 | 53.3 |
| 300 | 53.9 | 53.7 | 53.2 | 53.0 |
| 400 | 53.6 | 53.1 | 52.9 | 52.7 |
| 600 | 53.2 | 53.1 | 52.6 | 52.2 |
| 800 | 53.0 | 52.6 | 52.5 | 52.0 |
| 1000 | 53.0 | 52.7 | 52.5 | 52.0 |
As shown in Table 5: in water, magnesium ion concentration is within the scope of 0-1000ppm, the acrylic polymers fluorescence intensity that embodiment 1 has fluorescent characteristic is basicly stable, and variation range, within 5%, meets onsite application requirement.
Sulfate ion concentration is (with SO
4 2-mg/L counts) impact embodiment 2 to the acrylic polymers fluorescence intensity of fluorescent characteristic is as shown in table 6.
Table 6 sulfate ion is on the impact with the acrylic polymers fluorescence intensity of fluorescent characteristic of 10ppm
| Sulfate ion concentration ppm | 1 day | 2 days | 3 days | 4 days |
| 0(is blank) | 50.7 | 50.0 | 50.2 | 49.8 |
| 100 | 50.0 | 49.3 | 48.8 | 48.3 |
| 200 | 50.6 | 50.0 | 49. 5 | 49.3 |
| 300 | 50.8 | 50.9 | 50.1 | 49.9 |
| 400 | 50.8 | 49.7 | 49.4 | 49.1 |
| 600 | 50.3 | 49.2 | 49.0 | 48.8 |
| 800 | 50.1 | 48.8 | 48.1 | 47.9 |
| 1000 | 49.7 | 49.4 | 49.0 | 48.2 |
As shown in Table 6: in water, sulfate ion concentration is within the scope of 0-1000ppm, the acrylic polymers fluorescence intensity that embodiment 2 has fluorescent characteristic is basicly stable, and variation range, within 5%, meets onsite application requirement.
Carbon acid ion concentration (in calcium carbonate mg/L) has the acrylic polymers fluorescence intensity of fluorescent characteristic impact on embodiment 3 is as shown in table 7.
Table 7 carbanion (in calcium carbonate mg/L) is to the fluorescent characteristic that has of 10ppm
The impact of acrylic polymers fluorescence intensity
| Carbon acid ion concentration ppm | 1 day | 2 days | 3 days | 4 days |
| 0(is blank) | 41.7 | 41.6 | 41.5 | 41.6 |
| 10 | 41.0 | 40.8 | 40.2 | 39.9 |
| 20 | 40.9 | 40.0 | 39.8 | 39.6 |
| 30 | 40.3 | 40.6 | 40.2 | 39.1 |
| 50 | 40.7 | 40.6 | 40.2 | 39.3 |
| 70 | 40.2 | 39.6 | 40.1 | 38.8 |
| 100 | 40.1 | 40.0 | 39.9 | 39.9 |
| 200 | 39.4 | 39.0 | 39.1 | 38.9 |
| 300 | 39.8 | 39.8 | 39.7 | 39.2 |
| 400 | 38.9 | 38.6 | 38.7 | 38.0 |
| 600 | 38.6 | 38.0 | 37.8 | 37.7 |
As shown in Table 7: in water, carbon acid ion concentration is within the scope of 0-600ppm, the acrylic polymers fluorescence intensity that embodiment 3 has fluorescent characteristic is basicly stable, and variation range, within 8%, meets onsite application requirement.
By above-mentioned test, can find out, the fluorescent stability of what the inventive method obtained the have acrylic polymers of fluorescent characteristic is good, immunity from interference is strong.
The acrylic polymers of fluorescent characteristic that what present method obtained have can be widely used in the antiscaling dispersion of industrial refrigeration cycle water treatment system and fluorescence detects automatically, fast monitored can be carried out to circulating water system, real-time adjustment adding consistency, effectively system is carried out to the control of fouling and corrosion, improve water treatment efficiency, and manual operation cost can be greatly reduced.
Claims (7)
1. one kind has the preparation method of the acrylic polymers of fluorescent characteristic, it is characterized in that, the method comprises: by monomer 2-allyloxy naphthalene-6,8-disulfonic acid potassium and monomeric acrylic mix in reaction vessel with solvent, initiator, under the condition of normal pressure passing into rare gas element, obtain after control temperature 80-120 DEG C, polyreaction 4-8 hour;
Wherein, described solvent is selected from dimethyl formamide, alcohol ethers, and described initiator is ammonium persulphate; 2-allyloxy naphthalene-6,8-disulfonic acid potassium: vinylformic acid: solvent: the mass ratio of initiator is 1% ~ 2%:1:50% ~ 80%:0.01% ~ 0.06%;
The described viscosity-average molecular weight with the acrylic polymers of fluorescent characteristic is 3000-6000, and its fluorescence maximum excitation wavelength is λ ex=239nm, and maximum emission wavelength is λ em=355nm;
The preparation method of described monomer 2-allyloxy naphthalene-6,8-disulfonic acid potassium is: after beta naphthal-6,8-disulfonic acid potassium is dissolved in dimethylsulfoxide solvent, at the uniform velocity drip propenyl chloride, wherein the mol ratio of beta naphthal-6,8-disulfonic acid potassium and propenyl chloride is 1:1.1 ~ 1:1.3; Water bath heating temperature controls at 40 ~ 50 DEG C, is incubated after 6 ~ 8 hours, and underpressure distillation is fallen solvent and obtained.
2. preparation method according to claim 1, is characterized in that, described 2-allyloxy naphthalene-6,8-disulfonic acid potassium and acrylic acid mass ratio are 1.5%.
3. preparation method according to claim 1, is characterized in that, described initiator also comprises S-WAT, and described initiator and acrylic acid mass ratio are 0.04% ~ 0.05%.
4. preparation method according to claim 1, is characterized in that, described alcohol ether solvent is selected from one or more of ethylene glycol monomethyl ether, butyl glycol ether and butyl, and described solvent and acrylic acid mass ratio are 60% ~ 70%.
5. preparation method according to claim 1, is characterized in that, described rare gas element is nitrogen.
6. preparation method according to claim 1, is characterized in that, described polymeric reaction temperature is 90 ~ 100 DEG C.
7. preparation method according to claim 1, is characterized in that, described polymerization reaction time is 6 ~ 7 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310170744.3A CN103242476B (en) | 2013-05-10 | 2013-05-10 | A kind of preparation method with the acrylic polymers of fluorescent characteristic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310170744.3A CN103242476B (en) | 2013-05-10 | 2013-05-10 | A kind of preparation method with the acrylic polymers of fluorescent characteristic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103242476A CN103242476A (en) | 2013-08-14 |
| CN103242476B true CN103242476B (en) | 2015-09-23 |
Family
ID=48922377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310170744.3A Active CN103242476B (en) | 2013-05-10 | 2013-05-10 | A kind of preparation method with the acrylic polymers of fluorescent characteristic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103242476B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107108812B (en) * | 2014-10-17 | 2021-03-23 | 香港科技大学 | Pure oxygen non-conjugated polymer with strong light emission and lyotropic discoloration performance for amine detection and preparation method thereof |
| CN105859973B (en) * | 2016-05-18 | 2018-07-06 | 苏州知益微球科技有限公司 | A kind of monodisperse fluorescent microsphere preparation method |
| CN112867920B (en) * | 2019-05-28 | 2022-07-15 | 诺力昂化学品国际有限公司 | Method for controlling scale formation in water systems |
| CN110961071B (en) * | 2019-12-20 | 2022-05-27 | 湖北海汇化工科技有限公司 | Wastewater treatment agent, preparation method and application thereof, and wastewater treatment method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6312644B1 (en) * | 1999-12-16 | 2001-11-06 | Nalco Chemical Company | Fluorescent monomers and polymers containing same for use in industrial water systems |
| CN101624237A (en) * | 2009-08-19 | 2010-01-13 | 中国海洋石油总公司 | Preparation method of water treatment trace type dirt inhibition dispersion agent |
-
2013
- 2013-05-10 CN CN201310170744.3A patent/CN103242476B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6312644B1 (en) * | 1999-12-16 | 2001-11-06 | Nalco Chemical Company | Fluorescent monomers and polymers containing same for use in industrial water systems |
| CN101624237A (en) * | 2009-08-19 | 2010-01-13 | 中国海洋石油总公司 | Preparation method of water treatment trace type dirt inhibition dispersion agent |
Non-Patent Citations (3)
| Title |
|---|
| 一种不饱和荧光单体的制备与性能研究;于瑞香等;《工业水处理》;20100331(第03期);第1.2节、结论部分 * |
| 含荧光基团的丙烯酸共聚物阻垢剂的合成及其性能研究;张光华等;《精细石油化工》;20120931;第29卷(第05期);第1.2-1.3节 * |
| 荧光标识水处理剂的研究进展;蔡超等;《工业水处理》;20031125(第11期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103242476A (en) | 2013-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104891684B (en) | Without phosphorus composite slow-corrosion scale resistor for bitter recirculated water and preparation method thereof | |
| CN101781028B (en) | High-efficiency low-phosphorous corrosion and scale inhibition dispersant as well as preparation method and application thereof | |
| CN103242476B (en) | A kind of preparation method with the acrylic polymers of fluorescent characteristic | |
| US9714181B2 (en) | Terpolymerized corrosion and scale inhibitor used in circulating cooling water of central air conditioning and its preparation method | |
| CN102198982A (en) | Scale and corrosion inhibitor for circulating cooling water | |
| CN101289257A (en) | Fluorescence labeling polyether carboxyl acids antisludging agent and preparation | |
| CN101125714B (en) | Fluorescence polyether antisludging agent and preparation method | |
| CN102616946A (en) | Biodegradable corrosion and scale inhibitor epoxy succinic acid copolymer and its preparation method | |
| CN101475266A (en) | Fluorescent tracing scale inhibitor and preparation thereof | |
| CN102774969A (en) | Biodegradable non-phosphorous anti-scale corrosion inhibitor and preparation method thereof | |
| CN102689992A (en) | Terpolymer antisludging agent and preparation process thereof | |
| CN105084561B (en) | Non-phosphorus scale and corrosion inhibitor containing fulvic acid and preparation method thereof | |
| CN112010405B (en) | Water treatment comprehensive control treatment method for cooling circulating water of central air conditioner | |
| CN101781027B (en) | High-efficiency non-phosphate corrosion and scale inhibiting dispersing agent and preparation method and application thereof | |
| CN103265125A (en) | Quaternary non-phosphorus aggregate type corrosion and scale inhibitor PIAAM and preparation method thereof | |
| CN100410287C (en) | Phosphine-based Marpropy multipolymer containing fluorescent base-group and its production | |
| CN112978944A (en) | Fluorescent tracing type non-phosphorus corrosion and scale inhibitor PESA-X and preparation method and application thereof | |
| CN109879451B (en) | Preparation method of copolymer water treatment agent | |
| CN113121025B (en) | Trace type bio-based scale inhibitor and preparation method and application thereof | |
| CN109626604A (en) | A kind of non-phosphate environment-friendly type imidazoline system's corrosion inhibiting and descaling agent and preparation method | |
| CN102898576B (en) | High solid content crylic acid-sulfonate copolymer and preparation method thereof | |
| CN102645427A (en) | Method for detecting content of water treatment agent by adopting fluorescent tracer | |
| CN102139966B (en) | Phosphorus-free corrosion inhibitor as well as preparation method and application thereof | |
| CN1781857A (en) | Methoxy group naphthyl fluorescence marked water treating agent and its preparing method | |
| CN108192099A (en) | Poly-aspartate/tryptamines graft copolymer and its synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: China National Offshore Oil Corporation Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: China National Offshore Oil Corporation Patentee before: CNOOC Tianjin Chemical Research & Design Institute |
|
| CP01 | Change in the name or title of a patent holder |