CN1243833A - Polyamine compounds containing phosphonic, sulfonic and carboxylic radicals and their preparing process - Google Patents
Polyamine compounds containing phosphonic, sulfonic and carboxylic radicals and their preparing process Download PDFInfo
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Abstract
A process for preparing polyamine compound containing phosphonic, sulfonic and carboxylic radicals includes such steps as reaction of polyvinyl polyamine on chloroacetic acid to obtain carboxy methyl polyvinylpolyamin hydrochloride as intermediate, reaction of said intermediate on sodium carboxysulfonate to obtain carboxymethyl polyvinylpolyaminosulfonic acid as another intermediate, and reaction of said another intermediate on polyformaldehyde and PCl3 to obtain the product [A(NACH2CH2)nNA2, where n=1-6; A=mCH2PO3H2; m'CH2SO3H; m"CH2CO2H; m, m' or m"=1-n and m+m'+m"=m+[3]]. Said product can be used as anticorrosion scaling-resistant disperser for treating industrial circulated water.
Description
The present invention relates to a kind of polyfunctional group water conditioner (corrosion inhibiting and descaling agent), particularly a kind of invention that contains phosphonate group-sulfonic group-carboxylic acid group's polyamine compounds.
Because the shortage day by day of Freshwater resources, and metallic corrosion etc. has brought enormous economic loss [Shi Shengtai etc. for the industrial and agricultural production of countries in the world, corrosion and protection, 1990,11 (4): 1], industrial cycle water treatment medicament more and more is subject to people's attention [Jiang Liren, corrosion and protection, 1984, (1)].The organic multicomponent phosphonic acids is a present widely used class water conditioner [GWofford, C Slezak, M Bukay.Industrial Water Treatment, 1991], and they have solved the problem of system's generation calcium carbonate scale, anti-higher temperatures.Its defective is that organic phospho acid can not suppress phosphorus system effectively and phosphorus zinc is calcium phosphate scale, zinc dirt and the ferric oxide deposition problems that produces in the water treatment prescription.The eighties, the co-polymer of sulfonate that contains of domestic and international Application and Development had good restraining ability to calcium phosphate scale, and dispersing iron oxide effectively, stablize zine ion, thereby developing [A Pryor rapidly, M Bukay.Industry Water Treatment, 1991], the polyethylene polyamine polymethylene sulfonate that meanwhile contains single sulfonic acid group obtains research [Yao Cheng etc.Treatment of Industrial Water, 1998, (5): 18], and the introducing sulfonic acid group also obtains research [Han Yinglin etc. in the organic phospho acid molecule.Nanjing University of Chemical Technology's journal, 1997, (3): 7].As everyone knows, contain phosphonate group and carboxylic acid group in the molecule of phosphine carboxylic acid compound, be that a class has the scale inhibition inhibiter in New Year concurrently, many distinctive features are arranged in water quality stabilizer, developed PBTCA (2-phosphonic acid butane-1,2 both at home and abroad at present, the 4-tricarboxylic acid) and HPA (2-hydroxyl phosphine acetate) [Ji Yongliang, Treatment of Industrial Water, 1995, (6): 1].These water conditioners only contain one or both functional groups, all also having some shortcomings aspect the corrosion-mitigation scale-inhibition dispersion, if any scale inhibition effect can, but corrosion mitigating effect is relatively poor, over-all properties is difficult to satisfy the demand, when reality is used, usually want composite use, need to adjust prescription every now and then, make the user very inconvenient in use by the professional.Therefore developing novel polyfunctional group water conditioner easy to use just becomes domestic and international problem demanding prompt solution.
The object of the invention is to develop the polyamine compounds water conditioner that contains phosphonate group-sulfonic group-carboxylic acid group, makes it multiple functional, and is easy to use, and inhibition, scale inhibition, dispersing property are good.
Novel polyfunctional group water conditioner of the present invention is to introduce sulfonic group (SO simultaneously in a molecule
3H), phosphonate group (PO
3H
2) and carboxylic acid group (CO
2H), its concrete structure is as follows:
(n=1～6; A=m CH
2PO
3H
2M ' CH
2SO
3H; M " CH
2CO
2H; M, m ', m "=1～n; M+m '+m "=n+3) make product have inhibition preferably, scale inhibition, dispersing property simultaneously, and can produce based on inhibition or with scale inhibition according to the water quality needs and be separated into main product, to remedy the deficiency of currently available products performance.
Preparation method's the first step is: drip the chloroacetic aqueous solution of 1～7mol in the aqueous solution of 1mol polyethylene polyamine, dropwise the back and reacted 4～12 hours down at 20～90 ℃, get intermediate carboxymethyl polyethylene polyamine hydrochloride [A (NACH
2CH
2)
nNA
2(HCl)
M "(II), n=1～6; A=m " (CH
2CO
2H), (n+3-m ") H].
Second step was: to intermediate (II) in, add a certain amount of NaOH and regulate pH to 3～9, add 1～7mol sodium hydroxymethane sulfonate again, 20～100 ℃ of reactions 4～12 hours down, intermediate carboxymethyl polyethylene polyamine base is pitched sulfonic acid [A (NACH
2CH
2)
nNA
2(III), n=1～6; A=m " (CH
2CO
2H), m ' (CH
2SO
3H), (n+3-m '-m ") H].
The 3rd step was: add 1～9mol Paraformaldehyde 96 in intermediate (III), and drip 1～8mol phosphorus trichloride, reacted 4～18 hours down at 20～120 ℃ then, get product carboxymethyl methylenephosphonic acid polyethylene polyamine base methylsulfonic acid [A (NACH
2CH
2)
nNA
2(I), n=1～6; A=mCH
2PO
3H
2M ' CH
2SO
3H; M " CH
2CO
2H; M, m ', m "=1～n; M+m '+m "=n+3].
Its synthetic route is as follows:
(n=1～6; A=m CH
2PO
3H
2M ' CH
2SO
3H; M " CH
2CO
2H; M, m ', m "=1～n; M+m '+m "=n+3)
Above synthetic route is simple, and raw material is easy to get, and cost is low." synergistic effect " between institute's synthetic product utilization phosphonate group, sulfonic group and the carboxylic acid group, make its inhibition, scale inhibition, dispersing property better, and the different products of forming have different characteristics at aspects such as inhibition, scale inhibition, dispersions, thereby can adapt to various requirements in water quality, extensively in handling, uses industrial circulating cooling water.Therefore exploitation, the promotion and application of polyfunctional group water conditioner of the present invention have bigger social benefit and economic benefit.
Embodiment: embodiment 1, preparation N, N '-two methene phosphonic acids-N '-methene sulfonic acid-N-acetoxyl quadrol (CSDPE):
1.1 frozen water cooling down to quadrol (30g 0.5mol) and drip the chloroacetic aqueous solution (the 47.3g Mono Chloro Acetic Acid is dissolved in the 40ml water) in the mixture of 40ml water, dropwises the back 65～90 ℃ of reactions 6 hours down, intermediate carboxymethyl ethylenediamine-hydrochloride [H
2NCH
2CH
2NH
2(CH
2CO
2H) Cl (CE)] aqueous solution.
1.2 adding HCl adjusting pH in the aqueous solution of the said products is 5.8, adds 67g hydroxymethyl sodium sulfonate again, reacts down at 80～90 ℃ promptly to get intermediate carboxymethyl quadrol base methene sulfonic acid [HO in 7 hours
3SCH
2NHCH
2CH
2NHCH
2CO
2H (CSE)] aqueous solution.
1.3 in above-mentioned solution, add the 40g Paraformaldehyde 96, the frozen water cooling drips phosphorus trichloride 87.6ml (1.0mol) down, after dropwising, be warming up to 80～90 ℃ gradually, and after 12 hours, be cooled to filtering precipitation after the room temperature in reaction under this temperature, N, the aqueous solution 200g of N '-two methene phosphonic acids-N '-methene sulfonic acid-N-acetoxyl quadrol (CSDPE) concentrates and separates out CSDPE 168g (total recovery is 84%) under the effect of methyl alcohol.Product is through methanol-water recrystallization, results of elemental analyses: C:21.23, H:4.64, N:6.88 (theoretical value is C:21.01, H:4.53, N:7.00).This product is through static-state scale inhibition test, and the result shows under 2ppm concentration, can reach 85.4% to the scale inhibition performance of calcium carbonate scale; Corrosion inhibition test shows that the concentration of this product in tap water is that 5ppm is 99.4% to the carbon steel corrosion inhibition rate.Embodiment 2, preparation N-methylenephosphonic acid-N '-methene sulfonic acid-N, N '-diacetoxyl quadrol (DCSPE):
2.1 the frozen water cooling is down to quadrol (30g, 0.5mol) and the mixture of 40ml water in drip the chloroacetic aqueous solution (the 94.6g Mono Chloro Acetic Acid is dissolved in the 80ml water), dropwise the back and reacted 9 hours down, get intermediate dicarboxyl methyl ethylenediamine hydrochloride [HO at 70～90 ℃
2CCH
2NHCH
2CH
2NH
2(CH
2CO
2H) Cl (DCE)] aqueous solution.
2.2 adding NaOH adjusting pH in the aqueous solution of the said products is 7.6, adds 67g hydroxymethyl sodium sulfonate again, reacts down at 70～100 ℃ promptly to get intermediate carboxymethyl quadrol base methene sulfonic acid [HO in 7 hours
3SCH
2(HO
2CCH
2) NCH
2CH
2NHCH
2CO
2H (DCSE)] aqueous solution.
2.3 in above-mentioned solution, add the 20g Paraformaldehyde 96, the frozen water cooling drips phosphorus trichloride 43.8ml (0.55mol) down, after dropwising, be warming up to 70～100 ℃ gradually, and after 7 hours, be cooled to filtering precipitation after the room temperature in reaction under this temperature, N-two methene phosphonic acids-N '-methene sulfonic acid-N, the aqueous solution 181g of N '-diacetoxyl quadrol (DCSPE) (contain DCSPE 150g, total recovery is 83%).This product is through static-state scale inhibition test, and the result shows under 2ppm concentration, can reach 87.3% to the scale inhibition performance of calcium carbonate scale; Corrosion inhibition test shows that the concentration of this product in tap water is that 5ppm is 99.0% to the carbon steel corrosion inhibition rate.Embodiment 3, preparation N-methylenephosphonic acid-N, N '-two methene sulfonic acid-N-acetoxyl quadrol (CDSPE):
3.1 adding HCl adjusting pH in the aqueous solution of 1.1 products is 6.7, adds 134g hydroxymethyl sodium sulfonate again, reacts down at 60～90 ℃ promptly to get intermediate carboxymethyl quadrol base methene sulfonic acid [HO in 9 hours
3SCH
2NHCH
2CH
2N (CH
2SO
3H) CH
2CO
2H (CDSE)] aqueous solution.
3.2 in above-mentioned solution, add the 20g Paraformaldehyde 96, the frozen water cooling drips phosphorus trichloride 43.8ml (0.5mol) down, after dropwising, be warming up to 60～90 ℃ gradually, and after 9 hours, be cooled to filtering precipitation after the room temperature in reaction under this temperature, N, the aqueous solution 200g of N '-two methene phosphonic acids-N '-methene sulfonic acid-N-acetoxyl quadrol (CDSPE) (contain CDSPE 162g, total recovery is 81%).This product is through static-state scale inhibition test, and the result shows under 2ppm concentration, can reach 90.1% to the scale inhibition performance of calcium carbonate scale; Corrosion inhibition test shows that the concentration of this product in tap water is that 5ppm is 99.1% to the carbon steel corrosion inhibition rate.Embodiment 4, preparation N, N ', N "-three methene phosphonic acids-N "-methene sulfonic acid-N-acetoxyl diethylenetriamine (CSDPE):
4.1 the frozen water cooling is down to diethylenetriamine (51.5g, 0.5mol) and the mixture of 50ml water in drip the chloroacetic aqueous solution (the 47.3g Mono Chloro Acetic Acid is dissolved in the 50ml water), dropwise the back and reacted 6 hours down, get intermediate carboxymethyl diethylenetriamine hydrochloride [H at 40～85 ℃
2NCH
2CH
2NHCH
2CH
2NH
2(CH
2CO
2H) Cl (CE)] aqueous solution.
4.2 adding HCl adjusting pH in the aqueous solution of the said products is 7, adds 67g hydroxymethyl sodium sulfonate again, reacts down at 40～85 ℃ promptly to get intermediate carboxymethyl quadrol base methene sulfonic acid [HO in 6 hours
3SCH
2NHCH
2CH
2NHCH
2CO
2H (CSE)] aqueous solution.
4.3 in above-mentioned solution, add the 60g Paraformaldehyde 96, the frozen water cooling drips phosphorus trichloride 131.4ml (1.2mol) down, after dropwising, be warming up to 60～90 ℃ gradually, and after 16 hours, be cooled to filtering precipitation after the room temperature in reaction under this temperature, get N, N ', N " aqueous solution 270g (contain CSDPE 205g, total recovery is 81%) of-three methene phosphonic acids-N '-methene sulfonic acid-N-acetoxyl diethylenetriamine (CSDPE).This product is through static-state scale inhibition test, and the result shows under 2ppm concentration, can reach 86.0% to the scale inhibition performance of calcium carbonate scale; Corrosion inhibition test shows that the concentration of this product in tap water is that 5ppm is 99.6% to the carbon steel corrosion inhibition rate.
Synthesis condition, result and the performance of other intermediate (II), intermediate (III) and the finished product sees Table 1 respectively, table 2, table 3 and table 4.
Synthesis condition, the result of table 1 intermediate (II)
Synthesis condition, the result of table 2 intermediate (III)
| Sequence number | ????A(NACH 2CH 2) nNA 2(HCl) m”(I) ????A＝m”(CH2CO2H)，(n+3-m”)H ????n/m” | Mol ratio polyethylene polyamine/Mono Chloro Acetic Acid | Temperature ℃ | Reaction times | Productive rate % |
| ??1 | ????1/1 | ????1∶1 | ??65-90 | ????6h | ????92 |
| ??2 | ????1/2 | ????1∶2.1 | ??70-90 | ????10h | ????89 |
| ??3 | ????2/1 | ????1∶1 | ??40-85 | ????6h | ????93 |
| ??4 | ????2/2 | ????1∶2 | ??20-85 | ????6h | ????90 |
| ??5 | ????3/1 | ????1∶1 | ??30-70 | ????6h | ????91 |
| ??6 | ????4/1 | ????1∶1 | ??20-60 | ????4h | ????93 |
| ??7 | ????5/2 | ????1∶2.2 | ??20-70 | ????6h | ????94 |
| ??8 | ????6/3 | ????1∶3.2 | ??70-90 | ????12h | ????89 |
| Sequence number | ????A(NACH 2CH 2) nNA 2(III) ??A＝m”(CH2CO2H)，m’CH 2SO 3H， ????(n+3-m’-m”)H ????n/m’/m” | Mol ratio I/HO 3SCH 2OH | Temperature ℃ | Reaction times | Productive rate % |
| ???1 | ????1/1/1 | ????1∶1 | ??80-90 | ??7h | ????92 |
| ???2 | ????1/1/2 | ????1∶1 | ??70-100 | ??7h | ????89 |
| ???3 | ????1/2/1 | ????1∶2.1 | ??60-90 | ??9h | ????87 |
| ???4 | ????2/1/1 | ????1∶1 | ??40-85 | ??6h | ????93 |
| ???5 | ????2/2/1 | ????1∶2.1 | ??65-100 | ??10h | ????86 |
| ???6 | ????2/1/2 | ????1∶2 | ??20-85 | ??6h | ????90 |
| ???7 | ????3/1/1 | ????1∶1 | ??30-70 | ??6h | ????91 |
| ???8 | ????3/2/1 | ????1∶2.1 | ??70-90 | ??9h | ????88 |
| ???9 | ????3/1/2 | ????1∶1 | ??40-100 | ??9h | ????89 |
| ??10 | ????4/1/1 | ????1∶1 | ??40-90 | ??9h | ????91 |
| ??11 | ????4/3/1 | ????1∶3.4 | ??50-100 | ??12h | ????86 |
| ??12 | ????5/1/2 | ????1∶1 | ??40-90 | ??8h | ????92 |
| ??13 | ????5/3/2 | ????1∶3.4 | ??60-90 | ??12h | ????86 |
| ??14 | ????6/3/3 | ????1∶3.4 | ??60-90 | ??12h | ????86 |
Synthesis condition, the result of table 3 the finished product (I)
| Sequence number | ????A(NACH 2CH 2) nNA 2??(I) ?A＝m”(CH 2CO 2H)，m’(CH 2SO 3H)， ????m(CH 2PO 3H 2) ????n/m/m’/m” | Mol ratio II/ (CH 2O) n/PCl 3 | Temperature ℃ | Reaction times | Productive rate % |
| ??1 | ????1/2/1/1 | ????1∶3∶2.1 | ??80-90 | ??12h | ????92 |
| ??2 | ????1/1/1/2 | ????1∶1.5∶1.1 | ??70-100 | ??7h | ????89 |
| ??3 | ????1/1/2/1 | ????1∶1.5∶1.1 | ??60-90 | ??9h | ????87 |
| ??4 | ????2/3/1/1 | ????1∶4.1∶3.2 | ??40-85 | ??16h | ????93 |
| ??5 | ????2/2/2/1 | ????1∶3∶2.1 | ??65-100 | ??10h | ????86 |
| ??6 | ????2/2/1/2 | ????1∶3∶2.1 | ??20-85 | ??8h | ????90 |
| ??7 | ????3/4/1/1 | ????1∶5.2∶4.3 | ??30-70 | ??18h | ????91 |
| ??8 | ????3/3/2/1 | ????1∶4.1∶3.2 | ??50-110 | ??16h | ????86 |
| ??9 | ????3/3/1/2 | ????1∶4.1∶3.2 | ??40-110 | ??12h | ????90 |
| ?10 | ????4/5/1/1 | ????1∶7∶5.6 | ??40-80 | ??14h | ????91 |
| ?11 | ????4/3/3/1 | ????1∶4.1∶3.2 | ??50-100 | ??12h | ????86 |
| ?12 | ????5/5/1/2 | ????1∶7∶5.6 | ??40-90 | ??14h | ????92 |
| ?13 | ????5/3/3/2 | ????1∶4.1∶3.2 | ??60-110 | ??16h | ????86 |
| ?14 | ????6/3/3/3 | ????1∶4.1∶3.2 | ??40-120 | ??18h | ????86 |
The performance of table 4 sintetics (I)
A: drug concentration is 5mg/L; B: drug concentration is 2mg/L; C: drug concentration is 10mg/L.
| Sequence number | ????A(NACH 2CH 2) nNA 2(I) ?A＝m”(CH 2CO 2H)，m’(CH 2SO 3H)，m(CH 2PO 3H 2) ????n/m/m’/m” | Corrosion inhibition rate a????％ | Scale inhibition performance b??(CaCO 3) ????％ | Stablize zinc c????％ |
| ??1 | ????1/2/1/1 | ????99.4 | ????85.4 | ????82.4 |
| ??2 | ????1/1/1/2 | ????99.0 | ????87.3 | ????88.8 |
| ??3 | ????1/1/2/1 | ????99.1 | ????90.1 | ????89.1 |
| ??4 | ????2/3/1/1 | ????99.6 | ????86.0 | ????89.4 |
| ??5 | ????2/2/2/1 | ????99.4 | ????92.0 | ????90.1 |
| ??6 | ????2/2/1/2 | ????99.4 | ????91.8 | ????93.5 |
| ??7 | ????3/4/1/1 | ????99.7 | ????90.5 | ????89.2 |
| ??8 | ????3/3/2/1 | ????99.6 | ????95.4 | ????93.3 |
| ??9 | ????3/3/1/2 | ????99?6 | ????93.7 | ????94.7 |
| ??10 | ????4/5/1/1 | ????99.9 | ????91.9 | ????90.6 |
| ??11 | ????4/3/3/1 | ????99.8 | ????95.3 | ????94.2 |
| ??12 | ????5/5/1/2 | ????99.9 | ????94.9 | ????96.2 |
| ??13 | ????5/3/3/2 | ????99.8 | ????99.1 | ????99.5 |
| ??14 | ????6/3/3/3 | ????99.8 | ????99.6 | ????99.8 |
Claims (4)
1 one kinds of polyamine compounds that contain phosphonic, sulfonic and carboxylic radicals is characterized in that containing simultaneously in the molecule phosphonate group, sulfonic group and carboxylic acid group's polyamine compounds, and it has following general formula: A (NACH
2CH
2) NA
2(I), n=1～6 wherein; A=m CH
2PO
3H
2M ' CH
2SO
3H; M " CH
2CO
2H; M, m ', m "=1～n; M+m '+m "=n+3.
2 contain the preparation method of the polyamine compounds of phosphonic, sulfonic and carboxylic radicals, it is characterized in that the first step, in the aqueous solution of every 1mol polyethylene polyamine, drip the chloroacetic aqueous solution of 1～7mol, dropwise the back and reacted 4～12 hours down, get intermediate carboxymethyl polyethylene polyamine hydrochloride [A (NACH at 20～90 ℃
2CH
2)
nNA
2(HCl)
M "(II), n=1～6; A=m " (CH
2CO
2H), (n+3-m ") H].Second step was: adding NaOH or HCl regulate pH in intermediate (II), and pH is 3～9 in control, adds 1～7mol sodium hydroxymethane sulfonate again, and reaction is 4～12 hours under 20～100 ℃, get intermediate carboxymethyl polyethylene polyamine base fork sulfonic acid [A (NACH
2CH
2)
nNA
2(III), n=1～6; A=m " (CH
2CO
2H), m ' (CH
2SO
3H), (n+3-m '-m ") H].The 3rd step was: add 1～9mol Paraformaldehyde 96 in intermediate (III), and drip 1～8mol phosphorus trichloride, reacted 4～18 hours down at 20～120 ℃ then, get product carboxymethyl methylenephosphonic acid polyethylene polyamine base methylsulfonic acid [A (NACH
2CH
2)
nNA
2(I), n=1～6; A=m CH
2PO
3H
2M ' CH
2SO
3H; M " CH
2CO
2H; M, m ', m "=1～n; M+m '+m "=n+3].
3 preparation methods that contain the polyamine compounds of phosphonic, sulfonic and carboxylic radicals according to claim 2 is characterized in that the optimal ph in second step is 3～9.
4 contain the polyamine compounds A (NACH of phosphonic, sulfonic and carboxylic radicals
2CH
2) NA
2(n=1～6 wherein; A=m CH
2PO
3H
2M ' CH
2SO
3H; M " CH
2CO
2H; M, m ', m "=1～n; M+m '+m "=n+3) make inhibiter, Scale inhibitors, dispersive purposes at industrial circulating cooling water as water conditioner.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99114320A CN1074419C (en) | 1999-07-12 | 1999-07-12 | Polyamine compounds containing phosphonic, sulfonic and carboxylic radicals and their preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99114320A CN1074419C (en) | 1999-07-12 | 1999-07-12 | Polyamine compounds containing phosphonic, sulfonic and carboxylic radicals and their preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1243833A true CN1243833A (en) | 2000-02-09 |
| CN1074419C CN1074419C (en) | 2001-11-07 |
Family
ID=5277420
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99114320A Expired - Fee Related CN1074419C (en) | 1999-07-12 | 1999-07-12 | Polyamine compounds containing phosphonic, sulfonic and carboxylic radicals and their preparing process |
Country Status (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100059C (en) * | 2000-05-19 | 2003-01-29 | 中国石油化工集团公司 | Sulfonic acid-containing organic phosphine carboxylic acid compound and its prepn. and application |
| CN100360546C (en) * | 2004-10-20 | 2008-01-09 | 西南师范大学 | Process for one-pot preparation of chloromethyl monosodium phosphonate |
| CN102321462A (en) * | 2011-06-14 | 2012-01-18 | 北京科技大学 | Method for preparing pH regulating stabilizer of oil gas field |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5534611A (en) * | 1993-10-29 | 1996-07-09 | Nalco Chemical Company | Sulfonated and carboxylated aminoethylenephosphonic acid and aminobis (methylene) phosphinic acid |
-
1999
- 1999-07-12 CN CN99114320A patent/CN1074419C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100059C (en) * | 2000-05-19 | 2003-01-29 | 中国石油化工集团公司 | Sulfonic acid-containing organic phosphine carboxylic acid compound and its prepn. and application |
| CN100360546C (en) * | 2004-10-20 | 2008-01-09 | 西南师范大学 | Process for one-pot preparation of chloromethyl monosodium phosphonate |
| CN102321462A (en) * | 2011-06-14 | 2012-01-18 | 北京科技大学 | Method for preparing pH regulating stabilizer of oil gas field |
| CN102321462B (en) * | 2011-06-14 | 2013-07-03 | 北京科技大学 | Method for preparing pH regulating stabilizer of oil gas field |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1074419C (en) | 2001-11-07 |
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