CN104086590A - Preparation method of abietylamino methylene phosphonic acid - Google Patents
Preparation method of abietylamino methylene phosphonic acid Download PDFInfo
- Publication number
- CN104086590A CN104086590A CN201410333005.6A CN201410333005A CN104086590A CN 104086590 A CN104086590 A CN 104086590A CN 201410333005 A CN201410333005 A CN 201410333005A CN 104086590 A CN104086590 A CN 104086590A
- Authority
- CN
- China
- Prior art keywords
- rosin amine
- preparation
- formaldehyde
- methylenephosphonic acid
- abietylamino
- 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.)
- Pending
Links
Abstract
The invention discloses a preparation method of abietylamino methylene phosphonic acid. The abietylamino methylene phosphonic acid is prepared by carrying out Mannich reaction on abietylamine, formaldehyde and phosphorous acid in a hydrochloric acid environment. The abietylamino methylene phosphonic acid contains carboxylic acid group, organic phosphonic acid group and tertiary amine group, and therefore, has the functions of scale prevention, corrosion inhibition and sterilization. The abietylamino methylene phosphonic acid is widely used for scale prevention and corrosion inhibition of circulating cooling water systems, low-pressure boilers and oilfield flooding and oil pipelines in electric power, chemical engineering, metallurgy, chemical fertilizers and other industries.
Description
Technical field
The invention belongs to Water Treatment Chemicals field, a kind of preparation method of rosin Amine D methylenephosphonic acid is provided.
Background technology
Rosin Amine D is a kind of light yellow thickness oily liquids, irritant ammonia taste.That repeated hydrogenation makes by first rosin nitrile processed of sylvic acid catalytic ammoniation.As lubricant additive, wood preservative, is used as inhibiter, Biocidal algae-killing agent in Treatment of Industrial Water, make mud stripper in sink drainage.
In state-owned abundant rosin resource, have and produce the maturation process of rosin skin and the condition of expanding production, rosin Amine D and derivative thereof have again unique valuable performance, along with this series products of development of Chinese industrial will have good development prospect.But because its poorly water-soluble has limited it in the application aspect industrial technology processing.
Organic phospho acid is due to its excellent scale inhibition and corrosion inhibition, and chemical stability is good and the composite synergetic property of other water conditioner is good, is widely used in the industry-by-industries such as chemical industry, oil, metallurgy, electric power, mineral products for a long time as a kind of important water conditioner.In recent years research find that organic phosphine class decomposes nutritive substances such as producing the required phosphorus of water body plant-growth, cause body eutrophication, cause the explosive breeding of the planktonic organisms such as algae, the biological mortality such as fish, and the phenomenons such as " wawter bloom " " red tide " occur.Therefore reduce the content of Phosphorus From Wastewater, developing low-phosphorous or without phosphorus water-treated prod is a permanent relevant research.
Summary of the invention
The present invention, by reacting and synthesize rosinyl methylenephosphonic acid with formaldehyde, phosphorous acid by biodegradable natural compounds rosin Amine D, has reduced phosphorus content, has promoted the degradation speed of compound in environment simultaneously.This compound has the effect of inhibition and scale inhibition.
A preparation method for rosin Amine D methylenephosphonic acid, its reaction formula is:
，
The processing step that this preparation method is concrete is as follows:
(1) phosphorous acid is joined in reactor, the rosin Amine D of metering 1/3 is joined in reactor, with 32% hydrochloric acid regulation system pH value, stir;
(2) control temperature, drip formaldehyde solution;
(3) divide and add remaining rosin Amine D 3 times;
(4) formaldehyde dropwises, and improves temperature, and insulation continues reaction to terminal;
(5) negative pressure is steamed outward, removes responseless formaldehyde and hydrogenchloride.
The pH value < 3 that adds hydrochloric acid control reaction system that above-mentioned steps (1) is described.
In above-mentioned steps (2), the mol ratio of rosin Amine D and phosphorous acid, formaldehyde is 1:1.8 ~ 2.1:2 ~ 2.5.
The dropping temperature of the formaldehyde solution described in above-mentioned steps (2) is 30 ~ 50 DEG C.
The time for adding of the formaldehyde solution described in above-mentioned steps (2) is 0.5 ~ 2.5 hour.
Described the adding in 2 hours of residue rosin Amine D of above-mentioned steps (3) completes.
The described raising temperature of above-mentioned steps (4) refers to be warming up to 90 ~ 120 DEG C; The insulation reaction time is 2 ~ 5 hours.
The described outer pressure steaming of negative pressure of above-mentioned steps (5) is-0.03 ~-0.08MPa; The outer temperature of steaming of negative pressure is 90 ~ 120 DEG C.
The outstanding advantages of patent of the present invention is: synthesis technique of the present invention has invested the biological degradability of organic phosphine compound as the polyamine of methylenephosphonic acid with rosin Amine D; Because the introducing of methylenephosphonic acid water soluble group has improved the water-soluble of rosin Amine D, expand its Application Areas; The compounds of this invention has effect of scale inhibition, inhibition, sterilization simultaneously, is a kind of potion multiple-effect, the water-treated prod of excellent performance.
Embodiment
Object for a better understanding of the present invention and meaning, now set forth concrete synthesis technique of the present invention by following specific embodiment.But content of the present invention is not limited only to following examples.
Embodiment 1
A kind of rosin Amine D methylenephosphonic acid composition principle as shown in the formula:
Concrete synthesis technique step is:
(1) phosphorous acid is joined in reactor, the rosin Amine D of metering 1/3 is joined in reactor, with 32% hydrochloric acid regulation system pH value to 1.5, stir;
(2) control temperature≤35 DEG C, drip formaldehyde solution, within 2 hours, dropwise, the mol ratio of reaction mass rosin Amine D and phosphorous acid, formaldehyde is 1:2:2.3;
(3) divide and add remaining rosin Amine D 3 times, reaction starts to add in 1.5 hours complete;
(4) formaldehyde dropwises, and improves temperature to 100 DEG C, and insulation continues reaction 3 hours;
(5) react complete, keep 110 DEG C of temperature, pressure-0.06MPa steams responseless formaldehyde and hydrogenchloride outward.
Embodiment 2
A kind of rosin Amine D methylenephosphonic acid composition principle as shown in the formula:
Concrete synthesis technique step is:
(1) phosphorous acid is joined in reactor, the rosin Amine D of metering 1/3 is joined in reactor, with 32% hydrochloric acid regulation system pH value to 1.0, stir;
(2) control temperature≤35 DEG C, drip formaldehyde solution, within 1.5 hours, dropwise, the mol ratio of reaction mass rosin Amine D and phosphorous acid, formaldehyde is 1:1.8:2.2;
(3) divide and add remaining rosin Amine D 3 times, reaction starts to add in 2 hours complete;
(4) formaldehyde dropwises, and improves temperature to 90 DEG C, and insulation continues reaction 5 hours;
(5) react complete, keep 90 DEG C of temperature, pressure-0.08MPa steams responseless formaldehyde and hydrogenchloride outward.
Embodiment 3
A kind of rosin Amine D methylenephosphonic acid composition principle as shown in the formula:
Concrete synthesis technique step is:
(1) phosphorous acid is joined in reactor, the rosin Amine D of metering 1/3 is joined in reactor, with 32% hydrochloric acid regulation system pH value to 2, stir;
(2) control 30 DEG C of temperature, drip formaldehyde solution, within 1 hour, dropwise, the mol ratio of reaction mass rosin Amine D and phosphorous acid, formaldehyde is 1:2.1:2.5;
(3) divide and add remaining rosin Amine D 3 times, reaction starts to add in 2 hours complete;
(4) formaldehyde dropwises, and improves temperature to 115 DEG C, and insulation continues reaction 2 hours;
(5) react complete, keep 100 DEG C of temperature, pressure-0.06MPa steams responseless formaldehyde and hydrogenchloride outward.
Embodiment 4
A kind of rosin Amine D methylenephosphonic acid composition principle as shown in the formula:
Concrete synthesis technique step is:
(1) phosphorous acid is joined in reactor, the rosin Amine D of metering 1/3 is joined in reactor, with 32% hydrochloric acid regulation system pH value to 2, stir;
(2) control temperature≤45 DEG C, drip formaldehyde solution, within 2.5 hours, dropwise, the mol ratio of reaction mass rosin Amine D and phosphorous acid, formaldehyde is 1:2.1:2.5;
(3) divide and add remaining rosin Amine D 3 times, reaction starts to add in 2 hours complete;
(4) formaldehyde dropwises, and improves temperature to 95 DEG C, and insulation continues reaction 4 hours;
(5) react complete, keep 120 DEG C of temperature, pressure-0.03MPa steams responseless formaldehyde and hydrogenchloride outward.
Claims (7)
1. a preparation method for rosin Amine D methylenephosphonic acid, its reaction formula is:
, the processing step that this preparation method is concrete is as follows:
(1) phosphorous acid is joined in reactor, the rosin Amine D of metering 1/3 is joined in reactor, with 32% hydrochloric acid regulation system pH value, stir;
(2) control temperature, drip formaldehyde solution;
(3) divide and add remaining rosin Amine D 3 times;
(4) formaldehyde dropwises, and improves temperature, and insulation continues reaction to terminal;
(5) negative pressure is steamed outward, removes responseless formaldehyde and hydrogenchloride.
2. the preparation method of a kind of rosin Amine D methylenephosphonic acid according to claim 1
, it is characterized in that:in step (1), add the pH value < 3 of hydrochloric acid control reaction system.
3. the preparation method of a kind of rosin Amine D methylenephosphonic acid according to claim 1
, it is characterized in that:in step (2), the mol ratio of rosin Amine D and phosphorous acid, formaldehyde is 1:1.8 ~ 2.1:2 ~ 2.5.
4. the preparation method of a kind of rosin Amine D methylenephosphonic acid according to claim 1
, it is characterized in that:in step (2), the dropping temperature of formaldehyde solution is 30 ~ 50 DEG C; The time for adding of formaldehyde solution is 0.5 ~ 2.5 hour.
5. the preparation method of a kind of rosin Amine D methylenephosphonic acid according to claim 1
, it is characterized in that:in step (3), adding in 2 hours of rosin Amine D of residue completes.
6. the preparation method of a kind of rosin Amine D methylenephosphonic acid according to claim 1
, it is characterized in that:the described raising temperature of step (4) refers to be warming up to 90 ~ 120 DEG C; The insulation reaction time is 2 ~ 5 hours.
7. the preparation method of a kind of rosin Amine D methylenephosphonic acid according to claim 1
, it is characterized in that:in step (5), the outer pressure steaming of negative pressure is-0.03 ~-0.08MPa; The outer temperature of steaming of negative pressure is 90 ~ 120 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410333005.6A CN104086590A (en) | 2014-07-14 | 2014-07-14 | Preparation method of abietylamino methylene phosphonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410333005.6A CN104086590A (en) | 2014-07-14 | 2014-07-14 | Preparation method of abietylamino methylene phosphonic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104086590A true CN104086590A (en) | 2014-10-08 |
Family
ID=51634376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410333005.6A Pending CN104086590A (en) | 2014-07-14 | 2014-07-14 | Preparation method of abietylamino methylene phosphonic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104086590A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891685A (en) * | 2015-05-19 | 2015-09-09 | 山东省泰和水处理有限公司 | A synthesis process of 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) |
| CN105754670A (en) * | 2016-04-06 | 2016-07-13 | 山东泰和水处理科技股份有限公司 | Coal water slurry dispersion stabilizer |
| CN108003189A (en) * | 2017-12-30 | 2018-05-08 | 枣庄学院 | A kind of anil and preparation method thereof |
| CN108276441A (en) * | 2018-01-31 | 2018-07-13 | 山东大学 | The preparation method of two methylenephosphonic acid of cyclohexylamine |
| CN110819330A (en) * | 2019-11-18 | 2020-02-21 | 西安石油大学 | Phosphonate type oil-gas field surfactant derived from natural oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101158043A (en) * | 2007-09-28 | 2008-04-09 | 新疆石油学院 | Method for synthesizing mannich alkali steel inhibitor mother liquor and steel inhibitor mother liquor |
| CN103435641A (en) * | 2013-08-13 | 2013-12-11 | 浙江皇马科技股份有限公司 | Method for preparing disproportionated rosin amine polyoxyethylene phosphonate |
| CN103819010A (en) * | 2014-02-24 | 2014-05-28 | 山东省泰和水处理有限公司 | Efficient scale and corrosion inhibitor and preparation method thereof |
-
2014
- 2014-07-14 CN CN201410333005.6A patent/CN104086590A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101158043A (en) * | 2007-09-28 | 2008-04-09 | 新疆石油学院 | Method for synthesizing mannich alkali steel inhibitor mother liquor and steel inhibitor mother liquor |
| CN103435641A (en) * | 2013-08-13 | 2013-12-11 | 浙江皇马科技股份有限公司 | Method for preparing disproportionated rosin amine polyoxyethylene phosphonate |
| CN103819010A (en) * | 2014-02-24 | 2014-05-28 | 山东省泰和水处理有限公司 | Efficient scale and corrosion inhibitor and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891685A (en) * | 2015-05-19 | 2015-09-09 | 山东省泰和水处理有限公司 | A synthesis process of 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) |
| CN105754670A (en) * | 2016-04-06 | 2016-07-13 | 山东泰和水处理科技股份有限公司 | Coal water slurry dispersion stabilizer |
| CN108003189A (en) * | 2017-12-30 | 2018-05-08 | 枣庄学院 | A kind of anil and preparation method thereof |
| CN108003189B (en) * | 2017-12-30 | 2020-03-24 | 枣庄学院 | Aniline derivative and preparation method thereof |
| CN108276441A (en) * | 2018-01-31 | 2018-07-13 | 山东大学 | The preparation method of two methylenephosphonic acid of cyclohexylamine |
| CN110819330A (en) * | 2019-11-18 | 2020-02-21 | 西安石油大学 | Phosphonate type oil-gas field surfactant derived from natural oil |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104086590A (en) | Preparation method of abietylamino methylene phosphonic acid | |
| CN104817345A (en) | Nutrient solution formula for plant | |
| CN105076201A (en) | Complex oilfield water flooding bactericide | |
| CN105010387B (en) | A kind of preparing process of modified oil field composite sterilizing agent | |
| TN2016000043A1 (en) | Method and liquid compound that improves the efficiency of ammoniacal nitrogenated fertilisers and the ammonium present in the ground. | |
| CN103086796B (en) | Amino acid micro element fertilizer for preventing and treating sugarcane yellow and white seedling, and production method thereof | |
| CN103254428A (en) | Trimethylolpropane dendritic polymer with nuclear-end phosphonic acid end group as well as preparation method and application for same | |
| CN104150617A (en) | Phosphorus-free scale and corrosion inhibitor and preparation method thereof | |
| CN105130829A (en) | Preparation method of high-efficiency high-temperature acidizing slow-released agent | |
| CN103771974A (en) | Multifunctional liquid calcium fertilizer and production method thereof | |
| CN202542959U (en) | Novel ethylenediamine tetramethylene sodium phosphonate composite corrosion and scale inhibitor production device | |
| EA201500800A1 (en) | SUBSTANCE FOR WATER PURIFICATION FROM SOLID SUSPENDED PARTICLES AND HYDROCARBONS, INCLUDING OIL AND PETROLEUM PRODUCTS, AND METHOD | |
| CN105712759A (en) | Crop composite fertilizer processing special-purpose production equipment | |
| CN107353051A (en) | A kind of liquid organic fertilizer and preparation method thereof | |
| CN104945196A (en) | Method for producing iron potassium humate | |
| CN105585143A (en) | Scale inhibitor for industrial water treatment and preparation method and application method thereof | |
| CN110278952B (en) | Efficient corrosion inhibition bactericide for oilfield water injection | |
| CN105585342B (en) | Amino trimethylene methylenephosphonic acid chelated microelement fertilizer, and preparation method thereof and Preparation equipment | |
| CN105272916A (en) | Novel rosin imidazoline corrosion inhibitor | |
| CN103588578A (en) | Humic acid ecological fertilizer and production method thereof | |
| CN103483380B (en) | A kind of ethylenediamine tetramethylene phosphonic acid continuous production method | |
| CN100348516C (en) | Composite phosphorus-free water-treating corrosion inhibitor and preparing process thereof | |
| CN103013484B (en) | Corrosion inhibitor for controlling carbon dioxide and hypersalinity corrosion | |
| CN102351587B (en) | Methods for producing high efficiency fertilizer by using iminodiacetonitrile and waste mother liquor thereof | |
| CN104987266A (en) | Method for producing zinc and potassium humate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Applicant after: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES CO., LTD. Address before: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Applicant before: Shandong Taihe Water Treatment Co., Ltd. |
|
| COR | Change of bibliographic data | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141008 |