CN1948509A - Preparation method of tetra hydroxy methyl phosphonium salt chromium-less tanning agent - Google Patents
Preparation method of tetra hydroxy methyl phosphonium salt chromium-less tanning agent Download PDFInfo
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- CN1948509A CN1948509A CN 200610154592 CN200610154592A CN1948509A CN 1948509 A CN1948509 A CN 1948509A CN 200610154592 CN200610154592 CN 200610154592 CN 200610154592 A CN200610154592 A CN 200610154592A CN 1948509 A CN1948509 A CN 1948509A
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Abstract
The invention discloses a method to prepare tannic agent of modified tetramethylol phosphate (THP) without chromium. To prepare the tannic agent, the mixture of THP, amino-compound, acrylic compound, catalyst and water is heated up to 50-90deg.C in reactor. After stirred for 2 to 4 hours, the mixture is cooled to 40-45deg.C for discharge. The finished product is efficient and clean leather tannic agent. With strongpoint including convenient operation, easy mastery, easily get materials and cheap price, the tannic agent has obvious ascendancy of market competition. In addition, the product can't bring new pollution in the process of preparing and using. It's a clean method to prepare tannic agent without chromium, which favors environmental protection.
Description
Technical field
The present invention relates to a kind of preparation method of tetra hydroxy methyl phosphonium salt chromium-less tanning agent, belong to the synthetic field of low-molecular weight compound.
Background technology
The matter of utmost importance that modern process hides is faced is a problem of environmental pollution, since the eighties, along with the adjustment of world's industrial structure and the transfer of world's leather industry center of gravity, China developed into the leather industry machining center of World Focusing and commerce trading center (Zhang Zongcai. Pollutant analysis in the process hides discharge " leather science and engineering ", 2002 (15): p44～48).Cr
3+Tannage has been widely used in tanning industry and dominate since invention, especially aspect the production of light leather product, and Cr
3+Tannage almost has irreplaceable advantage.But along with the raising of people's environmental consciousness, Cr
3+The pollution problem of tannage receives publicity day by day, Cr
6+Be proved to be and had carinogenicity, Cr
6+Waste water, massfraction in useless solid all classified as by various countries environmental administration one of index of strict control (Tang Keyong. the source of pollution of chromium and harm thereof " leather science and engineering ", 1997 (7): p33-48), how to solve the key that pollution problem in the tanning industry becomes the development of China leather industry Sustainable development, wherein the no Cr of exploitation
3+The material of tanning becomes the focus of current research.But also do not have to replace fully the chrome-free tanning agent of chrome tanning up to now, existing chrome-free tanning agent generally is used as retanning agent based on aminoresin and aldehydes tanning agent, such tanning agent synthesis technique complexity, and kind is single, and price is higher.
THP salt is a kind of novel auxiliary chemicals, is commonly used for the fire retardant of textiles, and THP salt also is a kind of novel sterilant, is widely used in cooling water treatment system and oil-field water treatment system.Just be used in the process hides at THP salt in 1956, U.S. Pat: 3104151 have proposed THP salt and the phenols method in conjunction with tanning, EP0681030 has described THPS as the application of casein linking agent in leather finish, CN1278304A proposes THP salt-melamine resin, THP salt-acid amides etc. uses as pretanning agent, proposition THPS such as A.D.Convigton and aminoresin performed polymer are used, can make Ts reach more than 100 ℃ (Zhang Ting has. " tanning chemistry ", 2003, press of Sichuan University, p49-50), but these technology all do not applied industrial.The FCC tanning agent of Clariant company is exactly the organic tanning agent that contains THP salt, is applicable to no Cr
3+The tanner skill, but the Ts of finished leather is not high, and finished leather performance and chrome tanned leather also have certain gap, and the FCC osmotic effect is bad, costs an arm and a leg, and also is not used widely.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art so that a kind of preparation method of tetra hydroxy methyl phosphonium salt chromium-less tanning agent to be provided, be characterized in that with four methylol phosphonium salts and aminocompound and/or acrylic compounds, water, catalyzer be raw material, make by condensation reaction.
Purpose of the present invention is realized that by following technical measures wherein raw materials used umber is mass fraction except that specified otherwise.
The composition of raw materials component of tetra hydroxy methyl phosphonium salt chromium-less tanning agent preparation is:
Four methylol phosphonium salt [P
+(CH
2OH)
4]
n50～200 parts of X
15～80 parts of aminocompounds
Acrylic compounds CH
2=CR
1COOR
20～30 part
2～5 parts of catalyzer
400～1000 parts in water
Wherein the X in the four methylol phosphonium salts is Cl
-, SO
4 2-, PO
4 3-, n=1 or 2 or 3, the R in the acrylic compounds
1Be H, CH
3, R
2Be H or CH
3Or CH
2CH
2OH; By claim 2 described aminocompounds for containing amido compounds or diamino compounds or Dyhard RU 100 or three cyanamides; By claim 3 described amido compounds is CH
2=CHCONH
2Or CH
2=CHCONHCH
2OH or H
2NCONH
2, be diethylenetriamine or triethylene tetramine by claim 4 described diamino compounds.
Said components is rendered in the reactor that has agitator, thermometer and reflux exchanger, heating, under 50 ℃～90 ℃ of temperature, stirring reaction is after 2～4 hours, and transferring product pH is 3～5, is cooled to 40～45 ℃, discharging, its molecular formula is:
[P (CH
2OH)
X(CH
2)
4-X-NH-R-]
n-or
X=1～3 wherein,
-(CH
2)
2NH (CH
2)
2HN-.
Starting material used among the present invention are domestic raw materials, and are cheap, and synthetic technology is simple; has tangible market competition advantage; and product the preparation and use in do not produce new pollution, be a kind of preparation method of clean, help environment protection.Utilize the chrome-free tanning agent of this method preparation can be widely used in the bad chrome-free tannings of multiple leather such as pig, ox, sheep, finished leather is plentiful, and color is light, is suitable for the production of white leather, and can gives finished leather certain flame retardant resistance.
Embodiment
Below by embodiment the present invention is specifically described, the person skilled in the art in this field can content according to the present invention make some nonessential improvement and adjustment.The feed composition (by mass) of preparation tetra hydroxy methyl phosphonium salt chromium-less tanning agent is:
Four methylol phosphonium salt [P
+(CH
2OH)
4]
n50～200 parts of X
15～80 parts of aminocompounds
Acrylic compounds CH
2=CR
1COOR
20～30 part
2～5 parts of catalyzer
400～1000 parts in water
Add in the reactor of belt stirrer, thermometer and reflux exchanger by above-mentioned each component, under 50 ℃～90 ℃ of temperature, stirring reaction is after 2～4 hours, and transferring pH is 3～5, is cooled to 40～45 ℃, discharging.
Embodiment 1
With 50 parts of tetra methylol sulfuric acid phosphoniums (THPS), 20 parts of acrylamides are in the reactor of 500 parts of addings of water belt stirrer, thermometer and reflux exchanger, each 2 parts of ammonium persulphate and sodium bisulfites are dissolved in 20 parts of water, slowly are added drop-wise in the reactor, under agitation behind 60 ℃ of reaction 2h, add 15 parts in vinylformic acid, be warming up to 90 ℃, continue reaction 2 hours, transferring product pH is 3～5, be cooled to 40～45 ℃, discharging, product is a milky white liquid.
Embodiment 2
THPS70 part, 400 parts in water, 20 parts in vinylformic acid adds in the conversion unit identical with embodiment 1, reacts 2h for 90 ℃ in temperature.Add 18.5 parts of hydroxyethyl methylacrylates then, each 2 parts of ammonium persulphate and sodium bisulfites are dissolved in 20 parts of water, slowly be added drop-wise in the reactor, and reaction 1h, product pH is 3.5, is cooled to about 40 ℃ discharging.
Embodiment 3
With THPS100 part, 500 parts in water, 35 parts in urea adds in the conversion unit identical with embodiment 1, is heated with stirring to 60 ℃, reacts 1.5h.20 parts of Methacrylamides, ammonium persulphate and sodium bisulfite are dissolved in 20 parts of water for each 2 parts again, slowly are added drop-wise in the conversion unit, and in 60 ℃ of reaction 2h, product pH is 4.5, is cooled to 40 ℃, discharging.
Embodiment 4
With THPS100 part, 400 parts in water adds in the conversion unit identical with embodiment 1, be heated with stirring to 60 ℃ after, 30 parts of diethylenetriamines with the dilution of 150 parts of water after, slowly be added drop-wise in the conversion unit, 80 ℃ of temperature, reaction 2h, transferring product pH value with dilute sulphuric acid is 3～5, be cooled to 40 ℃, discharging, product is faint yellow emulsion liquid.
Embodiment 5
With 200 parts of THPS, 400 parts of water adds in the conversion unit identical with embodiment 1, is heated with stirring to 60 ℃, 50 parts of diethylenetriamines with the dilution of 100 parts of water after, slowly be added drop-wise in the reactor, temperature is controlled at 60 ℃, reaction 2h adds 30 parts of acrylamides again, stirs, respectively 5 parts of ammonium persulphates and sodium bisulfite are dissolved in 50 parts of water then, slowly be added drop-wise in the conversion unit, at 80 ℃ of reaction 2h, transferring product pH value with dilute sulphuric acid is 3～5, be cooled to 40 ℃, discharging.
Embodiment 6
With THPS150 part, 500 parts in water adds in the conversion unit identical with embodiment 1 stirring 0.5h.With 45 parts of Dyhard RU 100s, be dissolved in 500 parts 50 ℃ the hot water, join in the reactor, at 50 ℃ of reaction 1h.In 5 parts of adding conversion units of Tai-Ace S 150, be warming up to 70 ℃, reaction 2h is cooled to 40 ℃, and product pH is 5.0, discharging.
Embodiment 7
With THPS100 part, 18 parts of acrylamides are in the reactor of 500 parts of addings of water belt stirrer, thermometer and reflux exchanger, each 3 parts of ammonium persulphate and sodium bisulfites, be dissolved in 30 parts of water, slowly be added drop-wise in the reactor, under agitation behind 60 ℃ of reaction 2h, add 30 parts of methacrylic acids, be warming up to 90 ℃, continue reaction 2h, product pH is 4.5, be cooled to 40～45 ℃, discharging.
Embodiment 8
With THPS150 part, 500 parts in water, 20 parts in vinylformic acid adds in the conversion unit identical with embodiment 1, reacts 2h for 90 ℃ in temperature.Add 37 parts of n-methylolacrylamide then, 2 parts of Potassium Persulphates are dissolved in 20 parts of water, slowly be added drop-wise in the conversion unit, and reaction 1h, product pH is 4.5, is cooled to about 40 ℃ discharging.
Embodiment 9
With 30 parts of diethylenetriamines with the dilution of 300 parts of water after, add in the conversion unit identical with embodiment 1, after being heated with stirring to 60 ℃, with THPS100 part with the dilution of 300 parts of water after, slowly be added drop-wise in the conversion unit, 60 ℃ of temperature, reaction 2h, transferring product pH value with dilute sulphuric acid is 3～5, is cooled to 40 ℃, discharging.
Embodiment 10
With 200 parts of THPS, 400 parts of water adds in the conversion unit identical with embodiment 1, is heated with stirring to 60 ℃, 50 parts of diethylenetriamines with the dilution of 300 parts of water after, slowly be added drop-wise in the reactor, temperature is controlled at 60 ℃, reaction 2h adds 15 parts of Methacrylamides again, stirs, respectively 3 parts of ammonium sulfate and sodium bisulfite are dissolved in 30 parts of water then, slowly be added drop-wise in the conversion unit, at 80 ℃ of reaction 2h, transferring product pH value with dilute sulphuric acid is 3～5, be cooled to 40 ℃, discharging.
Claims (5)
1. the preparation method of a tetra hydroxy methyl phosphonium salt chromium-less tanning agent is characterized in that the feed composition for preparing this chrome-free tanning agent is by mass:
Four methylol phosphonium salt [P
+(CH
2OH)
4]
n50～200 parts of X
15～80 parts of aminocompounds
Acrylic compounds CH
2=CR
1COOR
20～30 part
2～5 parts of catalyzer
400～1000 parts in water
Wherein the X in the four methylol phosphonium salts is Cl
-, Br
-, SO
4 2-, PO
4 3-, n=1 or 2 or 3, the R in the acrylic compounds
1Be H or CH
3, R
2Be H or CH
3Or CH
2CH
2OH, catalyzer is at least a of ammonium persulphate, sodium bisulfite, Potassium Persulphate, by said components four methylol phosphonium salts, aminocompound and acrylic compounds and catalyzer, water are added in the reactor of belt stirrer, thermometer and reflux exchanger, 50 ℃～90 ℃ of temperature, stirring reaction 2～4 hours, transferring product pH is 3～5, is cooled to 40～45 ℃, discharging, its molecular formula are [P (CH
2OH)
X(CH
2)
4-x-NH-R-]
n-or
X=1～3 wherein,
-(CH
2)
2NH (CH
2)
2HN-.
2. by the described preparation method of claim 1, it is characterized in that aminocompound is compound or diamino compounds or Dyhard RU 100 or three cyanamides that contain amido.
3. by the described preparation method of claim 2, the compound that it is characterized in that containing amido is CH
2=CHCONH
2Or CH
2=CHCONH-CH
2OH or H
2NCONH
2
4. by the described preparation method of claim 2, it is characterized in that diamino compounds is diethylenetriamine or triethylene tetramine.
5. by claim 1 or 2 or 3 or 4 described preparation methods, it is characterized in that described four methylol phosphonium salt [P
+(CH
2OH)
4]
mX among the X is Cl
-Or Br
-Or SO
4 2-Or PO
4 3-, n=1 or 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101545928A CN100500870C (en) | 2006-11-09 | 2006-11-09 | Preparation method of tetra hydroxy methyl phosphonium salt chromium-less tanning agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101545928A CN100500870C (en) | 2006-11-09 | 2006-11-09 | Preparation method of tetra hydroxy methyl phosphonium salt chromium-less tanning agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1948509A true CN1948509A (en) | 2007-04-18 |
| CN100500870C CN100500870C (en) | 2009-06-17 |
Family
ID=38018131
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101545928A Expired - Fee Related CN100500870C (en) | 2006-11-09 | 2006-11-09 | Preparation method of tetra hydroxy methyl phosphonium salt chromium-less tanning agent |
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|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101965412A (en) * | 2008-02-26 | 2011-02-02 | 罗地亚-恒昌（张家港）精细化工有限公司 | Poly hydroxyl alkyl phosphine-organic silicon tanning agent, its preparation and application in fur tanning |
| CN102453775A (en) * | 2010-10-26 | 2012-05-16 | 北京泛博科技有限责任公司 | Chromium-containing tanning agent and preparation method thereof |
| CN102586509A (en) * | 2011-12-31 | 2012-07-18 | 河北东明皮革有限公司 | Tanning method of sheep skins |
| CN101643799B (en) * | 2009-03-11 | 2012-09-05 | 齐河力厚化工有限公司 | Method for preparing formaldehyde-free retanning agent |
| CN101781689B (en) * | 2009-01-19 | 2012-09-05 | 北京泛博科技有限责任公司 | Environment-friendly tanning agent for leather, preparation method and application thereof |
| CN105154598A (en) * | 2015-08-24 | 2015-12-16 | 齐鲁工业大学 | Preparing method for modifying organophosphorus tanning agent through compound containing amidogen and carboxyl functional groups simultaneously |
| CN106755628A (en) * | 2016-12-12 | 2017-05-31 | 温州大学 | A kind of preparation method for complexing agent of the leather without chrome tanning tanning processes |
-
2006
- 2006-11-09 CN CNB2006101545928A patent/CN100500870C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101965412A (en) * | 2008-02-26 | 2011-02-02 | 罗地亚-恒昌（张家港）精细化工有限公司 | Poly hydroxyl alkyl phosphine-organic silicon tanning agent, its preparation and application in fur tanning |
| CN101965412B (en) * | 2008-02-26 | 2013-09-25 | 罗地亚-恒昌（张家港）精细化工有限公司 | Poly hydroxyl alkyl phosphine-organic silicon tanning agent, its preparation and application in fur tanning |
| CN101781689B (en) * | 2009-01-19 | 2012-09-05 | 北京泛博科技有限责任公司 | Environment-friendly tanning agent for leather, preparation method and application thereof |
| CN101643799B (en) * | 2009-03-11 | 2012-09-05 | 齐河力厚化工有限公司 | Method for preparing formaldehyde-free retanning agent |
| CN102453775A (en) * | 2010-10-26 | 2012-05-16 | 北京泛博科技有限责任公司 | Chromium-containing tanning agent and preparation method thereof |
| CN102453775B (en) * | 2010-10-26 | 2014-04-30 | 北京泛博科技有限责任公司 | Chrome containing tanning agent and preparation method thereof |
| CN102586509A (en) * | 2011-12-31 | 2012-07-18 | 河北东明皮革有限公司 | Tanning method of sheep skins |
| CN105154598A (en) * | 2015-08-24 | 2015-12-16 | 齐鲁工业大学 | Preparing method for modifying organophosphorus tanning agent through compound containing amidogen and carboxyl functional groups simultaneously |
| CN105154598B (en) * | 2015-08-24 | 2018-06-15 | 齐鲁工业大学 | A kind of preparation method of compound modified organophosphor tanning agent with simultaneously containing amino and carboxyl functional group |
| CN106755628A (en) * | 2016-12-12 | 2017-05-31 | 温州大学 | A kind of preparation method for complexing agent of the leather without chrome tanning tanning processes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100500870C (en) | 2009-06-17 |
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Granted publication date: 20090617 Termination date: 20111109 |