CN101367773B - Bicyclo oxazolidine tanning agent and method of preparing the same - Google Patents
Bicyclo oxazolidine tanning agent and method of preparing the same Download PDFInfo
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- CN101367773B CN101367773B CN2008100462202A CN200810046220A CN101367773B CN 101367773 B CN101367773 B CN 101367773B CN 2008100462202 A CN2008100462202 A CN 2008100462202A CN 200810046220 A CN200810046220 A CN 200810046220A CN 101367773 B CN101367773 B CN 101367773B
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Abstract
The present invention discloses a bicyclic oxazole alkane tanning agent. The agent is characterized by being prepared with hydroxymethyl amine, polyhydroxy alcohol and aliphatic aldehydes. The appearance of the agent is pale yellow dense liquid, the 1162cm-1 and 1060cm-1 of the infrared spectrogram have an O-C-N skeleton vibration absorbing peak, and the content of hydroxymethyl after hydrolysis is 10 to 45 percent. The present invention also discloses a preparation method of the bicyclic oxazole alkane tanning agent. In the preparation method, 60 to 120 portions of hydroxymethyl amine, 30 to 110 portions of polyhydroxy alcohol and 65 to 125 portions of aliphatic aldehydes are mixed for 4 to 9 hours for reaction at the temperature between 50 DEG C and 80 DEG C, the dehydration reaction is performed for 2 to 4 hours at the temperature between 80 DEG C and 100 DEG C, and the agent can be prepared after the temperature is lowered to be between 40 DEG C and 55 DEG C. The agent is cheap, the tanning effect is good, and no dehydrant is used in the preparation process. Therefore, the present invention has the advantages that the method is simple, the feasibility is high, the production cost is low, and the possible environmental pollution is prevented.
Description
Technical field
The invention belongs to leather retanning agent and preparing technical field thereof, be specifically related to a kind of bicyclo oxazolidine tanning agent and preparation method thereof.
Background technology
The tanning technological revolution that the chromic tanning of coming out in 19th century realizes chrome-tanned shrinkage temperature can be reached more than 100 ℃, and the over-all properties of finished leather is superior to other tannages.Therefore, over more than 100 year, chromic tanning be always prevailing process for tanning during leather is produced (Luo Jianxun, Dan Zhihua. Chrome-free combines the research of tanning. Chinese leather .2006,35:39-42.).But, the reinforcement of Along with people's environmental protection and resource consciousness and to the pay attention to day by day of quality of life, chromic tanning is being faced with stern challenge.Therefore, the research and development chrome-free tanning agent is the important content that process hides cleans with no chromic tanning.
But the finished leather hydrothermal stability of existing single non-chrome tanning agent tanning is relatively poor, limited they practical application (Ding Jianhua, Wang Xuechuan. the few chromium of Chrome-free combines the progress of tanning. western leather .2007,29:16-18.).Famous tanning chemistry man Covington confirms; Adopt two kinds of non-chrome tanning agent combination tannages can prepare the leather of high hydrothermal stability; And " link-lock " non-chrome tanning theoretical (Covington AD, song L, suparno O proposed; Et al.Link-lock:anexplanation of the chemical stabilisation of collagen.Journal of the Leather Technologistsand Chemists.2008,92:1-7.).And in numerous combination tannages; Because of plant-the aldehyde finished leather hydrothermal stability that combines to tan is high; Water-fast washing most possibly replaces chrome tanning, and particularly black wattle plant skin tannin extract and bicyclo oxazolidine combine to tan; Can make the finished leather shrinkage temperature be higher than 110 ℃ (stone is green. vegetable tanning agent-aldehyde compound combination tannage (II). Chinese leather .2006; 35:1-4.), than black wattle plant skin and modified glutaraldehyde combine to tan the finished leather shrinkage temperature exceed nearly 20 ℃ (stone is green. vegetable tanning agent-aldehyde compound combination tannage (I). Chinese leather .2006,35:1-3.).But; Bicyclo oxazolidine tanning agent wherein is owing to used (homemade 75000 yuan/ton of the more expensive trihydroxy-aminomethanes of price; Import is more than 100000 yuan/ton) and 2-amino-2-ethyl-1,3-Ucar 35 (have only import, price and trihydroxy-aminomethane are similar) as raw material; Use benzene or acid anhydrides as dewatering agent in the production process more in addition; This not only causes product cost high (price is up to 60～80 yuan/kilogram), and used dewatering agent is again toxic substance, also possibly cause environmental pollution.
Summary of the invention
The objective of the invention is to the deficiency of prior art and a kind of new bicyclo oxazolidine tanning agent is provided, this tanning agent can well combine with collagen in the process hides process, both can be used as main tanning agent, can combine to tan with other tanning agents again, and cheap.
Another object of the present invention provides a kind of method for preparing above-mentioned bicyclo oxazolidine tanning agent.
Bicyclo oxazolidine tanning agent provided by the invention is to be prepared from methylol amine, polyhydroxy-alcohol and fatty aldehyde, and its chemical structure of general formula is following:
R wherein
1=-H ,-CH
3,-CHO or-CH
2CH
2CH
2CHO; R
2=-CH
2CH
2OCH
2-,-CH
2OCH
2CH
2N (CH
2CH
2OH) CH
2CH
2OCH
2-or-CH
2OCH
2CH (OH) CH
2OCH
2-,-CH
2OCH
2CH
2OCH
2-; R
3=-H ,-CH
3,-CHO or-CH
2CH
2CH
2CHO, this tanning agent outward appearance is light yellow thick liquid, at the 1162cm of its ir spectra spectrogram
-1And 1060cm
-1The skeletal vibration absorption peak that O-C-N is arranged, the methylol group content after the hydrolysis are 10-45%.
The master that this bicyclo oxazolidine tanning agent can be used for pig, ox, sheepskin tans and combination is tanned.
The method of the above-mentioned bicyclo oxazolidine tanning agent of preparation provided by the invention is earlier with 60～120 parts of methylol amine; 30～110 parts of polyhydroxy-alcohols; 65～125 parts of fatty aldehyde; In 50～80 ℃ of following stirring reactions of temperature after 4～9 hours, and then, be cooled to 40～55 ℃ of dischargings and promptly get in 80～100 ℃ of following vacuum hydro-extractions reactions of temperature 2～4 hours.
At least a in Soviet Union's amino acid, thanomin, the 2-amino-2-methyl-1-propanol of used methylol amine in the aforesaid method.
Used polyhydroxy-alcohol is at least a in terepthaloyl moietie, USP Kosher, diethylolamine, the trolamine in the aforesaid method.
In the aforesaid method used fatty aldehyde be formaldehyde, Paraformaldehyde 96, acetaldehyde, oxalic dialdehyde, LUTARALDEHYDE at least a.
The present invention has following advantage:
1, because bicyclo oxazolidine tanning agent provided by the invention is that the origin source is extensive; The synthetic gained of the starting material that price is lower; Thereby the comparable existing bicyclo oxazolidine tanning agent of its price low nearly half the (price is about 30～40 yuan/kilogram), have very strong market competition advantage.
When 2, tanning (tanning separately) the master who is used for pig, ox, sheepskin owing to bicyclo oxazolidine tanning agent provided by the invention; Its finished leather shrinkage temperature>80 ℃; And when combining to tan with vegetable tanning agent; Its finished leather shrinkage temperature>110 ℃, thereby tanning is effective, can match in excellence or beauty with existing bicyclo oxazolidine tanning agent fully.
3, because bicyclo oxazolidine tanning agent provided by the invention does not use any dewatering agent in the preparation process, thereby not only method is simple, and workable, production cost is low, and has avoided the environmental pollution that possibly cause.
Description of drawings
Accompanying drawing is the infrared spectrogram of the bicyclo oxazolidine tanning agent of the embodiment of the invention 3 preparations.
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
In addition; What be worth explanation is, below the aldehyde group content of each embodiment product measure according to ordinary method, methylol group content is to measure according to such method: take by weighing and (be accurate to 0.0001g) about 1g sample is put into the 250ml iodine flask; With distilled water diluting to the 50ml; Add 5 thymol phthalein indicators, transfer to atomic blueness, behind the sodium sulfite solution 50ml of adding 1mol/L with hydrochloric acid soln; Room temperature is deposited 30min, is that atomic blueness is a terminal point with the hydrochloric acid standard solution of 0.5mol/L from blue titration.Carry out blank test with same method.
Methylol group content is in mass percent w, and numerical value is represented with %, is calculated as follows
V
1: blank titration consumes the numerical value of hydrochloric acid standard solution volume, and unit is a milliliter (ml)
V
2: the sample titration consumes the numerical value of hydrochloric acid standard solution volume, and unit is a milliliter (ml)
C: the standard figures of hydrochloric acid standard titration solution concentration, unit are every liter (mol/L) of mole
M: the quality of sample, unit is gram (g)
0.031: the quality of suitable with 1.00ml hydrochloric acid standard titration solution (c (HCl)=1.00mol/L) methylol with the gram expression
The determining instrument of finished leather shrinkage temperature is in the application example: Hg shrinkage temperature registering instrument.
First with thanomin 65Kg, formaldehyde 35Kg, terepthaloyl moietie 35Kg; Adding has in the reaction kettle of whisking appliance, TM and reflux exchanger, reacts 3 hours down in 57 ± 3 ℃, adds oxalic dialdehyde 58Kg again; Reacted 5 hours down for 68 ± 3 ℃ in temperature; 83 ± 3 ℃ of following vacuum hydro-extraction reactions of temperature 2 hours, be cooled to 43 ± 3 ℃ of dischargings then, promptly get product.The dehydration rate 93.5% of this product, methylol group content 21.8% after the hydrolysis, aldehyde group content 21.1%.
Embodiment 2
First with Threonine 115Kg, Paraformaldehyde 96 25Kg, trolamine 75Kg; Adding has in the reaction kettle of whisking appliance, TM and reflux exchanger, reacts 3 hours down in 68 ± 3 ℃, adds acetaldehyde 45Kg again; Reacted 4 hours down for 72 ± 3 ℃ in temperature; 97 ± 3 ℃ of following vacuum hydro-extraction reactions of temperature 4 hours, be cooled to 52 ± 3 ℃ of dischargings then, promptly get product.The dehydration rate 90% of this product, methylol group content 13.8% after the hydrolysis.
Embodiment 3
First with thanomin 65Kg, diethylolamine 105Kg, formaldehyde 90Kg; Adding has in the reaction kettle of whisking appliance, TM and reflux exchanger, reacts 4 hours down in 63 ± 3 ℃, then 88 ± 3 ℃ of following vacuum hydro-extractions reactions of temperature 3 hours; Be cooled to 48 ± 3 ℃ of dischargings, promptly get product.The dehydration rate 90.6% of this product, methylol group content 41.2% after the hydrolysis, and its infrared spectrogram is shown in accompanying drawing.
Embodiment 4
Earlier with 2-amino-2 methyl isophthalic acids-propyl alcohol 90Kg, USP Kosher 50Kg, Paraformaldehyde 96 25Kg; Adding has in the reaction kettle of whisking appliance, TM and reflux exchanger, reacts 2 hours down in 63 ± 3 ℃, adds LUTARALDEHYDE 90Kg again; Reacted 7 hours down for 77 ± 3 ℃ in temperature; 97 ± 3 ℃ of following vacuum hydro-extraction reactions of temperature 3.5 hours, be cooled to 48 ± 3 ℃ of dischargings then, promptly get product.The dehydration rate 90% of this product, methylol group content is about 12.2% after the hydrolysis, aldehyde group content 11.4%.
Embodiment 5
First with thanomin 65Kg, diethylolamine 107Kg, formaldehyde 105Kg; Adding has in the reaction kettle of whisking appliance, TM and reflux exchanger, reacts 5 hours down in 58 ± 3 ℃, then 93 ± 3 ℃ of following vacuum hydro-extractions reactions of temperature 4 hours; Be cooled to 43 ± 3 ℃ of dischargings, promptly get product.The dehydration rate 92% of this product, methylol group content 39.5% after the hydrolysis.
Embodiment 6
First with Threonine 115Kg, diethylolamine 105Kg, formaldehyde 100Kg; Adding has in the reaction kettle of whisking appliance, TM and reflux exchanger, reacts 6 hours down in 53 ± 3 ℃, then 97 ± 3 ℃ of following vacuum hydro-extractions reactions of temperature 4 hours; Be cooled to 48 ± 3 ℃ of dischargings, promptly get product.The dehydration rate 91% of this product, methylol group content 34.4% after the hydrolysis.
The independent tanning pigskin of application example 1 bicyclo oxazolidine
Raw material: pickling pigskin (following materials are benchmark with the weight of pickling pigskin)
Disacidify: water 50%, salt 6%, normal temperature changes 20min; Sodium bicarbonate 0.5% with 20 times of hot water dilutions, adds at twice, and each 15min at interval changes 40min, pH=3.0.
Tanning (in disacidify liquid, carrying out): bicyclo oxazolidine tanning agent 5% enlarges liquor ratio to 1.5 times, changes 120min.
Carry alkali: sodium bicarbonate 2%, with 20 times of hot water dilutions, divide to add for three times, each 20min at interval changes 120min, pH=8.0.
After the bicyclo oxazolidine tanning, finished leather is soft and full, and the grain consolidation is fine and smooth, and shrinkage temperature reaches 83 ℃.
Application example 2 is planted-bicyclo oxazolidine combination tanning sheepskin
Raw material: pickling sheepskin (following materials are benchmark with the weight of pickling sheepskin)
Disacidify: water 50%, salt 8%, 20 ℃ of temperature are changeed 20min; Sodium formiate 2% changes 15min, and sodium bicarbonate 2% with 20 times of hot water dilutions, divides to add for three times, and each 15min at interval changes 45min, pH=6.6.
Tanning: water 30%, wattle extract 10% changes 120min, and wattle extract 10% changes 120min inspection full impregnated.
Fixing: water 100%, 40 ℃ of temperature are changeed 90min; 10 times of water dilutions of formic acid 0.5% usefulness divide to add for three times, and each 30min at interval changes 90min, pH=3.5.
Stopping drum spends the night
Washing: water 300%, 20 ℃ of temperature are changeed 5min, discharge opeing.
Rinsing: water 100%, 40 ℃ of temperature, S-WAT 0.5%, sodium sulfite anhy 96 0.5% changes 30min, discharge opeing.
Washing: water 300%, 20 ℃ of temperature are changeed 5min, discharge opeing.
Rinsing: water 100%, oxalic acid 0.5% changes 45min.
Retanning: water 200%, bicyclo oxazolidine tanning agent 6%, 20 ℃ of temperature are changeed 60min, and 60 ℃ of temperature are changeed 120min.
Measure finished leather shrinkage temperature and pH value.
Through plant-after bicyclo oxazolidine combined to tan, finished leather was soft and full, shrinkage temperature reaches 117 ℃.
Application example 3 is planted-bicyclo oxazolidine combination tanning ox-hide
Raw material: pickling ox-hide (following materials are benchmark with the weight of pickling ox-hide)
Disacidify: water 100%, salt 6%, 20 ℃ of temperature are changeed 20min; Bicyclo oxazolidine 3% (as pretanning agent) changes 45min, and sodium formiate 2% changes 20min, and 20 times of hot water dilutions of sodium bicarbonate 2% usefulness divide to add for three times, and each 20min at interval changes 60min, pH=6.6.
Taking horse spends the night
Tanning: water 30%, wattle extract 10% changes 120min, and wattle extract 10% changes 180min, the inspection full impregnated.
Fixing: water 100%, 40 ℃ of temperature are changeed 90min; 10 times of water dilutions of formic acid 0.5% usefulness add at twice, and each 30min at interval changes 90min, and pH=3.5-4.0 stops drum and spends the night.
Washing: water 300%, 20 ℃ of temperature are changeed 5min, discharge opeing.
Rinsing: water 100%, 40 ℃ of temperature, S-WAT 0.5%, sodium sulfite anhy 96 0.5% changes 30min, discharge opeing.
Washing: water 300%, 20 ℃ of temperature are changeed 5min, discharge opeing.
Rinsing: water 100%, oxalic acid 0.5% changes 45min.
Retanning: water 200%, bicyclo oxazolidine tanning agent 4%, 20 ℃ of temperature are changeed 60min, and 60 ℃ of temperature are changeed 120min.
Measure finished leather shrinkage temperature and pH value.
Through plant-after bicyclo oxazolidine combined to tan, finished leather was plentiful, the grain consolidation, shrinkage temperature reaches 118 ℃.
Claims (6)
1. a synthetic tanning agent is characterized in that this tanning agent is to be prepared from methylol amine, polyhydroxy-alcohol and fatty aldehyde, and this tanning agent outward appearance is light yellow thick liquid, at the 1162cm of its ir spectra spectrogram
-1And 1060cm
-1The skeletal vibration absorption peak that O-C-N is arranged, the methylol group content after the hydrolysis are 10-45%.
2. method for preparing the described synthetic tanning agent of claim 1; This method is with 60～120 parts of methylol amine; 30～110 parts of polyhydroxy-alcohols, 65～125 parts of fatty aldehyde are in 50～80 ℃ of following stirring reactions of temperature after 4～9 hours; In 80～100 ℃ of following dehydration reactions of temperature 2～4 hours, be cooled to 40～55 ℃ of dischargings and promptly get again.
3. the method for preparing synthetic tanning agent according to claim 2, at least a in Soviet Union's amino acid, thanomin, the 2-amino-2-methyl-1-propanol of used methylol amine in this method.
4. according to claim 2 or the 3 described methods that prepare synthetic tanning agent, used polyhydroxy-alcohol is at least a in terepthaloyl moietie, USP Kosher, diethylolamine, the trolamine in this method.
5. according to claim 2 or the 3 described methods that prepare synthetic tanning agent, in this method used fatty aldehyde be formaldehyde, Paraformaldehyde 96, acetaldehyde, oxalic dialdehyde, at least a in the LUTARALDEHYDE.
6. the method for preparing synthetic tanning agent according to claim 4, in this method used fatty aldehyde be formaldehyde, Paraformaldehyde 96, acetaldehyde, oxalic dialdehyde, at least a in the LUTARALDEHYDE.
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| CN103451026B (en) * | 2013-09-13 | 2014-11-26 | 北京泛博化学股份有限公司 | Modified glutaraldehyde tanning agent and preparation method and applications thereof |
| GB201417487D0 (en) * | 2014-10-03 | 2014-11-19 | Xeros Ltd | Method for treating an animal substrate |
| CN105803134B (en) * | 2014-12-29 | 2017-10-10 | 焦作隆丰皮草企业有限公司 | A kind of process for tanning of sheepskin |
| CN112915260B (en) * | 2021-02-02 | 2022-07-12 | 四川大学 | Non-glutaraldehyde cross-linked biomaterial and preparation method thereof |
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| CN1465718A (en) * | 2002-06-21 | 2004-01-07 | 四川大学 | Chrome free or less chrome main tanning agent for leather and preparation process thereof |
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| CN1465718A (en) * | 2002-06-21 | 2004-01-07 | 四川大学 | Chrome free or less chrome main tanning agent for leather and preparation process thereof |
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