CN102643452A - Method for improving aziridine cross-linking agent stability - Google Patents
Method for improving aziridine cross-linking agent stability Download PDFInfo
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- CN102643452A CN102643452A CN2011100388121A CN201110038812A CN102643452A CN 102643452 A CN102643452 A CN 102643452A CN 2011100388121 A CN2011100388121 A CN 2011100388121A CN 201110038812 A CN201110038812 A CN 201110038812A CN 102643452 A CN102643452 A CN 102643452A
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Abstract
The invention belongs to the field of polymer chemistry, and discloses a method for improving aziridine cross-linking agent stability, wherein at least one micromolecular amine stabilizing agent is added into an aziridine cross-linking agent to greatly increase the storage stability of the aziridine cross-linking agent. The adding amount of the stabilizing agent is 0.01%-10% (w/w) of the weight of the aziridine cross-linking agent. The modified cross-linking agent has the advantages of room temperature crosslinking, improved wear resistant fastness, simple post-treatment, and the like, can be used for corsslinking of polyurethane emulsions and polyacrylate emulsions, and is widely applicable to fields of leather finishing agents, waterborne coatings, textile coating printing paste, adhesives, and the like.
Description
Technical field
The invention belongs to chemical field, relate to a kind of method of improving aziridine crosslinker stability.More specifically, the present invention relates to a kind of method that adopts small molecules amine stablizer to improve aziridine crosslinker stability.
Background technology
Aziridine crosslinker of the present invention, structure is shown in general formula (1):
Aziridine crosslinker shown in the formula (1) is the agent of a kind of trifunctional crosslinked at low temperature, is widely used in fields such as hide finishes, water-borne coatings, textile coating printing paste, tackiness agent.Be a kind of colourless or yellow liquid during this linking agent room temperature, storing is convenient, has advantages such as normal temperature crosslinked, as to improve leather or fabric wear resistance, aftertreatment be simple.
The compound method of the aziridine crosslinker shown in the formula (1) is known for the insider: carry out through 2-methyl ethylene imines and Viscoat 295 (being called for short TMPTA) that the Micheal addition reaction makes.For example " Chinese leather ", 1999,28 (7), disclosed following reaction equation among the 11-14:
But the aziridine crosslinker stability shown in the general formula (1) is not good, just solidifies inefficacy less than 30 days during room temperature, gives to store and transport and use and all bring difficulty.In order to prolong storage life, when synthetic aziridine crosslinker, it is excessive that 2-methyl ethylene imines needs, so that reaction finishes back residual a large amount of 2-methyl ethylene imines (account for usually product weight 1～10%) in product, plays function of stabilizer.This method can make product storage life when room temperature, extend to 24 months, or extends to 92 hours 100 ℃ the time, possesses certain practical commercial value.Domestic manufacturer all adopts this method at present.But there is following shortcoming in the method for intentional residual 2-methyl ethylene imines: (1) residual 2-methyl ethylene imines boiling point is lower, and high volatility, smell are very big, and the user is difficult to stand; (2) residual 2-methyl ethylene imines toxicity is high, and user of service and surrounding environment are worked the mischief; (3) though in use major part can ring-opening polymerization and be able to remove for residual 2-methyl ethylene imines, can not remove totally, cause residual the exceeding standard of 2-methyl ethylene imines in the derived product, influence quality product.When for example homemade aziridine crosslinker used in hide finishes, the fur clothing of producing gave out intensive amine flavor; Find that when fur clothing is detected 2-methyl ethylene imines is residual up to 36ppm, the user can not accept.Yet; Remove 2-methyl ethylene imines, reduce its residual quantity (below 15ppm) as if methods such as in preparation aziridine crosslinker process, adopting vacuum distilling; Then the storage life of aziridine crosslinker shortens significantly, and less than was just solidified in 1 month when room temperature, and perhaps less than was just solidified in 10 hours in the time of 100 ℃; Bring difficulty for transportation and storage, thereby do not possess industrial value.How to solve this difficult problem, do not appear in the newspapers in the prior art.
Summary of the invention
The objective of the invention is that a kind of 2-methyl ethylene imines residual quantity is low, the aziridine crosslinker of structure shown in general formula (1) of product stock excellent performance for the user provides.In order to realize this purpose, the contriver has developed a kind of method of improving aziridine crosslinker stability.
Through a large amount of research; The inventor finds; The stable principal recipient of above-mentioned aziridine crosslinker is the pH influence; Only linking agent can long storage in alkaline system, when Lewis acid exists, can solidify very soon, and for example carbon dioxide in air just is enough to make aziridine crosslinker to solidify very soon.In addition, the stability of aziridine crosslinker also receives Influence of Temperature, and linking agent solidifies very slowly during room temperature, solidifies when temperature raises and accelerates.
Through in aziridine crosslinker, adding the aqueous sodium hydroxide solution or the potassium hydroxide aqueous solution of q.s, can improve the stability of linking agent; But these strong base solutions can dilute the concentration of aziridine crosslinker, cause content to reduce, and strong base solution corrodibility are very strong, use to the user and bring danger and inconvenience, lack practical value.Add ammoniacal liquor or liquefied ammonia and also can improve aziridine crosslinker stability, but ammoniacal liquor or liquefied ammonia smell are too big, contaminate environment, the user refuses to accept, so these measures all are difficult to carry out.
2-amino-2-methyl-1-propanol (AMP-95) is the stablizer of U.S. DOW chemical prodn, is specifically designed to the pH regulation and control of water-based systems such as water miscible liquid, the aqueous solution, and adding 0.01～0.2% usually just has very good effect, and the market sales volume is very big.The contriver once added it in aziridine crosslinker to, but result of use is unsatisfactory; Even addition increases to 5%, the linking agent room temperature storage life-span after the processing also has only 2 months.
Further the contriver has established the method for the aziridine crosslinker stability shown in a kind of improvement general formula (1) satisfactory for result in the research process: in this linking agent, add an amount of small molecules amine stablizer; Make the pH value of system keep alkalescence, thus the storage life that prolongs linking agent significantly.
Small molecule amine compounds with used as stabilizers is selected from N-(2-hydroxyethyl) quadrol, N-(2-hydroxyethyl)-1,3-tn, N-methyl-N-(2-hydroxyethyl)-1,3-tn, polyetheramine JEFFAMINE D-230 or polyetheramine JEFFAMINEEDR-148.These small molecules amine stablizers are not new, can conveniently buy on the market, for example the product of U.S. HUNTSMAN company production.These are listed in table 1 with the small molecule amine of used as stabilizers and the structure and the physical data of comparison 2-amino-2-methyl-1-propanol.
Table 1
These small molecules amine stablizers have following characteristics: (1) intramolecularly contains two or more amino, and wherein having an amino at least is that end is amino; (2) intramolecularly contains hydroxyl or polyether group, and polyether group is meant oxyethane or propylene oxide polyethers, like CH
2CH
2O-, CH
2CH (CH
3) O-etc.; (3) atmospheric boiling point is above 200 ℃; (4) molecular weight is no more than 500.
In these small molecules amine stablizers, end is amino to have higher activity, but Lewis acids such as preferentially adsorbed carbonic acid gas, thus the not open loop of protection aziridine crosslinker is solidified; And a plurality of amino can be regulated and control pH better.Intramolecularly contains hydroxyl or polyether group, then can improve the water-soluble of stablizer, causes the profit demixing phenomenon to avoid stablizer poor solubility in water.Atmospheric boiling point is high, and then the room temperature steam of stablizer forces down, and evaporation rate is slow, can effectively reduce smell, reduces volatile matter, helps the producer and user's safety precaution.Molecular weight is low more, and then stabilization efficiency is higher.
The addition of small molecules amine stablizer is 0.01%～10% (w/w) of aziridine crosslinker weight.Stablizer is directly added in the aziridine crosslinker, mixes and get final product.Described stablizer both can have been chosen wantonly from wherein a kind of, also can be the mixture of several kinds of arbitrary proportions wherein.
Aziridine crosslinker shown in the formula (1) is that raw material carries out addition reaction according to currently known methods and makes with 2-methyl ethylene imines and Viscoat 295 (being called for short TMPTA).Remove the 2-methyl ethylene imines in the product after reaction finishes, for example adopt the vacuum distilling method, make that 2-methyl ethylene imines residual concentration is lower than 100ppm in the product.Directly add above-mentioned small molecules amine stablizer then, preferred addition is 0.1%～5% (w/w) of aziridine crosslinker weight.
The aziridine crosslinker that adds these small molecules amine stablizers not only stability improves greatly, and does not have the amine flavor of homemade linking agent in the past.Test result shows, adopts method of the present invention, and the aziridine crosslinker shown in the formula (1) at room temperature can be stablized storage 96 months; Under 100 ℃, thermostability was above 200 hours.And the present linking agent XR-2500 of like product-Dutch Stahl company, thermostability also can only reach 100 hours in the time of 100 ℃.
Aziridine crosslinker shown in the formula (1) can be used for the crosslinked of polyaminoester emulsion and polyacrylate emulsion etc.; Advantages such as that the linking agent after the modification has is normal temperature crosslinked, improve wear resistance, aftertreatment is simple are widely used in fields such as hide finishes, water-borne coatings, textile coating printing paste, tackiness agents.Therefore, the method for improvement aziridine crosslinker stability provided by the invention has very important practical value and commercial applications prospect.
Embodiment
Following examples are used to further describe and explain the present invention.These embodiment that provided are only as understanding the purpose of inventing, do not limit the present invention the claim of being stated.
Experimental drug:
2-methyl ethylene imines ... ... ... ... ... ... .. industrial goods, 99%
Viscoat 295 (being called for short TMPTA) ... ... .... industrial goods, ester value 99%
N-(2-hydroxyethyl) quadrol ... ... ... ... .... industrial goods, 99%, U.S. HUNTSMAN company
N-(2-hydroxyethyl)-1, the 3-tn ... ... ... .... industrial goods, 99%, U.S. HUNTSMAN company
N-methyl-N-(2-hydroxyethyl)-1, the 3-tn ... ... ... industrial goods, 99%, U.S. HUNTSMAN company
Polyetheramine JEFFAMINE D-230...................... industrial goods, 97%, U.S. HUNTSMAN company
Polyetheramine JEFFAMINE EDR-148.................... industrial goods, U.S. HUNTSMAN company
2-amino-2-methyl-1-propanol ... ... ... ... .. industrial goods, U.S. DOW chemistry
Aziridine crosslinker XR-2500........................ industrial goods, 99%, Dutch Stahl company
Embodiment 1
1) preparation aziridine crosslinker
In the 1000ml four-hole bottle that is equipped with stirring, efficient reflux exchanger, TM, tap funnel; Under room temperature, nitrogen protection, add 180 gram (3.15 moles) 2-methyl ethylene imines; Stir and drip 297 gram (1 mole) Viscoat 295s (TMPTA) down, dripped off in about 30 minutes.After adding, be warmed up to 40-80 ℃ of reaction 8 hours.After reaction finishes, vacuum distilling 6 hours, temperature 40-80 ℃, vacuum tightness 0.1～50mmHg steams and removes remaining 2-methyl ethylene imines.
The product cool to room temperature obtains purified aziridine crosslinker suc as formula (1), and achromaticity and clarification liquid weighs 466 grams, purity 99%, about 99.5% (in the Viscoat 295) of yield.Gas chromatographic analysis, 2-methyl ethylene imines residual quantity 15ppm in the product.(detect the linking agent XR-2500 of Dutch Stahl company, wherein 2-methyl ethylene imines residual quantity is 16ppm).
2) improve stable performance test
The aziridine crosslinker that makes is taken by weighing a certain amount of a series of vial of putting into respectively, add the small molecules amine stablizer of setting dosage respectively, after mixing, build stopper.Then a series of vial is put into baking oven, 100 ℃ of thermostatically heating.Observe the situation that viscosity increases in the bottle, and the record solidified time.Test result is listed in table 2.
100 ℃ of heat stability tests of table 2
Annotate: 7th, 14, No. 21 is Comparative Examples, with 2-amino-2-methyl-1-propanol (AMP-95) as stablizer;
No. 22 for not adding the blank assay of stablizer;
It is for No. 23 the control experiment of the linking agent XR-2500 of Dutch Stahl company.
Can find that from table 2 aziridine crosslinker that does not add small molecules amine stablizer is very poor 100 ℃ of stability, only just occur in 6 hours solidifying; Aziridine crosslinker stability behind the interpolation 2-amino-2-methyl-1-propanol (AMP-95) promotes not obvious; And the stability of adding the aziridine crosslinker of the small molecules amine stablizer that the present invention selects for use significantly improves, and only adds 0.1% amount can the heat-storage life-span be brought up to more than 200 hours, is more than 2 times of linking agent XR-2500 of Dutch Stahl company; Adding small molecules amine stablizer 1% can bring up to storage life more than 500 hours, is more than 5 times of XR-2500; Adding small molecules amine stablizer 5% can bring up to storage life more than 1000 hours, is more than 10 times of XR-2500.
Embodiment 2
1) preparation aziridine crosslinker
In the 1000ml four-hole bottle that is equipped with stirring, efficient reflux exchanger, TM, tap funnel; Under room temperature, nitrogen protection, add 297 gram (1 mole) Viscoat 295s (TMPTA); Stir and drip 189 gram (3.3 moles) 2-methyl ethylene imines down, dripped off in about 1 hour.After adding, be warmed up to 40-80 ℃ of reaction 6 hours.After reaction finishes, vacuum distilling 6 hours, temperature 40-80 ℃, vacuum tightness 0.1～50mmHg steams and removes remaining 2-methyl ethylene imines.
The product cool to room temperature obtains purified aziridine crosslinker suc as formula (1), and the achromaticity and clarification thick liquid weighs 464 grams, purity 99%, about 99% (in the Viscoat 295) of yield.Gas chromatographic analysis, wherein 2-methyl ethylene imines residual quantity 10ppm.
2) improve stable performance test
The aziridine crosslinker that makes is taken by weighing a certain amount of a series of vial of putting into respectively, add the small molecules amine stablizer of setting dosage respectively, after mixing, build stopper.Then a series of vial room temperature is placed (15～30 ℃ of temperature, about 15 ℃ of winter, about 30 ℃ of summer, about 20 ℃ of spring and autumn), observe the situation that viscosity increases in the bottle, and the record solidified time.Test result is listed in table 3.
Stability test under table 3 room temperature
Annotate: A7, A14, A21 number is Comparative Examples, with 2-amino-2-methyl-1-propanol (AMP-95) as stablizer;
A22 number for not adding the blank assay of stablizer;
It is for A23 number the control experiment of the linking agent XR-2500 of Dutch Stahl company.
Can find that from table 3 aziridine crosslinker that does not add small molecules amine stablizer is not good in room temperature stability, only just occur in 0.5 month solidifying; Aziridine crosslinker stability behind the interpolation 2-amino-2-methyl-1-propanol (AMP-95) promotes not obvious.And the stability of adding the aziridine crosslinker of small molecules amine stablizer significantly improves, and only adds 0.1% can the storage life under the room temperature be brought up to more than 96 months, prolongs one times than the linking agent XR-2500 of Dutch Stahl company.
Claims (5)
1. a method of improving aziridine crosslinker stability is characterized in that: in this linking agent, add an amount of small molecules amine stablizer; Described aziridine crosslinker is suc as formula shown in (1):
The addition of described small molecules amine stablizer is 0.01%～10% of an aziridine crosslinker weight.
2. according to the described method of claim 1; It is characterized in that: described small molecules amine stablizer is selected from N-(2-hydroxyethyl) quadrol, N-(2-hydroxyethyl)-1; 3-tn, N-methyl-N-(2-hydroxyethyl)-1,3-tn, polyetheramine JEFFAMINE D-230 or polyetheramine JEFFAMINE EDR-148.
3. according to claim 1 or 2 described methods, it is characterized in that: the addition of small molecules amine stablizer is 0.1%～5% of an aziridine crosslinker weight.
4. according to claim 1 or 2 described methods, it is characterized in that: the aziridine crosslinker shown in the formula (1) is to be that raw material carries out the addition reaction synthetic with 2-methyl ethylene imines and Viscoat 295; Remove the 2-methyl ethylene imines in the product after reaction finishes, make that 2-methyl ethylene imines residual concentration is lower than 100ppm in the product, again to wherein adding small molecules amine stablizer.
5. according to the method for claim 4, it is characterized in that: the stablizer of interpolation both can be a kind of, also can be the mixture of the small molecules amine stablizer of several kinds of arbitrary proportions.
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| CN104250939A (en) * | 2013-06-28 | 2014-12-31 | 桐乡市高桥皮革有限责任公司 | Method for re-fixing color of leather finished product |
| CN104746363A (en) * | 2013-12-30 | 2015-07-01 | 辽宁恒星精细化工有限公司 | Leather printing paste and preparation method thereof |
| CN104788721A (en) * | 2015-04-04 | 2015-07-22 | 成都育芽科技有限公司 | Aziridine crosslinker containing composition and preparation method thereof |
| CN105646317A (en) * | 2016-01-18 | 2016-06-08 | 上海华谊（集团）公司 | Preparation method for trimethylolpropane tri[3-(2-methyl aziridinyl)propionic ester] |
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| CN104250939B (en) * | 2013-06-28 | 2016-07-06 | 桐乡市高桥皮革有限责任公司 | Finished leather is color-fixing method again |
| CN104250939A (en) * | 2013-06-28 | 2014-12-31 | 桐乡市高桥皮革有限责任公司 | Method for re-fixing color of leather finished product |
| CN104746363A (en) * | 2013-12-30 | 2015-07-01 | 辽宁恒星精细化工有限公司 | Leather printing paste and preparation method thereof |
| CN104746363B (en) * | 2013-12-30 | 2016-11-23 | 辽宁恒星精细化工有限公司 | A kind of leather pattern-printing slurry and preparation method thereof |
| CN104788721B (en) * | 2015-04-04 | 2017-12-12 | 河南理工大学 | A kind of composition containing aziridine crosslinker and preparation method thereof |
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| CN105646317A (en) * | 2016-01-18 | 2016-06-08 | 上海华谊（集团）公司 | Preparation method for trimethylolpropane tri[3-(2-methyl aziridinyl)propionic ester] |
| CN106220543A (en) * | 2016-07-25 | 2016-12-14 | 南昌航空大学 | A kind of preparation method of trimethylolpropane tris (2 methyl 1 '-aziridino) propionic ester |
| CN107119473A (en) * | 2017-06-26 | 2017-09-01 | 王蒙 | A kind of cross linking agent |
| CN108485642A (en) * | 2018-03-29 | 2018-09-04 | 陕西科技大学 | A kind of application of star-like carboxylic acid group's zwitterionic surfactant as foaming agent |
| CN108485641A (en) * | 2018-03-29 | 2018-09-04 | 陕西科技大学 | A kind of application of star-like sulfonic base zwitterionic surfactant as foaming agent |
| CN108485641B (en) * | 2018-03-29 | 2020-05-12 | 陕西科技大学 | Application of star-shaped sulfonic acid group zwitterionic surfactant as foaming agent |
| CN108485642B (en) * | 2018-03-29 | 2020-05-12 | 陕西科技大学 | Application of star-shaped carboxylic acid group zwitterionic surfactant as foaming agent |
| CN109487593A (en) * | 2018-11-12 | 2019-03-19 | 广州市珠之江环保印花材料实业有限公司 | Printing and dyeing rubber cement and preparation method thereof |
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