CN102643452B - Method for improving aziridine cross-linking agent stability - Google Patents
Method for improving aziridine cross-linking agent stability Download PDFInfo
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- CN102643452B CN102643452B CN 201110038812 CN201110038812A CN102643452B CN 102643452 B CN102643452 B CN 102643452B CN 201110038812 CN201110038812 CN 201110038812 CN 201110038812 A CN201110038812 A CN 201110038812A CN 102643452 B CN102643452 B CN 102643452B
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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 as shown in general formula (1):
Aziridine crosslinker shown in formula (1) is the agent of a kind of trifunctional crosslinked at low temperature, is widely used in the 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 the advantages such as normal temperature crosslinked, as to improve leather or fabric wear resistance, aftertreatment be simple.
The synthetic method of the aziridine crosslinker shown in formula (1) is known for the insider: undertaken by 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 in 11-14:
But the aziridine crosslinker stability shown in general formula (1) is not good, just solidifies less than 30 days during room temperature and loses efficacy, and gives storing and uses and all bring difficulty.In order to extend storage life, when synthetic aziridine crosslinker, it is excessive that 2-methyl ethylene imines needs, so as reaction finish after in product residual a large amount of 2-methyl ethylene imines (usually account for product weight 1～10%), play the effect of stablizer.This method can make product storage life extend to 24 months when room temperature, 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 large, user's endurable; (2) residual 2-methyl ethylene imines toxicity is high, and user of service and surrounding environment are worked the mischief; (3) although in use major part can ring-opening polymerization and removed for residual 2-methyl ethylene imines, can not remove totally, cause residual the exceeding standard of 2-methyl ethylene imines in derived product, affect quality product.When for example domestic aziridine crosslinker used in hide finishes, the fur clothing of producing gave out strong amine flavor; Find that when fur clothing is detected 2-methyl ethylene imines is residual up to 36ppm, the user can not accept.Yet, if adopting the method such as vacuum distilling in preparation aziridine crosslinker process removes 2-methyl ethylene imines, reduces its residual quantity (below 15ppm), the storage life of aziridine crosslinker significantly shortens, less than was just solidified in 1 month when room temperature, 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, have no report in 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 as 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.
By a large amount of research, the inventor finds, the stable principal recipient of above-mentioned aziridine crosslinker is the pH impact, only linking agent can be stored for a long time in alkaline system, can solidify very soon when Lewis acid exists, for example airborne carbonic acid gas just is enough to make aziridine crosslinker to solidify very soon.In addition, the stability of aziridine crosslinker also is subjected to the impact of temperature, and during room temperature, linking agent solidifies very slowly, solidifies when temperature raises and accelerates.
By add aqueous sodium hydroxide solution or the potassium hydroxide aqueous solution of q.s in aziridine crosslinker, 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 large, 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 production, is specifically designed to the pH regulation and control of the water-based systems such as water miscible liquid, the aqueous solution, and usually adding 0.01～0.2% just has very good effect, and the market sales volume is very large.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 processing also only has 2 months.
Further in research process, the contriver has established the method for the aziridine crosslinker stability shown in a kind of improvement general formula (1) satisfactory for result: add appropriate small molecules amine stablizer in this linking agent, make the pH value of system keep alkalescence, thus the storage life that extends significantly linking agent.
Small molecule amine compounds with used as stabilizers is selected from N-(2-hydroxyethyl) quadrol, N-(2-hydroxyethyl)-1,3-propylene diamine, N-methyl-N-(2-hydroxyethyl)-1,3-propylene diamine, polyetheramine JEFFAMINE D-230 or polyetheramine JEFFAMINEEDR-148.These small molecules amine stablizers are not new, can conveniently buy on market, for example the product produced of U.S. HUNTSMAN company.These are listed in table 1 with the small molecule amine of used as stabilizers and structure and the physical data of comparison 2-amino-2-methyl-1-propanol.
Table 1
These small molecules amine stablizers have following characteristics: (1) molecule contains two or more amino, and wherein having an amino at least is that end is amino; (2) molecule contains hydroxyl or polyether group, and polyether group refers to oxyethane or propylene oxide polyethers, as CH
2CH
2O-, CH
2CH (CH
3) O-etc.; (3) atmospheric boiling point is over 200 ℃; (4) molecular weight is no more than 500.
In these small molecules amine stablizers, end is amino has a higher activity, the preferential Lewis acid such as absorbing carbon dioxide, thus protect not curing reaction of aziridine crosslinker; And a plurality of amino can regulate and control pH better.Molecule contains hydroxyl or polyether group, 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 the room temperature steam of stablizer forces down, and evaporation rate is slow, can effectively reduce smell, reduces volatile matter, is conducive to the producer and user's safety precaution.Molecular weight is lower, and 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 aziridine crosslinker, mixes and get final product.Described stablizer both can have been chosen wantonly from wherein a kind of, can be also the mixture of several arbitrary proportions wherein.
Aziridine crosslinker shown in formula (1) makes as raw material carries out addition reaction according to currently known methods take 2-methyl ethylene imines and Viscoat 295 (being called for short TMPTA).Remove the 2-methyl ethylene imines in product after reaction finishes, for example adopt the vacuum distilling method, make in product 2-methyl ethylene imines residual concentration lower than 100ppm.Then directly add above-mentioned small molecules amine stablizer, 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 there is no the amine flavor of domestic linking agent in the past.Test result shows, adopts method of the present invention, and the aziridine crosslinker shown in formula (1) at room temperature can be stablized storage 96 months; Under 100 ℃, thermostability was over 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 formula (1) can be used for the crosslinked of polyaminoester emulsion and polyacrylate dispersion etc., the advantages such as that the linking agent after 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 for further describing and illustrating the present invention.These embodiment that provide only as the purpose of understanding invention, do not limit the claim that the present invention states.
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-propylene diamine ... ... ... .... industrial goods, 99%, U.S. HUNTSMAN company
N-methyl-N-(2-hydroxyethyl)-1, the 3-propylene diamine ... ... ... 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 backflow condenser, thermometer, dropping funnel; add 180 grams (3.15 moles) 2-methyl ethylene imines under room temperature, nitrogen protection; stir lower dropping 297 grams (1 mole) Viscoat 295s (TMPTA), approximately dripped off in 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 except remaining 2-methyl ethylene imines.
The product cool to room temperature obtains the pure aziridine crosslinker suc as formula (1), and achromaticity and clarification liquid weighs 466 grams, purity 99%, and yield is 99.5% (in Viscoat 295) approximately.Gas chromatographic analysis, 2-methyl ethylene imines residual quantity 15ppm in product.(detect the linking agent XR-2500 of Dutch Stahl company, wherein 2-methyl ethylene imines residual quantity is 16ppm).
2) improve the performance test of stability
The aziridine crosslinker that makes is taken a certain amount of a series of vial of putting into respectively, add respectively the small molecules amine stablizer of setting dosage, after mixing, build stopper.Then a series of vial is put into baking oven, 100 ℃ of thermostatically heating.Observe the situation that in bottle, viscosity increases, and record the time of solidifying.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.
As can be found from Table 2, the aziridine crosslinker that does not add small molecules amine stablizer is very poor 100 ℃ of stability, only just occurs in 6 hours solidifying; Aziridine crosslinker stability after 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 significantly improves, and only adds 0.1% amount the heat-storage life-span to 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 backflow condenser, thermometer, dropping funnel; add 297 grams (1 mole) Viscoat 295s (TMPTA) under room temperature, nitrogen protection; stir lower 189 grams (3.3 moles) the 2-methyl ethylene imines that drips, approximately dripped off in 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 except remaining 2-methyl ethylene imines.
The product cool to room temperature obtains the pure aziridine crosslinker suc as formula (1), and the achromaticity and clarification thick liquid weighs 464 grams, purity 99%, and yield is 99% (in Viscoat 295) approximately.Gas chromatographic analysis, wherein 2-methyl ethylene imines residual quantity 10ppm.
2) improve the performance test of stability
The aziridine crosslinker that makes is taken a certain amount of a series of vial of putting into respectively, add respectively the small molecules amine stablizer of setting dosage, after mixing, build stopper.Then a series of vial room temperature is placed (15～30 ℃ of temperature, approximately 15 ℃ of winters, approximately 30 ℃ of summers, approximately 20 ℃ of spring and autumns), the situation that in the observation bottle, viscosity increases, and the time of record curing.Test result is listed in table 3.
Stability test under table 3 room temperature
Annotate: A7, A14, be for No. A21 Comparative Examples, with 2-amino-2-methyl-1-propanol (AMP-95) as stablizer;
No. A22 for not adding the blank assay of stablizer;
It is for No. A23 the control experiment of the linking agent XR-2500 of Dutch Stahl company.
As can be found from Table 3, the aziridine crosslinker that does not add small molecules amine stablizer is not good in room temperature stability, only just occurs in 0.5 month solidifying; Aziridine crosslinker stability after 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% the storage life under room temperature to be brought up to more than 96 months, extends one times than the linking agent XR-2500 of Dutch Stahl company.
Claims (4)
1. a method of improving aziridine crosslinker stability, is characterized in that: add appropriate small molecules amine stablizer in this linking agent; Described aziridine crosslinker is as the formula (1):
Described small molecules amine stablizer is selected from N-(2-hydroxyethyl) quadrol, N-(2-hydroxyethyl)-1,3-propylene diamine, N-methyl-N-(2-hydroxyethyl)-1,3-propylene diamine, polyetheramine JEFFAMINE D-230 or polyetheramine JEFFAMINE EDR-148;
The addition of described small molecules amine stablizer is 0.01%～10% of aziridine crosslinker weight.
2. it is characterized in that in accordance with the method for claim 1: the addition of small molecules amine stablizer is 0.1%～5% of aziridine crosslinker weight.
3. according to the described method of claim 1 or 2, it is characterized in that: the aziridine crosslinker shown in formula (1) is synthetic as raw material carries out addition reaction take 2-methyl ethylene imines and Viscoat 295; Remove the 2-methyl ethylene imines in product after reaction finishes, make in product 2-methyl ethylene imines residual concentration lower than 100ppm, then add wherein small molecules amine stablizer.
4. according to the method for claim 3, it is characterized in that: the stablizer of interpolation can be both a kind of, also can be the mixture of the small molecules amine stablizer of several arbitrary proportions.
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| 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 |
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| CN1030230A (en) * | 1987-06-25 | 1989-01-11 | 日本触媒化学工业株式会社 | Produce the method for aziridines |
| CN1234041A (en) * | 1996-10-23 | 1999-11-03 | 美国3M公司 | Organoborane amine complex initiator systems and polymerizable compositions made therewith |
| CN101392108A (en) * | 2008-11-06 | 2009-03-25 | 武汉市强龙化工新材料有限责任公司 | Stabilizer for stabilization of triaziridines room temperature crosslinking agent in water |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62192355A (en) * | 1986-02-20 | 1987-08-22 | Res Assoc Util Of Light Oil | Stabilization of aziridine-2-carboxylic acid salt |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030230A (en) * | 1987-06-25 | 1989-01-11 | 日本触媒化学工业株式会社 | Produce the method for aziridines |
| CN1234041A (en) * | 1996-10-23 | 1999-11-03 | 美国3M公司 | Organoborane amine complex initiator systems and polymerizable compositions made therewith |
| CN101392108A (en) * | 2008-11-06 | 2009-03-25 | 武汉市强龙化工新材料有限责任公司 | Stabilizer for stabilization of triaziridines room temperature crosslinking agent in water |
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