CN104961657A - Spandex yellow inhibitor UDT synthesis technology - Google Patents
Spandex yellow inhibitor UDT synthesis technology Download PDFInfo
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- CN104961657A CN104961657A CN201510246598.7A CN201510246598A CN104961657A CN 104961657 A CN104961657 A CN 104961657A CN 201510246598 A CN201510246598 A CN 201510246598A CN 104961657 A CN104961657 A CN 104961657A
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Abstract
The present invention discloses a spandex yellow inhibitor UDT (N, N-dimethyl-amino-4-phenyl-hydrazide) synthesis technology, by drop-wise addition of a MDI (methylene diphenyl diisocyanate) toluene solution into an unsymmetrical dimethylhydrazine toluene solution for reaction, the synthesis technology effectively avoids raw material MDI inclusion in product, and the synthesized product is high in purity, good in character, even and easy to crush. Compared with conventional synthesis process, the synthesis process effectively avoids raw material MDI inclusion in the product, so that the synthesized product spandex yellow inhibitor UDT (N, N-dimethyl-amino-4-phenyl-hydrazide) has high purity and low chroma, and the product has a good character. Meanwhile, the process provides an efficient way for processing UDMH (unsymmetrical dimethylhydrazine) waste solution, and can turn waste into treasure.
Description
Technical field
The present invention relates to the processing method that two (N, the N-dimethyl-hydrazine amino-4-phenyl) methane of a kind of synthesis has another name called the anti-yellow agent UDT of spandex, the anti-yellow agent UDT product purity of spandex of this method synthesis is high, proterties good.
Background technology
The anti-yellow agent UDT of spandex (having another name called anti-yellow agent HN-150) is the derived product of unsymmetrical dimethyl hydrazine (UDMH, i.e. 1,1-dimethylhydrazine), is one of required auxiliary agent during spandex is produced.Spandex and polyurethane elastomeric fiber a kind ofly have that fiber number is thin, elastic force is high, Young's modulus is large, proportion is little, dyeability is good and the tencel of the premium properties such as fastness is good.China's spandex is as the maximum producing country in the whole world, and annual production in 2013 reaches 38.97 ten thousand tons, and turnout is in rising tendency year by year.The anti-yellow agent UDT of spandex is a kind of special photostabilizer, light fastness stability and the color fastness to nitrogen oxides of fiber can be improved, prevent fiber yellowing, ensure that fiber has some strength and favorable elasticity simultaneously, in addition, the anti-yellow agent UDT of spandex can also be used as the tamanori of fabric paint (pigment printing paste) stamp.Yellow agent is pressed down as one efficient spandex material, its market requirement mainly relies on polyurethane industries among others, as materials such as spandex fibre, synthetic leather, leatheroids, industry addition, usually in 0.5% ~ 1% scope, is spandex fibre 89%, synthetic leather 6%, leatheroid 5% at the consumption proportion of each Application Areas successively.The each Application Areas average growth rate per annum of the anti-yellow agent of efficient spandex is spandex fibre 11%, synthetic leather 9%, leatheroid 8% successively.The characteristic that can not be substituted had in view of polyurethane industries among others and advantage, make the anti-yellow agent UDT demand of spandex rise year by year, not only have very large demand at home, also has the very large market requirement the external of industrial develop rapidly.At present, domestic spandex anti-yellow agent (UDT) demand is considerable, annual needs about 3000 tons.For a long time, due to technique imperfection and starting material restriction, the anti-yellow agent of domestic spandex can not effective supply, undue dependence on import, the sound development of the whole Textile Chain of containing.
The raw material unsymmetrical dimethyl hydrazine of the anti-yellow agent UDT of synthesis spandex is a kind of liquid rocket fuel of excellent property, have a wide range of applications in national defence and space industry, the application on the weaponrys such as space vehicles rocket, torpedo, space, exoatmosphere mouse and guided missile occupies critical role.As very high (purity >=98% of unsymmetrical dimethyl hydrazine index request that propelling agent uses, moisture content≤0.25%), the weaponry being much mounted with unsymmetrical dimethyl hydrazine propelling agent is completed the term of service to be needed to eliminate, or a large amount of dimazine spent liquor will certainly be produced in production, storage, use procedure, if method process such as burning traditionally, degradeds, very large resource and energy dissipation certainly will be caused, also can cause certain environmental pollution simultaneously.Therefore, scrapping in unsymmetrical dimethyl hydrazine problem in process, be translated into the derived product of high added value, will be the approach be more of practical significance.As Test System for Rocket Engine Test unit, my unit all can produce dimazine spent liquor every year, waste liquid for the production of the anti-yellow agent UDT of product for civilian use spandex, can save energy, reduce Pollutant Treatment cost, unit income can be increased again.
At present, all correlative study is had both at home and abroad to the synthesis technique of the anti-yellow agent UDT of spandex, existing production technique that is domestic and Japanese use is and the mixing solutions of unsymmetrical dimethyl hydrazine and solvent is added to 4, reacts in 4 '-methylene two phenylene diisocyanate (MDI) and the mixing solutions of solvent.In this technique, product is relatively more serious to the double team of raw material MDI, in product drying process, because heating makes the raw material MDI polymerization reaction take place of double team, thus has a strong impact on quality product.In addition, the charging capacity of external use unsymmetrical dimethyl hydrazine excessive relative to MDI 20% is produced, although this mode can ensure the complete reaction of MDI, the greatly excessive of unsymmetrical dimethyl hydrazine causes reaction product color yellowing because of residual unsymmetrical dimethyl hydrazine generation oxidizing reaction, affects quality product.Meanwhile, the unsymmetrical dimethyl hydrazine solution purity used in aforesaid method requires very high, generally select purity must be greater than >=98%.
Summary of the invention
In order to solve the problem in background technology, the invention provides a kind of simple process, efficient, practical, product purity is high, proterties good, for the synthesis of the anti-yellow agent UDT technique of spandex.
Concrete technical scheme of the present invention is:
Synthesize a technique of the anti-yellow agent UDT of spandex, it is characterized in that, comprise the following steps:
1) under agitation raw material MDI is dissolved in toluene solution, is mixed with the MDI toluene solution that concentration is 0.2 ~ 0.4g/ml;
2) in reaction vessel, by toluene solution and unsymmetrical dimethyl hydrazine solution by volume 3:1 ~ 5:1 mixed preparing go out unsymmetrical dimethyl hydrazine toluene solution;
3) by step 1) gained MDI toluene solution joins step 2 with the speed of 30 ~ 60mL/min) in gained unsymmetrical dimethyl hydrazine toluene solution, after dropwising, at temperature is 30 DEG C, by the stir speed (S.S.) of 20 ~ 30r/min, reaction 30min, after leaving standstill 0.5 ~ 1.5h, filtering separation obtains the anti-yellow agent UDT of crude product spandex and toluenic filtrate;
4) by step 3) the anti-yellow agent UDT of gained crude product spandex vacuum-drying 2 ~ 3h under 120 ~ 130 DEG C of conditions obtains final product.
Above-mentioned steps 1) in raw material MDI solution and step 2) in the mass ratio of unsymmetrical dimethyl hydrazine solution be 100:52 ~ 100:57.
Further scheme is: above-mentioned steps 2) in toluene solution and unsymmetrical dimethyl hydrazine liquor capacity than 3.5:1 ~ 4.5:1.
Optimized scheme is: above-mentioned steps 2) in toluene solution and unsymmetrical dimethyl hydrazine liquor capacity compare 4:1.
Above-mentioned steps 3) toluenic filtrate of gained is directly back to step 2) in use; The number of times used is for 3-4 time.
Above-mentioned through claim 4 use after toluene solvant adopt distillation method reclaim be directly used in step 1) or step 2) solution preparation in.
The purity of above-mentioned unsymmetrical dimethyl hydrazine solution is >=96%.
The invention has the advantages that:
1, the present invention adopts the anti-yellow agent UDT of method production spandex being added in the toluene solution of unsymmetrical dimethyl hydrazine by the toluene solution of MDI and carry out reacting.The solution dropping order products obtained therefrom of this method effectively prevent the double team of product to raw material MDI, and product purity high (purity >=99.6%) proterties is good, and product is evenly easily pulverized, and is convenient to spandex manufacturer and uses.
2, the present invention can adopt purity be greater than >=unsymmetrical dimethyl hydrazine of 96% carries out the synthesis of the anti-yellow agent UDT of spandex, reduces production cost, increase economic efficiency as raw material, simultaneously can save energy, avoid environmental pollution.
3, gained reaction filtrate of the present invention is reusable, greatly saves the production cost of product.
Embodiment
The present invention is based on following chemical principle:
Embodiment 1
52g raw material unsymmetrical dimethyl hydrazine 250mL dilution with toluene is placed in 2L there-necked flask, 100g raw material MDI is dissolved in 750mL toluene, be 52:100 according to raw material unsymmetrical dimethyl hydrazine and MDI mass ratio, with constant pressure funnel, MDI solution is joined in unsymmetrical dimethyl hydrazine solution with the rate of addition of 25mL/min, continuously stirring reaction 30min at 30 DEG C.After question response, in the still aging 1h of room temperature, the anti-yellow agent UDT of target product spandex is separated out, decompress filter, washing obtain the anti-yellow agent UDT product crude product of spandex, and drying process obtains UDT product, and calculate productive rate, and carry out purity check, data are in table 1.
Embodiment 2
53g raw material unsymmetrical dimethyl hydrazine 250mL dilution with toluene is placed in 2L there-necked flask, 100g raw material MDI is dissolved in 750mL toluene, be 53:100 according to raw material unsymmetrical dimethyl hydrazine and MDI mass ratio, with constant pressure funnel, MDI solution is joined in unsymmetrical dimethyl hydrazine solution with the rate of addition of 25mL/min, continuously stirring reaction 30min at 30 DEG C.After question response, in the still aging 1h of room temperature, the anti-yellow agent UDT of target product spandex is separated out, decompress filter, washing obtain the anti-yellow agent UDT product crude product of spandex, and drying process obtains UDT product, and calculate productive rate, and carry out purity check, data are in table 1.
Embodiment 3
54g raw material unsymmetrical dimethyl hydrazine 250mL dilution with toluene is placed in 2L there-necked flask, 100g raw material MDI is dissolved in 750mL toluene, be 54:100 according to raw material unsymmetrical dimethyl hydrazine and MDI mass ratio, with constant pressure funnel, MDI solution is joined in unsymmetrical dimethyl hydrazine solution with the rate of addition of 25mL/min, continuously stirring reaction 30min at 30 DEG C, after question response, in the still aging 1h of room temperature, the anti-yellow agent UDT of target product spandex is separated out, decompress filter, washing obtains the anti-yellow agent UDT product crude product of spandex, drying process obtains UDT product, calculate productive rate, and carry out purity check, data are in table 1.
Embodiment 4
55g raw material unsymmetrical dimethyl hydrazine 250mL dilution with toluene is placed in 2L there-necked flask, 100g raw material MDI is dissolved in 750mL toluene, be 55:100 according to raw material unsymmetrical dimethyl hydrazine and MDI mass ratio, with constant pressure funnel, MDI solution is joined in unsymmetrical dimethyl hydrazine solution with the rate of addition of 25mL/min, continuously stirring reaction 30min at 30 DEG C, after question response, in the still aging 1h of room temperature, the anti-yellow agent UDT of target product spandex is separated out, decompress filter, washing obtains the anti-yellow agent UDT product crude product of spandex, drying process obtains UDT product, calculate productive rate, and carry out purity check, data are in table 1.
Embodiment 5
56g raw material unsymmetrical dimethyl hydrazine 250mL dilution with toluene is placed in 2L there-necked flask, 100g raw material MDI is dissolved in 750mL toluene, be 56:100 according to raw material unsymmetrical dimethyl hydrazine and MDI mass ratio, with constant pressure funnel, MDI solution is joined in unsymmetrical dimethyl hydrazine solution with the rate of addition of 25mL/min, continuously stirring reaction 30min at 30 DEG C, after question response, in the still aging 1h of room temperature, the anti-yellow agent UDT of target product spandex is separated out, decompress filter, washing obtains the anti-yellow agent UDT product crude product of spandex, drying process obtains UDT product, calculate productive rate, and carry out purity check, data are in table 1.
Embodiment 6
57g raw material unsymmetrical dimethyl hydrazine 250mL dilution with toluene is placed in 2L there-necked flask, 100g raw material MDI is dissolved in 750mL toluene, be 57:100 according to raw material unsymmetrical dimethyl hydrazine and MDI mass ratio, with constant pressure funnel, MDI solution is joined in unsymmetrical dimethyl hydrazine solution with the rate of addition of 25mL/min, continuously stirring reaction 30min at 30 DEG C, after question response, in the still aging 1h of room temperature, the anti-yellow agent UDT of target product spandex is separated out, decompress filter, washing obtains the anti-yellow agent UDT product crude product of spandex, drying process obtains UDT product, calculate productive rate, and carry out purity check, data are in table 1.
Embodiment 7
58g raw material unsymmetrical dimethyl hydrazine 250mL dilution with toluene is placed in 2L there-necked flask, 100g raw material MDI is dissolved in 750mL toluene, be 58:100 according to raw material unsymmetrical dimethyl hydrazine and MDI mass ratio, with constant pressure funnel, MDI solution is joined in unsymmetrical dimethyl hydrazine solution with the rate of addition of 25mL/min, continuously stirring reaction 30min at 30 DEG C, after question response, in the still aging 1h of room temperature, the anti-yellow agent UDT of target product spandex is separated out, decompress filter, washing obtains the anti-yellow agent UDT product crude product of spandex, drying process obtains UDT product, calculate productive rate, and carry out purity check, data are in table 1.
Embodiment 8
The raw material unsymmetrical dimethyl hydrazine 250mL dilution with toluene of 54g is placed in 2L there-necked flask, 100g raw material MDI is dissolved in 750mL toluene, be 54:100 according to raw material unsymmetrical dimethyl hydrazine and MDI mass ratio, with constant pressure funnel, MDI solution is joined in unsymmetrical dimethyl hydrazine solution with the rate of addition of 25mL/min, continuously stirring reaction 40min at 30 DEG C, after question response, in the still aging 1h of room temperature, the anti-yellow agent UDT of target product spandex is separated out, decompress filter, washing obtains the anti-yellow agent UDT product crude product of spandex, drying process obtains UDT product, calculate productive rate, and carry out purity check, data are in table 1.
Embodiment 9
The raw material unsymmetrical dimethyl hydrazine 250mL dilution with toluene of 54g is placed in 2L there-necked flask, 100g raw material MDI is dissolved in 750mL toluene, be 54:100 according to raw material unsymmetrical dimethyl hydrazine and MDI mass ratio, with constant pressure funnel, MDI solution is joined in unsymmetrical dimethyl hydrazine solution with the rate of addition of 25mL/min, continuously stirring reaction 30min at 40 DEG C, after question response, in the still aging 1h of room temperature, the anti-yellow agent UDT of target product spandex is separated out, decompress filter, washing obtains the anti-yellow agent UDT product crude product of spandex, drying process obtains UDT product, calculate productive rate, and carry out purity check, data are in table 1.
Table 1 to be depicted as under embodiment condition accordingly result after completion of the reaction
Pass through, above-mentioned 1-7 group embodiment can be found out, when MDI solution and unsymmetrical dimethyl hydrazine solution quality ratio are 100:52 ~ 100:57, temperature of reaction controls at 30 DEG C, and the reaction times controls when 30min, and the UDT product yield obtained is greater than 96%, product purity is more than or equal to 99.7%, all meets the requirements; Particularly MDI solution and unsymmetrical dimethyl hydrazine solution quality are than during for 100:54, and product purity reaches 99.9%, should be optimum embodiment.
But, as above-mentioned 8,9 liang of group embodiments can draw, when change temperature of reaction and time, same employing MDI solution and unsymmetrical dimethyl hydrazine solution quality are tested than for 100:54, obviously can find out that the productive rate of product and purity have significantly to decline, therefore, when carrying out this technique, control temperature of reaction and time are also vital.
Note: test the unsymmetrical dimethyl hydrazine (rocket propellant waste liquid) that purity is 96% in experimentation, experiment also can reach the product yield of 96%, and product purity is higher than 99.6%, and black increment is 20.
Claims (7)
1. synthesize a technique of the anti-yellow agent UDT of spandex, it is characterized in that, comprise the following steps:
1) under agitation raw material MDI is dissolved in toluene solution, is mixed with the MDI toluene solution that concentration is 0.2 ~ 0.4g/ml;
2) in reaction vessel, by toluene solution and unsymmetrical dimethyl hydrazine solution by volume 3:1 ~ 5:1 mixed preparing go out unsymmetrical dimethyl hydrazine toluene solution;
3) by step 1) gained MDI toluene solution joins step 2 with the speed of 30 ~ 60mL/min) in gained unsymmetrical dimethyl hydrazine toluene solution, after dropwising, at temperature is 30 DEG C, by the stir speed (S.S.) of 20 ~ 30r/min, reaction 30min, after leaving standstill 0.5 ~ 1.5h, filtering separation obtains the anti-yellow agent UDT of crude product spandex and toluenic filtrate;
4) by step 3) the anti-yellow agent UDT of gained crude product spandex vacuum-drying 2 ~ 3h under 120 ~ 130 DEG C of conditions obtains final product.
2. the technique of the anti-yellow agent UDT of synthesis spandex according to claim 1, is characterized in that: described step 1) in raw material MDI solution and step 2) in the mass ratio of unsymmetrical dimethyl hydrazine solution be 100:52 ~ 100:57.
3. the technique of the anti-yellow agent UDT of synthesis spandex according to claim 1 and 2, is characterized in that, comprise the following steps: described step 2) in toluene solution and unsymmetrical dimethyl hydrazine liquor capacity than 3.5:1 ~ 4.5:1.
4. the technique of the anti-yellow agent UDT of synthesis spandex according to claim 3, is characterized in that, comprise the following steps: described step 2) in toluene solution and unsymmetrical dimethyl hydrazine liquor capacity compare 4:1.
5. the technique of the anti-yellow agent UDT of synthesis spandex according to claim 1, is characterized in that: described step 3) toluenic filtrate of gained is directly back to step 2) in use; The number of times used is for 3-4 time.
6. the technique of the anti-yellow agent UDT of synthesis spandex according to claim 1, is characterized in that: through claim 4 use after toluene solvant adopt distillation method reclaim be directly used in step 1) or step 2) solution preparation in.
7. the technique of the anti-yellow agent UDT of synthesis spandex according to claim 1, is characterized in that: the purity of described unsymmetrical dimethyl hydrazine solution is >=96%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115246782A (en) * | 2021-04-28 | 2022-10-28 | 西安航洁化工科技有限责任公司 | Industrial production process of anti-yellowing agent HN-150 |
| CN116082196A (en) * | 2023-01-31 | 2023-05-09 | 郑州中远氨纶工程技术有限公司 | Carbamide terminated carbamate compound and preparation method and application thereof |
| CN116082196B (en) * | 2023-01-31 | 2024-05-31 | 郑州中远氨纶工程技术有限公司 | Carbamide terminated carbamate compound and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151205A (en) * | 2014-07-15 | 2014-11-19 | 绍兴文理学院 | Preparation method of anti-yellowing agent HN-150 |
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- 2015-05-14 CN CN201510246598.7A patent/CN104961657A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151205A (en) * | 2014-07-15 | 2014-11-19 | 绍兴文理学院 | Preparation method of anti-yellowing agent HN-150 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115246782A (en) * | 2021-04-28 | 2022-10-28 | 西安航洁化工科技有限责任公司 | Industrial production process of anti-yellowing agent HN-150 |
| CN116082196A (en) * | 2023-01-31 | 2023-05-09 | 郑州中远氨纶工程技术有限公司 | Carbamide terminated carbamate compound and preparation method and application thereof |
| CN116082196B (en) * | 2023-01-31 | 2024-05-31 | 郑州中远氨纶工程技术有限公司 | Carbamide terminated carbamate compound and preparation method and application thereof |
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Application publication date: 20151007 |