CN104710366B - Improved preparation method of dimethylol dihydroxy ethylene urea - Google Patents

Improved preparation method of dimethylol dihydroxy ethylene urea Download PDF

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CN104710366B
CN104710366B CN201310692507.3A CN201310692507A CN104710366B CN 104710366 B CN104710366 B CN 104710366B CN 201310692507 A CN201310692507 A CN 201310692507A CN 104710366 B CN104710366 B CN 104710366B
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sulfonic acid
alkali metal
preparation
metal salt
biformyl
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CN104710366A (en
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李正雄
顾喆栋
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Zhejiang Zhendong New Material Co.,Ltd.
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YAYUN TEXILE AGENTS CO Ltd SHANGHAI
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Abstract

The invention provides a preparation method of dimethylol dihydroxy ethylene urea. The method comprises the following steps: 1, reacting urea with glyoxal in the presence of sulfonic acid and sulfonic acid alkali metal salt at 30-60DEG C for 3-6h to prepare a dihydroxy ethylene urea intermediate; and 2, reacting the dihydroxy ethylene urea intermediate obtained in step 1 with a formaldehyde and optional organic alcohol amine mixture in the presence of dialkali metal hydrogen phosphate and alkali metal dihydrogen phosphate at 40-60DEG C for 2-4h to obtain a target product. The preparation method has the advantages of stable reaction and high conversion rate, and the product has the advantages of high content of active groups, and strong responsivity.

Description

The improvement preparation method of hydroxymethyl-2 dihydroxy-ethylene urea
Technical field
The present invention relates in finishing functions of textile fabrics field a kind of wash and wear finisher improvement preparation method, more specifically two The preparation method of methylol dihydroxy ethylene urea.
Technical background
Bafta is favored the features such as with soft, comfortable, ventilative, good hygroscopicity by people, but it exist it is easy The shortcoming of easy wrinkle of shrinking.The effect that resin finishing can reach Shrinkproof crease-resistant is carried out to bafta.At present, conventional resin finishing agent It is divided into two big class:Low aldehyde finishing agent and without aldehyde finishing agent.Formaldehydeless finishing agent safety and environmental protection, meets current development trend, but The bafta resilience arranged with it is relatively low, it is difficult to meet the requirement of pure cotton fabric crease and shrink resistance, and it is expensive.Without aldehyde non-tree The finishing agent of lipid, such as BTCA, price is even more 5-6 times of low urea formaldehyde, and the fabric xanthochromia for arranging is larger.At present Market is prevailing to be still modified N- methylol amide resinoids, wherein with hydroxymethyl-2 dihydroxy-ethylene urea(2D Resin)Modified resin application is most.
High-quality hydroxymethyl-2 dihydroxy-ethylene urea is the basis for obtaining the modified 2D resins of high-quality.2D resins are by urinating Element, Biformyl, formaldehyde are primary raw material preparation.Typically synthetic method is《Printing and dyeing handbook》(The second edition)(2003, china textile Publishing house)The method of recommendation.Will Biformyl, carbamide and formaldehyde be added to " one-step method " work of synchronized compound in reactor together Skill and Biformyl and carbamide are first cyclized into dihydroxy ethylene urea, then " two-step method " technique that hydroxymethylation is carried out with formaldehyde. One-step method time-saving energy-saving, but by-product is more, it is more difficult to control.Two-step method can make proportioning raw materials accurately, and reaction is relatively easy to control, synthesis Resin quality is more stable.Whether one-step method or two step method, Biformyl conversion ratio is not high in reaction, and the presence of Biformyl affects The application performance of product, causes fabric xanthochromia.In addition, the concentration of 2D naval stores is higher, follow-up 2D resins are more conducive to be etherified The carrying out of modified-reaction.And 2D resins prepared by traditional two step method, storage stability is bad during high concentration, affects product etherificate to change Property reaction.
For two-step process, despite many professional journals the improvement of many synthetic methods is reported, but be mostly from The conditions such as proportioning raw materials, reaction temperature, response time are optimized to reduce content of formaldehyde, are improving Biformyl conversion ratio, height Strength products are stable and the aspect such as reactivity is seldom related to.
Therefore, in the urgent need to a kind of process is simple, reacting balance, the dihydroxymethyl dihydroxy second of high conversion rate in this area The improvement preparation method of alkene urea.
The content of the invention
In order to overcome the shortcomings of existing hydroxymethyl-2 dihydroxy-ethylene urea two step method preparation technology, it is an object of the invention to A kind of preparation method of the good DP finish of cotton fabric agent of high conversion, high reactive group, high-concentration and stable is provided.This system Preparation Method is innovated on the basis of existing technology of preparing.Sulfonic acid catalyst is introduced in first step reaction, Biformyl is made Conversion ratio is greatly improved.Second step optional organic alcohol amine and formaldehyde preneutralization, replace in conjunction with phosphate-based buffer system The sodium carbonate or sodium hydroxide of routine, overcoming conventional two-step process causes reaction system pH-value fluctuation range big, difficult With the defect for controlling, so that stable reaction conditions are easily-controllable, beneficial to hydroxymethylation, the active group improved in product contains Amount.Meanwhile, significantly improve the stability of strength products.
Specifically, the invention provides the preparation method of hydroxymethyl-2 dihydroxy-ethylene urea that represents of following formula I,
The method is comprised the following steps:
1)In the presence of sulfonic acid and sodium sulfonate, carbamide is reacted 3~6 hours at 30~60 DEG C with Biformyl, dihydroxy is obtained Base ethylene urea intermediate;With
2)In the presence of the alkali metal salt of phosphoric acid hydrogen two and biphosphate alkali metal salt, step 1 is made)The dihydroxy second of middle gained React 2~4 hours at 40~60 DEG C with the mixture of formaldehyde and optional organic alcohol amine in alkene urea intermediate, obtain title product Thing.
The preparation method process is simple of the present invention, reacting balance, high conversion rate.The Product Activity group content of preparation is high, Highly concentrated product stability is good.
Specific embodiment
High conversion of the present invention, the preparation of high reactive group wash and wear finisher can use following reaction equation to represent:
The first step of the present invention is carbamide and Biformyl ring structure, and dihydroxy ethylene urea intermediate is obtained.Then, intermediate with Formaldehyde hydroxymethylation is obtained target product.
In the inventive method, the step(1)Middle reaction temperature is 30~60 DEG C, preferably 35~60 DEG C.Response time For 3~6 hours, preferably 4~5 hours.
The step(2)Middle reaction temperature is 40~60 DEG C, preferably 50~60 DEG C.Response time is 2~4 hours, excellent Elect 3~4 hours as.
The step(2)In organic alcohol amine be dimethylaminoethanol, diethylaminoethanol, lignocaine propanol, diformazan Amino butanol one or two.
In the methods of the invention, the Biformyl:Carbamide:The ratio 1 of the amount of the material of formaldehyde:(1.0~1.2):(1.8~ 2.0), the ︰ 1.9 of 1.02 ︰ of preferably 1 ︰, 1.8~1 ︰ 1.1.
In one preferred embodiment, the method for the present invention is additionally included in 50~80 DEG C, preferably 55~70 DEG C, very Reciprocal of duty cycle be -0.080~-0.1MPa, vacuum distillation step under conditions of preferably -0.085~-0.1MPa(2)In the product that obtains Thing.
In one preferred embodiment, step 1)In the mass ratio of sulfonic acid and sulfonic acid alkali metal salts be 1:2~1: 15, preferably 1:3~1:10.
In a particularly preferred embodiment, step 1)In the gross mass of sulfonic acid and sulfonic acid alkali metal salts be second two The 0.2-2% of aldehyde quality, preferably 0.4-1.6%.
In one preferred embodiment, above-mentioned sulfonic acid includes C1-3Alkyl sulfonic acid, C6-10Aryl sulfonic acid or they Mixture.Above-mentioned sulfonic acid alkali metal salts include C1-3Alkyl sulfonic acid alkali metal salt, C6-10Aryl sulfonic acid alkali metal salt or they Mixture.
In a particularly preferred embodiment, above-mentioned C1-3Alkyl sulfonic acid is pyrovinic acid, above-mentioned C1-3Alkyl Sulfonic acid alkali metal salts are novalgin, pyrovinic acid potassium or their mixture;Above-mentioned C6-10Aryl sulfonic acid is benzenesulfonic acid, benzene Sulfonic acid or their mixture;Above-mentioned C6-10Aryl sulfonic acid alkali metal salt is benzene sulfonic acid sodium salt, benzenesulfonic acid potassium or their mixture.
In one preferred embodiment, step 2)In the alkali metal salt of phosphoric acid hydrogen two and biphosphate alkali metal salt Mass ratio 6:1~25:1, preferably 10:1~20:1.
In a particularly preferred embodiment, step 2)In the alkali metal salt of phosphoric acid hydrogen two and biphosphate alkali metal The gross mass of salt is the 1-4%, preferably 2-3% of Biformyl quality.
In a particularly preferred embodiment, the above-mentioned alkali metal salt of phosphoric acid hydrogen two is disodium hydrogen phosphate, phosphoric acid hydrogen Dipotassium or their mixture, above-mentioned biphosphate alkali metal salt is sodium dihydrogen phosphate, potassium dihydrogen phosphate or their mixing Thing.
In one preferred embodiment, step 2)In organic alcohol amine quality for formaldehyde quality 0-5%, preferably 0.5%-5%, more preferably 1~4%.
In sum, the present invention provides the preparation method of wash and wear finisher, and reacting balance is easily controlled;The product of preparation Reactive high, high conversion rate, high concentration product stability are good.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than restriction the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.
Experimental data in each embodiment is measured with the following method:
1)The residual rate of Biformyl adopts KOH dropping point methods.
1.000g samples are accurately weighed in iodine flask, the dilution of 30ml deionized waters is added, drop Bromothymol blue refers to plus 2 Show agent, with the NaOH solution of 0.1mol/L micro- blueness is titrated to, keep 5s not fade for terminal.It is subsequently adding 1.5mol/L's KOH standard solution 10.00ml, place 15min, and with the HCl standard solution of 0.5mol/L blue disappearance is titrated to.Write down consumption Volume V.
Biformyl residual rate R%=[(C1V1- C2V2)×0.05804/m]×100
In formula:C1:Add the actual volume of KOH standard solution, ml;
V1:The actual concentrations of KOH standard solution, mol/L;
C2:HCl standard solution actual concentrations, mol/L
V2:Titration consumes the volume of HCl standard solution, ml.
m:The quality of sample, g.
0.05804:0.001mol KOH are converted into the quality of Biformyl.
Biformyl conversion ratio is then calculated according to Biformyl residual rate, specially:
Biformyl conversion ratio %=[(M2-R×M1)/M2]×100
In formula:
M2:Biformyl gross mass, g
M1:Reactant gross mass when determining Biformyl residual rate, g
R:Biformyl residual rate.
2)Active group-hydroxymethyl formaldehyde content is determined according to GB5543-2006.
3)The measure of index of refraction:With abbe's refractometer in 25 DEG C of measure.
4)High concentration product stability is determined:Concentration is put at ambient temperature for the product of solid content 80% or so, observation Whether product becomes cloudy or particulate matter is separated out.
Embodiment 1
In 1 liter of four round flask equipped with agitator, thermometer and condensing tube, 290 grams of Biformyl is added(Content 40%), it is subsequently adding 126 grams of carbamide(Content 99%), in 35 DEG C of stirring and dissolving.It is subsequently adding pyrovinic acid 0.12g(Content 70%), novalgin 0.60g(Content 98%), in 40 DEG C, react 2 hours;Novalgin 0.20g is added, 55 are warming up to DEG C, continue to react 2 hours.Determine the residual quantity of Biformyl(The results are shown in Table 1).
Then reactant is cooled to into 50 DEG C, adds disodium hydrogen phosphate 2.6g, sodium dihydrogen phosphate 0.16g, 1-2 hour Deca 300g formalins(37%)With the mixed liquor of 2.5g dimethylaminoethanol(Dimethylaminoethanol is previously added in formalin), Continue to react 4 hours at 50 DEG C, obtain light yellow transparent liquid.Determine active group hydroxymethyl formaldehyde content(The results are shown in Table 1).
By above-mentioned light yellow transparent liquid at 60 DEG C, under the conditions of vacuum -0.090~-0.098Mpa, vacuum distillation goes out not The raw material of reaction and other waste liquids, the solid content 80% of remaining light yellow transparent liquid stops distillation to alembic, as makes The high concentration wash and wear finisher for obtaining.It is 1.4266 to determine product index of refraction.The stability of observation product(The results are shown in Table 1).
Embodiment 2
In the 1L four round flask equipped with agitator, thermometer and condensing tube, 290 grams of Biformyl is added(Content 40%), it is subsequently adding 130 grams of carbamide(Content 99%), in 35 DEG C of stirring and dissolving.It is subsequently adding ethylsulfonic acid 0.21g(Content 70%), ethylsulfonic acid sodium 0.82g(Content 98%), in 40 DEG C, react 2 hours;Ethylsulfonic acid sodium 0.50g is added, 50 are warming up to DEG C, continue to react 2 hours.Determine the residual quantity of Biformyl(The results are shown in Table 1).
It is subsequently adding disodium hydrogen phosphate 2.8g, sodium dihydrogen phosphate 0.20g, 1-2 hour Deca 300g formalin(37%)With The mixed liquor of 2.5g dimethylaminoethanol, 1.5g lignocaine propanol(Dimethylaminoethanol and lignocaine propanol are previously added In formalin), continue to react 3 hours at 55 DEG C, obtain light yellow transparent liquid.Determine active group hydroxymethyl formaldehyde content (The results are shown in Table 1).
By above-mentioned light yellow transparent liquid at 60 DEG C, under the conditions of vacuum -0.090~-0.098Mpa, vacuum distillation goes out not The raw material of reaction and other waste liquids, the solid content 80% of remaining light yellow transparent liquid stops distillation to alembic, as makes The high concentration wash and wear finisher for obtaining.It is 1.4268 to determine product index of refraction.The stability of observation product(The results are shown in Table 1).
Embodiment 3
In the four round flask equipped with agitator, thermometer and condensing tube, 290 grams of Biformyl is added(Content 40%), It is subsequently adding 130 grams of carbamide(Content 99%), in 35 DEG C of stirring and dissolving.It is subsequently adding benzenesulfonic acid 0.30g(Content 80%), benzenesulfonic acid Sodium 0.80g(Content 98%), in 40 DEG C, react 2 hours;Benzene sulfonic acid sodium salt 0.45g is added, 50 DEG C are warming up to, continues reaction 2 little When.Determine the residual quantity of Biformyl(The results are shown in Table 1).
It is subsequently adding dipotassium hydrogen phosphate 2.8g, potassium dihydrogen phosphate 0.20g, 1-2 hour Deca 300g formalin(37%)With The mixed liquor of 2.5g dimethylaminoethanol, 1.5g lignocaine propanol(Dimethylaminoethanol and lignocaine propanol are previously added In formalin), continue to react 3 hours at 55 DEG C, obtain light yellow transparent liquid.Determine active group hydroxymethyl formaldehyde content (The results are shown in Table 1).
By above-mentioned light yellow transparent liquid at 60 DEG C, under the conditions of vacuum -0.090~-0.098Mpa, vacuum distillation goes out not The raw material of reaction and other waste liquids, the solid content 80% of remaining light yellow transparent liquid stops distillation to alembic, as makes The high concentration wash and wear finisher for obtaining.It is 1.4265 to determine product index of refraction.The stability of observation product(The results are shown in Table 1).
Reference Example 1(It is prepared by traditional two step method,《Printing and dyeing handbook》(The second edition))
In the 1L four round flask equipped with agitator, thermometer and condensing tube, 290 grams of Biformyl is added(Content 40%), it is subsequently adding 126 grams of carbamide(Content 99%), 35 DEG C are warming up to, stop heating.25% soda 4g is subsequently adding, is adjusted PH5-5.5, reacts 2 hours in 50 DEG C.Determine the residual quantity of Biformyl(The results are shown in Table 1).
It is subsequently adding 300g formalins(37%), then with 25% soda adjust pH8.2-8.5,50 DEG C react 3 hours, Cooling, adjusts pH6-6.5, obtains light yellow transparent liquid.Determine active group hydroxymethyl formaldehyde content(The results are shown in Table 1).
By above-mentioned light yellow transparent liquid at 60 DEG C, under the conditions of vacuum -0.090~-0.098Mpa, vacuum distillation goes out not The raw material of reaction and other waste liquids, the solid content 80% of remaining light yellow transparent liquid stops distillation to alembic, as makes The high concentration wash and wear finisher for obtaining.It is 1.4263 to determine product index of refraction.The stability of observation product(The results are shown in Table 1).
The determination data of the embodiment of table 1 and Reference Example
Note:Embodiment 1, embodiment 2, embodiment 3 and the product of comparative example 1, Theoretical Calculation and 100% solid content, methylol first Aldehyde is 32.19%;During the hydroxymethyl formaldehyde content of practical measurement product, product solid content is 45%.
The data explanation of table 1, the improved method of the present invention significantly reduces the residual of Biformyl compared with traditional two step method Allowance, i.e. Biformyl conversion ratio is significantly improved, and the active group hydroxymethyl formaldehyde content of product is far above traditional method preparation Product, meanwhile, the storage stability of product is significantly improved.

Claims (13)

1. the preparation method of the hydroxymethyl-2 dihydroxy-ethylene urea that a kind of following formula I is represented,
The method is comprised the following steps:
1) in the presence of sulfonic acid and sulfonic acid alkali metal salts, carbamide is reacted 3~6 hours at 30~60 DEG C with Biformyl, be obtained Dihydroxy ethylene urea intermediate;With
2) in the presence of the alkali metal salt of phosphoric acid hydrogen two and biphosphate alkali metal salt, make step 1) in gained dihydroxy ethylene urea Intermediate reacts 2~4 hours with the mixture of formaldehyde and organic alcohol amine at 40~60 DEG C, obtains title product;
Wherein described sulfonic acid is C1-3Alkyl sulfonic acid, C6-10Aryl sulfonic acid or their mixture, described sulfonic acid alkali metal salts It is C1-3Alkyl sulfonic acid alkali metal salt, C6-10Aryl sulfonic acid alkali metal salt or their mixture;
Described organic alcohol amine is dimethylaminoethanol, diethylaminoethanol, lignocaine propanol, one kind of dimethylamino butanol Or two kinds.
2. preparation method as claimed in claim 1, it is characterised in that described sulfonic acid is with the mass ratio of sulfonic acid alkali metal salts 1:2~1:15.
3. preparation method as claimed in claim 2, it is characterised in that described sulfonic acid is with the mass ratio of sulfonic acid alkali metal salts 1:3~1:10.
4. preparation method as claimed in claim 1, it is characterised in that the described alkali metal salt of phosphoric acid hydrogen two and biphosphate alkali The mass ratio of slaine is 6:1~25:1.
5. preparation method as claimed in claim 4, it is characterised in that the described alkali metal salt of phosphoric acid hydrogen two and biphosphate alkali The mass ratio of slaine is 10:1~20:1.
6. preparation method as claimed in claim 1 or 2, it is characterised in that total matter of described sulfonic acid and sulfonic acid alkali metal salts Measure as the 0.2~2% of Biformyl quality.
7. preparation method as claimed in claim 6, it is characterised in that described sulfonic acid is with the gross mass of sulfonic acid alkali metal salts The 0.4-1.6% of Biformyl quality.
8. the preparation method as described in claim 1 or 4, it is characterised in that the described alkali metal salt of phosphoric acid hydrogen two and di(2-ethylhexyl)phosphate The gross mass of hydrogen alkali metal salt is the 1.0-4.0% of Biformyl quality.
9. preparation method as claimed in claim 8, it is characterised in that the described alkali metal salt of phosphoric acid hydrogen two and biphosphate alkali The gross mass of slaine is the 2-3% of Biformyl quality.
10. preparation method as claimed in claim 1, it is characterised in that described organic alcohol amine quality is formaldehyde quality 0.5%-5%.
11. preparation methoies as claimed in claim 10, it is characterised in that described organic alcohol amine quality is the 1 of formaldehyde quality ~4%.
12. preparation methoies as claimed in claim 1, it is characterised in that Biformyl:Carbamide:The mol ratio of formaldehyde is 1:(1.0 ~1.2):(1.8~2.0).
13. preparation methoies as claimed in claim 1, it is characterised in that described C1-3Alkyl sulfonic acid is pyrovinic acid, described C1-3Alkyl sulfonic acid alkali metal salt is novalgin, pyrovinic acid potassium or their mixture, the C6-10Aryl sulfonic acid is Benzenesulfonic acid, the C6-10Aryl sulfonic acid alkali metal salt is benzene sulfonic acid sodium salt, benzenesulfonic acid potassium or their mixture, described phosphoric acid hydrogen Two alkali metal salts are disodium hydrogen phosphate, dipotassium hydrogen phosphate or their mixture, and described biphosphate alkali metal salt is phosphoric acid Sodium dihydrogen, potassium dihydrogen phosphate or their mixture.
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