CN104710366B - Improved preparation method of dimethylol dihydroxy ethylene urea - Google Patents
Improved preparation method of dimethylol dihydroxy ethylene urea Download PDFInfo
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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
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- metal salt
- biformyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- ZEYUSQVGRCPBPG-UHFFFAOYSA-N 4,5-dihydroxy-1,3-bis(hydroxymethyl)imidazolidin-2-one Chemical compound OCN1C(O)C(O)N(CO)C1=O ZEYUSQVGRCPBPG-UHFFFAOYSA-N 0.000 title abstract 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 sulfonic acid alkali metal salt Chemical class 0.000 claims abstract description 48
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 36
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- NNTWKXKLHMTGBU-UHFFFAOYSA-N 4,5-dihydroxyimidazolidin-2-one Chemical compound OC1NC(=O)NC1O NNTWKXKLHMTGBU-UHFFFAOYSA-N 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims abstract 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 21
- 235000013877 carbamide Nutrition 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 8
- 229960002887 deanol Drugs 0.000 claims description 8
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 claims description 6
- 229960004194 lidocaine Drugs 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- DJGAAPFSPWAYTJ-UHFFFAOYSA-M metamizole sodium Chemical group [Na+].O=C1C(N(CS([O-])(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 DJGAAPFSPWAYTJ-UHFFFAOYSA-M 0.000 claims description 4
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- VJAGHZLYXAKQID-UHFFFAOYSA-N benzenesulfonic acid;potassium Chemical compound [K].OS(=O)(=O)C1=CC=CC=C1 VJAGHZLYXAKQID-UHFFFAOYSA-N 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 3
- RPPCFYFWGVIQFS-UHFFFAOYSA-N 1-(dimethylamino)butan-1-ol Chemical compound CCCC(O)N(C)C RPPCFYFWGVIQFS-UHFFFAOYSA-N 0.000 claims 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims 1
- NFIYTPYOYDDLGO-UHFFFAOYSA-N phosphoric acid;sodium Chemical group [Na].OP(O)(O)=O NFIYTPYOYDDLGO-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 229940015043 glyoxal Drugs 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 29
- 239000007788 liquid Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 0 **(CC(C(N1)O)O)*C1=O Chemical compound **(CC(C(N1)O)O)*C1=O 0.000 description 3
- 238000007031 hydroxymethylation reaction Methods 0.000 description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 3
- 235000019799 monosodium phosphate Nutrition 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical group [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- ZPLCXHWYPWVJDL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-1,3-oxazolidin-2-one Chemical compound C1=CC(O)=CC=C1CC1NC(=O)OC1 ZPLCXHWYPWVJDL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- GHGFADYXERRLID-UHFFFAOYSA-N NC(=O)N.C(O)C(=CO)O Chemical compound NC(=O)N.C(O)C(=CO)O GHGFADYXERRLID-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- QDPMLKBAQOZXEF-UHFFFAOYSA-N ethanesulfonic acid;sodium Chemical compound [Na].CCS(O)(=O)=O QDPMLKBAQOZXEF-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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
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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