CN104710366A - Improved preparation method of dimethylol dihydroxy ethylene urea - Google Patents
Improved preparation method of dimethylol dihydroxy ethylene urea Download PDFInfo
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- CN104710366A CN104710366A CN201310692507.3A CN201310692507A CN104710366A CN 104710366 A CN104710366 A CN 104710366A CN 201310692507 A CN201310692507 A CN 201310692507A CN 104710366 A CN104710366 A CN 104710366A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 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 48
- -1 sulfonic acid alkali metal salt Chemical class 0.000 claims abstract description 41
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 18
- NNTWKXKLHMTGBU-UHFFFAOYSA-N 4,5-dihydroxyimidazolidin-2-one Chemical compound OC1NC(=O)NC1O NNTWKXKLHMTGBU-UHFFFAOYSA-N 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims abstract description 9
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 229960002887 deanol Drugs 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 claims description 6
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 4
- 235000019800 disodium phosphate Nutrition 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
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical group [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-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
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- RPPCFYFWGVIQFS-UHFFFAOYSA-N 1-(dimethylamino)butan-1-ol Chemical class CCCC(O)N(C)C RPPCFYFWGVIQFS-UHFFFAOYSA-N 0.000 claims description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-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
- MMDSSERULWYGSW-UHFFFAOYSA-N methanesulfonic acid;potassium Chemical compound [K].CS(O)(=O)=O MMDSSERULWYGSW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 abstract 2
- 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 30
- 239000007788 liquid Substances 0.000 description 16
- 238000004821 distillation Methods 0.000 description 9
- 230000009466 transformation Effects 0.000 description 9
- 239000004744 fabric Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 239000008098 formaldehyde solution Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007031 hydroxymethylation reaction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QDPMLKBAQOZXEF-UHFFFAOYSA-N ethanesulfonic acid;sodium Chemical compound [Na].CCS(O)(=O)=O QDPMLKBAQOZXEF-UHFFFAOYSA-N 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 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
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000003377 acid catalyst 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
- 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
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 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
- 238000005259 measurement Methods 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance 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
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 to the improvement preparation method of a kind of wash and wear finisher in finishing functions of textile fabrics field, more specifically the preparation method of hydroxymethyl-2 dihydroxy-ethylene urea.
Technical background
Cotton fabric is subject to the favor of people because having the features such as softness, comfortable, ventilative, good hygroscopicity, but its exists the shortcoming of the easy wrinkle of easily shrinking.The effect that resination can reach Shrinkproof crease-resistant is carried out to cotton fabric.At present, conventional resin finishing agent is divided into two large classes: low aldehyde finishing composition and without aldehyde finishing composition.Formaldehydeless finishing agent safety and environmental protection, meets current development trend, but lower by its cotton fabric rebound resilience arranged, and be difficult to the requirement meeting pure cotton fabric crease and shrink resistance, and price is more expensive.Such as, without the finishing composition of aldehyde non-tree lipid, BTCA, price especially low urea formaldehyde 5-6 doubly, and the fabric xanthochromia arranged is larger.Existing market is prevailing is still the N-methylol amide resinoid of modification, wherein with the application of hydroxymethyl-2 dihydroxy-ethylene urea (2D resin) modified resin at most.
High-quality hydroxymethyl-2 dihydroxy-ethylene urea is the basis obtaining high-quality modification 2D resin.2D resin by urea, oxalic dialdehyde, formaldehyde be main raw material prepare.Typical synthetic method is the method that " printing and dyeing handbook " (second edition) (2003, China Textiles Press) are recommended.By oxalic dialdehyde, urea joins " single stage method " technique of synchronized compound in reactor and oxalic dialdehyde and urea and is first cyclized into dihydroxy ethylene urea, then carry out " two-step approach " technique of hydroxymethylation with formaldehyde together with formaldehyde.Single stage method time-saving energy-saving, but by product is many, more difficult control.Two-step approach can make proportioning raw materials accurate, and react more easy to control, the resin quality of synthesis is more stable.No matter be single stage method or two step method, in reaction, oxalic dialdehyde transformation efficiency is not high, oxalic dialdehyde existence affect the application performance of product, cause fabric xanthochromia.In addition, the concentration of 2D rosin products is higher, is more conducive to the carrying out of the etherification modified reaction of follow-up 2D resin.And 2D resin prepared by traditional two step method, during high density, storage stability is bad, affects the etherification modified reaction of product.
For two-step process, although there are many professional journals to report the improvement of many sections of synthetic methods, but be optimized to reduce formaldehyde content from conditions such as proportioning raw materials, temperature of reaction, reaction times mostly, seldom relate in raising oxalic dialdehyde transformation efficiency, high density product are stable and reactive etc.
Therefore, simple in the urgent need to a kind of technique in this area, reacting balance, the improvement preparation method of the hydroxymethyl-2 dihydroxy-ethylene urea that transformation efficiency is high.
Summary of the invention
In order to overcome the deficiency of existing hydroxymethyl-2 dihydroxy-ethylene urea two step method preparation technology, the object of the present invention is to provide the preparation method of the DP finish of cotton fabric agent that a kind of high conversion, high reactive group, high-concentration and stable are good.This preparation method innovates on existing technology of preparing basis.The first step reaction introduce sulfonic acid catalyst, make oxalic dialdehyde transformation efficiency greatly improve.Second step optional organic alcohol amine and formaldehyde pre-neutralization, conventional sodium carbonate or sodium hydroxide is replaced again in conjunction with phosphate-based buffer system, overcoming conventional two-step process causes reaction system pH-value fluctuation range large, unmanageable defect, thus stable reaction conditions is easily controlled, be beneficial to hydroxymethylation, improve the activity group content in product.Meanwhile, the stability of strength products is significantly improved.
Specifically, the invention provides the preparation method of the hydroxymethyl-2 dihydroxy-ethylene urea that following formula I represents,
The method comprises the following steps:
1) under sulfonic acid and sodium sulfonate exist, urea and oxalic dialdehyde is made to react 3 ~ 6 hours 30 ~ 60 DEG C, obtained dihydroxy ethylene urea intermediate; With
2) under phosphoric acid hydrogen two an alkali metal salt and biphosphate an alkali metal salt exist, make to react 2 ~ 4 hours with the mixture of formaldehyde and optional organic alcohol amine at 40 ~ 60 DEG C in the dihydroxy ethylene urea intermediate of gained in step 1), obtain title product.
Preparation method's technique of the present invention is simple, and reacting balance, transformation efficiency is high.The Product Activity group content of preparation is high, and high dense product stability is good.
Embodiment
The available following reaction equation of preparation of high conversion of the present invention, high reactive group wash and wear finisher represents:
The first step of the present invention is urea and oxalic dialdehyde ring structure, obtained dihydroxy ethylene urea intermediate.Then, intermediate and formaldehyde hydroxymethylation obtain target product.
In the inventive method, in described step (1), temperature of reaction is 30 ~ 60 DEG C, is preferably 35 ~ 60 DEG C.Reaction times is 3 ~ 6 hours, is preferably 4 ~ 5 hours.
In described step (2), temperature of reaction is 40 ~ 60 DEG C, is preferably 50 ~ 60 DEG C.Reaction times is 2 ~ 4 hours, is preferably 3 ~ 4 hours.
Organic alcohol amine in described step (2) be dimethylaminoethanol, diethylaminoethanol, diethylin propyl alcohol, dimethylamino butanols one or both.
In the methods of the invention, described oxalic dialdehyde: urea: ratio 1:(1.0 ~ 1.2 of the amount of substance of formaldehyde): (1.8 ~ 2.0), are preferably 1 ︰ 1.02 ︰ 1.8 ~ 1 ︰ 1.1 ︰ 1.9.
In one preferred embodiment, method of the present invention is also included in 50 ~ 80 DEG C, and be preferably 55 ~ 70 DEG C, vacuum tightness be-0.080 ~-0.1MPa, the product obtained in underpressure distillation step (2) under the condition of preferably-0.085 ~-0.1MPa.
In one preferred embodiment, the sulfonic acid in step 1) and the mass ratio of sulfonic acid alkali metal salts are 1:2 ~ 1:15, are preferably 1:3 ~ 1:10.
In a particularly preferred embodiment, the sulfonic acid in step 1) and the total mass of sulfonic acid alkali metal salts are the 0.2-2% of oxalic dialdehyde quality, are preferably 0.4-1.6%.
In one preferred embodiment, above-mentioned sulfonic acid comprises C
1-3alkylsulphonic acid, C
6-10aryl sulfonic acid or their mixture.Above-mentioned sulfonic acid alkali metal salts comprises C
1-3alkylsulphonic acid an alkali metal salt, C
6-10aryl sulfonic acid an alkali metal salt or their mixture.
In a particularly preferred embodiment, above-mentioned C
1-3alkylsulphonic acid is methylsulphonic acid, above-mentioned C
1-3alkylsulphonic acid an alkali metal salt is novalgin, methylsulphonic acid potassium or their mixture; Above-mentioned C
6-10aryl sulfonic acid is Phenylsulfonic acid, Phenylsulfonic acid or their mixture; Above-mentioned C
6-10aryl sulfonic acid an alkali metal salt is benzene sulfonic acid sodium salt, Phenylsulfonic acid potassium or their mixture.
In one preferred embodiment, step 2) in phosphoric acid hydrogen two an alkali metal salt and the mass ratio 6:1 ~ 25:1 of biphosphate an alkali metal salt, be preferably 10:1 ~ 20:1.
In a particularly preferred embodiment, step 2) in phosphoric acid hydrogen two an alkali metal salt and the total mass of biphosphate an alkali metal salt be the 1-4% of oxalic dialdehyde quality, be preferably 2-3%.
In a particularly preferred embodiment, above-mentioned phosphoric acid hydrogen two an alkali metal salt is Sodium phosphate dibasic, dipotassium hydrogen phosphate or their mixture, and above-mentioned biphosphate an alkali metal salt is SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate or their mixture.
In one preferred embodiment, step 2) in organic alcohol amine quality be the 0-5% of formaldehyde quality, be preferably 0.5%-5%, be more preferably 1 ~ 4%.
In sum, the invention provides the preparation method of wash and wear finisher, reacting balance, easily control; The product reactivity of preparation is high, and transformation efficiency is high, high density product stability is good.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Experimental data in each embodiment is measured with the following method:
1) oxalic dialdehyde residual rate adopt KOH dropping point method.
Accurately take 1.000g sample in iodine flask, add the dilution of 30ml deionized water, add 2 Bromothymol blue indicator, be titrated to micro-blueness by the NaOH solution of 0.1mol/L, keep 5s not fade for terminal.Then add the KOH standardized solution 10.00ml of 1.5mol/L, place 15min, be titrated to blue disappearance with the HCl standardized solution of 0.5mol/L.Write down the volume V of consumption.
Oxalic dialdehyde residual rate R%=[(C
1v
1-C
2v
2) × 0.05804/m] × 100
In formula: C1: the actual volume adding KOH standardized solution, ml;
The actual concentrations of V1:KOH standardized solution, mol/L;
C2:HCl standardized solution actual concentrations, mol/L
V2: titration consumes the volume of HCl standardized solution, ml.
M: the quality of sample, g.
0.05804:0.001mol KOH be converted into oxalic dialdehyde quality.
Oxalic dialdehyde transformation efficiency then calculates according to oxalic dialdehyde residual rate, is specially:
Oxalic dialdehyde transformation efficiency %=[(M
2-R × M
1)/M
2] × 100
In formula:
M2: oxalic dialdehyde total mass, g
M1: reactant total mass during mensuration oxalic dialdehyde residual rate, g
R: oxalic dialdehyde residual rate.
2) active group-hydroxymethyl formaldehyde content measures according to GB5543-2006.
3) mensuration of refractive index: with Abbe refractometer 25 DEG C of mensuration.
4) high density product stability measures: put at ambient temperature by the product of simmer down to solid content about 80%, observes product and whether becomes muddy or particulate matter precipitation.
Embodiment 1
In 1 liter of four mouthfuls of round-bottomed flask that agitator, thermometer and prolong are housed, add oxalic dialdehyde 290 grams (content 40%), then add 126 grams, urea (content 99%), 35 DEG C of stirring and dissolving.Then methylsulphonic acid 0.12g(content 70% is added), novalgin 0.60g(content 98%), in 40 DEG C, react 2 hours; Add novalgin 0.20g again, be warming up to 55 DEG C, continue reaction 2 hours.Measure oxalic dialdehyde residual quantity (the results are shown in Table 1).
Then reactant is cooled to 50 DEG C, add Sodium phosphate dibasic 2.6g, SODIUM PHOSPHATE, MONOBASIC 0.16g, within 1-2 hour, drip the mixed solution (dimethylaminoethanol adds in formaldehyde solution in advance) of 300g formaldehyde solution (37%) and 2.5g dimethylaminoethanol, continue reaction 4 hours at 50 DEG C, obtain light yellow transparent liquid.Measure active group hydroxymethyl formaldehyde content (the results are shown in Table 1).
By above-mentioned light yellow transparent liquid at 60 DEG C, under vacuum tightness-0.090 ~-0.098Mpa condition, underpressure distillation goes out unreacted raw material and other waste liquid, and the solid content 80% of light yellow transparent liquid remaining to matrass stops distillation, is obtained high density wash and wear finisher.Measuring product refractive index is 1.4266.Observe the stability (the results are shown in Table 1) of product.
Embodiment 2
In 1L tetra-mouthfuls of round-bottomed flasks that agitator, thermometer and prolong are housed, add oxalic dialdehyde 290 grams (content 40%), then add 130 grams, urea (content 99%), 35 DEG C of stirring and dissolving.Then ethylsulfonic acid 0.21g(content 70% is added), ethylsulfonic acid sodium 0.82g(content 98%), in 40 DEG C, react 2 hours; Add ethylsulfonic acid sodium 0.50g again, be warming up to 50 DEG C, continue reaction 2 hours.Measure oxalic dialdehyde residual quantity (the results are shown in Table 1).
Then Sodium phosphate dibasic 2.8g is added, SODIUM PHOSPHATE, MONOBASIC 0.20g, 1-2 hour drip 300g formaldehyde solution (37%) and 2.5g dimethylaminoethanol, 1.5g diethylin propyl alcohol mixed solution (dimethylaminoethanol and diethylin propyl alcohol add in formaldehyde solution in advance), continue reaction 3 hours at 55 DEG C, obtain light yellow transparent liquid.Measure active group hydroxymethyl formaldehyde content (the results are shown in Table 1).
By above-mentioned light yellow transparent liquid at 60 DEG C, under vacuum tightness-0.090 ~-0.098Mpa condition, underpressure distillation goes out unreacted raw material and other waste liquid, and the solid content 80% of light yellow transparent liquid remaining to matrass stops distillation, is obtained high density wash and wear finisher.Measuring product refractive index is 1.4268.Observe the stability (the results are shown in Table 1) of product.
Embodiment 3
In four mouthfuls of round-bottomed flasks that agitator, thermometer and prolong are housed, add oxalic dialdehyde 290 grams (content 40%), then add 130 grams, urea (content 99%), 35 DEG C of stirring and dissolving.Then Phenylsulfonic acid 0.30g(content 80% is added), benzene sulfonic acid sodium salt 0.80g(content 98%), in 40 DEG C, react 2 hours; Add benzene sulfonic acid sodium salt 0.45g again, be warming up to 50 DEG C, continue reaction 2 hours.Measure oxalic dialdehyde residual quantity (the results are shown in Table 1).
Then dipotassium hydrogen phosphate 2.8g is added, potassium primary phosphate 0.20g, 1-2 hour drip 300g formaldehyde solution (37%) and 2.5g dimethylaminoethanol, 1.5g diethylin propyl alcohol mixed solution (dimethylaminoethanol and diethylin propyl alcohol add in formaldehyde solution in advance), continue reaction 3 hours at 55 DEG C, obtain light yellow transparent liquid.Measure active group hydroxymethyl formaldehyde content (the results are shown in Table 1).
By above-mentioned light yellow transparent liquid at 60 DEG C, under vacuum tightness-0.090 ~-0.098Mpa condition, underpressure distillation goes out unreacted raw material and other waste liquid, and the solid content 80% of light yellow transparent liquid remaining to matrass stops distillation, is obtained high density wash and wear finisher.Measuring product refractive index is 1.4265.Observe the stability (the results are shown in Table 1) of product.
The preparation of reference example 1(tradition two step method, " printing and dyeing handbook " (second edition))
In 1L tetra-mouthfuls of round-bottomed flasks that agitator, thermometer and prolong are housed, add oxalic dialdehyde 290 grams (content 40%), then add 126 grams, urea (content 99%), be warming up to 35 DEG C, stop heating.Then add the soda ash 4g of 25%, regulate pH5-5.5, in 50 DEG C of reactions 2 hours.Measure oxalic dialdehyde residual quantity (the results are shown in Table 1).
Then add 300g formaldehyde solution (37%), then regulate pH8.2-8.5 with the soda ash of 25%, 50 DEG C of reactions 3 hours, cooling, regulated pH6-6.5, obtains light yellow transparent liquid.Measure active group hydroxymethyl formaldehyde content (the results are shown in Table 1).
By above-mentioned light yellow transparent liquid at 60 DEG C, under vacuum tightness-0.090 ~-0.098Mpa condition, underpressure distillation goes out unreacted raw material and other waste liquid, and the solid content 80% of light yellow transparent liquid remaining to matrass stops distillation, is obtained high density wash and wear finisher.Measuring product refractive index is 1.4263.Observe the stability (the results are shown in Table 1) of product.
The determination data of table 1 embodiment and reference example
Note: embodiment 1, embodiment 2, embodiment 3 and comparative example 1 product, Theoretical Calculation and 100% solid content, hydroxymethyl formaldehyde content is 32.19%; During the hydroxymethyl formaldehyde content of practical measurement product, product solid content is 45%.
The data declaration of table 1, of the present inventionly improve one's methods compared with traditional two step method, significantly reduce oxalic dialdehyde residual quantity, namely oxalic dialdehyde transformation efficiency significantly improves, the product that the active group hydroxymethyl formaldehyde content of product is prepared far above traditional method, meanwhile, the storage stability of product significantly improves.
Claims (10)
1. the preparation method of hydroxymethyl-2 dihydroxy-ethylene urea that represents of following formula I,
The method comprises the following steps:
1) under the existence of sulfonic acid and sulfonic acid alkali metal salts, urea and oxalic dialdehyde is made to react 3 ~ 6 hours 30 ~ 60 DEG C, obtained dihydroxy ethylene urea intermediate; With
2) under phosphoric acid hydrogen two an alkali metal salt and biphosphate an alkali metal salt exist, make the dihydroxy ethylene urea intermediate of gained in step 1) and the mixture of formaldehyde and optional organic alcohol amine react 2 ~ 4 hours at 40 ~ 60 DEG C, obtain title product.
2. preparation method as claimed in claim 1, is characterized in that, described organic alcohol amine be dimethylaminoethanol, diethylaminoethanol, diethylin propyl alcohol, dimethylamino butanols one or both.
3. preparation method as claimed in claim 1, it is characterized in that, described sulfonic acid and the mass ratio of sulfonic acid alkali metal salts are 1:2 ~ 1:15, are preferably 1:3 ~ 1:10.
4. preparation method as claimed in claim 1, is characterized in that, described phosphoric acid hydrogen two an alkali metal salt and the mass ratio 6:1 ~ 25:1 of biphosphate an alkali metal salt, is preferably 10:1 ~ 20:1.
5. the preparation method as described in claim 1 or 3, is characterized in that, described sulfonic acid and the total mass of sulfonic acid alkali metal salts are 0.2 ~ 2% of oxalic dialdehyde quality, is preferably 0.4-1.6%.
6. the preparation method as described in claim 1 or 4, is characterized in that, described phosphoric acid hydrogen two an alkali metal salt and the total mass of biphosphate an alkali metal salt are the 1.0-4.0% of oxalic dialdehyde quality, is preferably 2-3%.
7. preparation method as claimed in claim 1, it is characterized in that, described organic alcohol amine quality is the 0.5%-5% of formaldehyde quality, is preferably 1 ~ 4%.
8. preparation method as claimed in claim 1, is characterized in that, oxalic dialdehyde: urea: formaldehyde mol ratio 1:(1.0 ~ 1.2): (1.8 ~ 2.0).
9. preparation method as claimed in claim 1, it is characterized in that, described sulfonic acid comprises C
1-3alkylsulphonic acid, C
6-10aryl sulfonic acid or their mixture, described sulfonic acid alkali metal salts comprises C
1-3alkylsulphonic acid an alkali metal salt, C
6-10aryl sulfonic acid an alkali metal salt or their mixture.
10. preparation method as claimed in claim 9, is characterized in that, described C
1-3alkylsulphonic acid is methylsulphonic acid, described C
1-3alkylsulphonic acid an alkali metal salt is novalgin, methylsulphonic acid potassium or their mixture, described C
6-10aryl sulfonic acid is Phenylsulfonic acid, Phenylsulfonic acid or their mixture, described C
6-10aryl sulfonic acid an alkali metal salt is benzene sulfonic acid sodium salt, Phenylsulfonic acid potassium or their mixture, described phosphoric acid hydrogen two an alkali metal salt is Sodium phosphate dibasic, dipotassium hydrogen phosphate or their mixture, and described biphosphate an alkali metal salt is SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate or their mixture.
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