CN1291042C - Method for preparing modified cyanurotriamide resin for leather retanning and filling - Google Patents
Method for preparing modified cyanurotriamide resin for leather retanning and filling Download PDFInfo
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- CN1291042C CN1291042C CN 200510050474 CN200510050474A CN1291042C CN 1291042 C CN1291042 C CN 1291042C CN 200510050474 CN200510050474 CN 200510050474 CN 200510050474 A CN200510050474 A CN 200510050474A CN 1291042 C CN1291042 C CN 1291042C
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- leather
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- 239000010985 leather Substances 0.000 title claims abstract description 38
- 150000007974 melamines Chemical class 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000011049 filling Methods 0.000 title claims abstract description 16
- 229920005989 resin Polymers 0.000 title abstract description 13
- 239000011347 resin Substances 0.000 title abstract description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004640 Melamine resin Substances 0.000 claims abstract description 26
- 238000007259 addition reaction Methods 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 8
- 230000005494 condensation Effects 0.000 claims abstract description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003607 modifier Substances 0.000 claims description 23
- TZLNJNUWVOGZJU-UHFFFAOYSA-M sodium;3-chloro-2-hydroxypropane-1-sulfonate Chemical compound [Na+].ClCC(O)CS([O-])(=O)=O TZLNJNUWVOGZJU-UHFFFAOYSA-M 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 238000007031 hydroxymethylation reaction Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000006277 sulfonation reaction Methods 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000004503 fine granule Substances 0.000 abstract 1
- 230000002209 hydrophobic effect Effects 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 7
- 229910021538 borax Inorganic materials 0.000 description 7
- 239000006172 buffering agent Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000004328 sodium tetraborate Substances 0.000 description 7
- 235000010339 sodium tetraborate Nutrition 0.000 description 7
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- NWISHBWZLSLOBC-UHFFFAOYSA-N 3-chloro-2-hydroxypropane-1-sulfonic acid;sodium Chemical compound [Na].ClCC(O)CS(O)(=O)=O NWISHBWZLSLOBC-UHFFFAOYSA-N 0.000 description 4
- 229910004879 Na2S2O5 Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- CLHYKAZPWIRRRD-UHFFFAOYSA-N 1-hydroxypropane-1-sulfonic acid Chemical compound CCC(O)S(O)(=O)=O CLHYKAZPWIRRRD-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- AHCDZZIXAMDCBJ-UHFFFAOYSA-N CCC[Na] Chemical compound CCC[Na] AHCDZZIXAMDCBJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 241001248531 Euchloe <genus> Species 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- SUPOBRXPULIDDX-UHFFFAOYSA-N [[4-amino-6-(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound NC1=NC(NCO)=NC(NCO)=N1 SUPOBRXPULIDDX-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000031877 prophase Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 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
- 229920003002 synthetic resin Polymers 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to a method for preparing modified melamine resin for the retanning and the filling of leather. Melamine and formaldehyde make an addition reaction under the faintly alkali condition in the prior art and are polycondensed to generate modified melamine resin under the acid condition, the products are in a basically solid powder form and continue to release formaldehyde in leather because of incomplete resin condensation, less hydrophobic property, moisture sensitivity, tumefaction occurrence and large moisture absorption degree of the finished leather, and the formaldehyde has adverse effect on hide fibers. The present invention provides a new method for preparing modified melamine resin for the retanning and the filling of leather, 3-chlorine-2-hydroxyl sodium propyl xansonate is prepared by the reaction of epoxy chloropropane and sodium bisulfite and further modifies the hydroxymethylated and sulfonated melamine, and thereby, the stability of the products is enhanced. The products can be stored in a liquid form and can be used for the working procedures of the tanning and the filling of leather, and thereby, the leather has the advantages of smooth grain surface, fine granule patterns, and plumpy and soft leather body.
Description
Technical Field
The invention belongs to a preparation method of modified melamine resin, and particularly relates to a preparation method of modified melamine resin for leather retanning filling.
Background
The melamine resin prepolymer is prepared by addition reaction of melamine and formaldehyde, has good retanning and filling effects on leather, and has certain dyeing assisting capability because amino and imino in the molecule can show cationic property in a dyeing medium. Compared with other tanning agents, the tanning agents have weaker bonding force with collagen and mainly play a filling role in leather. The anionic amino resin has good selective filling property and very low convergence, can increase the fullness of leather when used for retanning chrome tanned leather, ensures that the grain surface of the leather is compact and smooth, does not obviously weaken the characteristics of the chrome tanned leather, can increase the level-dyeing property of the leather, and improves the buffing and embossing properties of the leather.
In the synthesis of melamine resin, melamine and formaldehyde are reacted in a molar ratio of 1: 3 to obtain water-soluble resin. The solution is further subject to continued condensation during storage, which increases the viscosity of the solution and results in a transparent jelly. When retanning with such resins, the retanning agent enters the skin and, during storage, becomes brittle, especially with vegetable tanning agents, as the pH decreases. The principle is as follows: the melamine resin is prepared by carrying out addition reaction on 1 mole of melamine and 2-3 moles of formaldehyde under the condition of alkalescence to generate dimethylolmelamine and trimethylolmelamine, and various methylolmelamines are further subjected to polycondensation under the acid condition to generate an initial polycondensate containing a methine bond and ether bond linkage structure, so that the storage stability of the resin is reduced, the resin is shrunk due to slow polycondensation of residual methylol, and internal stress can be generated to cause cracking of the surface of leather. Thus, the resin causes the following undesirable consequences in the leather retanning process:
(1) the resin is incompletely condensed, has low hydrophobicity, is sensitive to moisture, can swell and has high moisture absorption of finished leather.
(2) The formaldehyde is released continuously in the condensation process of forming insoluble resin in the leather, and the excessive formaldehyde has adverse effect on the state of leather fibers and reduces the mechanical strength of the leather in a short time.
The modified melamine resin retanning agents currently on the market are essentially sold in the form of solid powders.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of modified melamine, the modified melamine resin prepared by the invention has excellent performance when being used for leather retanning and filling, the finished leather is not hard and cracked, the dyeing is not influenced, and the storage stability and the water solubility are good.
The technical scheme adopted by the invention is as follows:
a method for preparing modified melamine resin for leather retanning filling is characterized by comprising the following steps of modifier synthesis, hydroxymethylation and sulfonation modification and modification by a self-made modifier:
(1) and (3) synthesis of a modifier: sodium bisulfite and epoxy chloropropane are synthesized into the 3-chloro-2-hydroxy sodium propane sulfonate modifier in a molar ratio of 1: 1, the reaction temperature in the synthesis process needs to be strictly controlled, the early reaction temperature is controlled to be 30-70 ℃, the early reaction time is 1-4 hr, the later reaction temperature is controlled to be 60-100 ℃, and the later reaction time is 0.5-3 hr;
(2) hydroxymethylation and sulfonation modification: performing addition reaction on formaldehyde and melamine at a molar ratio of 1.2-3.1: 1, then adding a sulfonating agent to further condense to generate hydroxymethylated and sulfonated melamine, wherein the molar ratio of the sulfonating agent to the melamine is 1-3: 1 in terms of sulfonic acid groups, and the pH value is adjusted to 8.0-10.0 in the reaction process;
(3) modifying by using a self-made modifier: modifying the hydroxymethylated and sulfonated melamine obtained in the step (2) by using the sodium 3-chloro-2-hydroxypropanesulfonate modifier obtained in the step (1) to obtain modified melamine resin, wherein the molar ratio of the modifier to the hydroxymethylated and sulfonated melamine is 0.5-2: 1, the pH value is adjusted to 8.0-10.0 in the modification process, the temperature is controlled to be 60-100 ℃, and the time is 1-6 hours.
In the synthesis process of the modifier in the step (1), the early reaction temperature is controlled to be 40-60 ℃, the early reaction time is 2-3 hr, the late reaction temperature is controlled to be 70-90 ℃, and the late reaction time is 1-2 hr.
In the step (2), the molar ratio of the addition reaction of the formaldehyde and the melamine is 1.5-2.8: 1, the molar ratio of the sulfonating agent to the further condensation of the melamine in terms of sulfonic acid groups is 1.5-2: 1, and the pH value is adjusted to 8.5-9.5 in the condensation process.
In the step (3), the mole ratio of the 3-chlorine-2-hydroxyl propyl sodium sulfonate modifier to the hydroxymethylation and the sulfonated melamine is 0.5-1.8: 1, the pH value is adjusted to 8.5-9.5 in the modification process, the temperature is controlled at 70-90 ℃, and the time is 2-5 hr.
The chemical reaction mechanism of the invention is as follows:
the preparation principle of the modifier 3-chloro-2-hydroxypropanesulfonic acid sodium salt is as follows:
the synthetic principle of the modified resin is as follows:
r-represents the residue of melamine.
In the synthesis process of the modifier 3-chloro-2-sodium hydroxypropanesulfonate, epichlorohydrin is easy to self-polymerize if the reaction is under an alkaline condition, and the hydroxymethylation of the resin is influenced if the pH value of the synthesized solution is too low. Therefore, the amount of sodium bisulfite in the reaction must be controlled. Experiments prove that the solution with good stability can be obtained by reacting the sodium bisulfite with the epichlorohydrin in a molar ratio of 1: 1 and adjusting the reaction temperature according to the progress of the reaction. Too high reaction temperature may cause excessive hydrolysis of chlorine in epichlorohydrin or sodium 3-chloro-2-hydroxypropanesulfonate to chloride ions, thereby reducing the yield of the product. Too low a temperature may reduce the reaction rate and may cause the reaction to proceed incompletely. The reaction prophase is selected according to the experiment: controlling the temperature to be 30-70 ℃, preferably 40-60 ℃, and the time to be 1-4 h, preferably 2-3 h; and (3) at the later stage of reaction: the temperature is 60-100 ℃, preferably 70-90 ℃, and the time is 0.5-3 h, preferably 1-2 h.
In the hydroxymethylation process, the molar ratio of the addition reaction of the formaldehyde and the melamine influences the subsequent reaction capability of the product, and simultaneously determines the formaldehyde content of the treated leather. Therefore, the molar ratio is required to be 3: 1 or less than 3: 1, preferably in the range of 3.1: 1 to 1.2: 1, more preferably in the range of 2.8: 1 to 1.5: 1, and the pH is adjusted to 8.0 to 10.0, more preferably 8.5 to 9.5.
After methylolation reaction of melamine and formaldehyde, water soluble resin is obtained, but the resin is condensed continuously during storage to raise the viscosity of the solution and form transparent jelly. Therefore, the initial polymer resin is not suitable for cooling and placing in the reaction, and the sulfonation reaction is directly carried out. Otherwise, white substances are likely to precipitate (solidify) and are less soluble even when heated later. Because the increase of the sulfonic group can influence the dyeing rate of the leather anionic dye after the leather anionic dye is retanned, and too few sulfonic groups can influence the water solubility of a final product, the molar ratio of the sulfonic group to the melamine is controlled within the range of 1: 1-3: 1, and the preferable molar ratio is 1.5: 1-2: 1; regulating deviceThe pH value is 8-10, preferably 8.5-9.5. The sulfonating agent used is various, generally NaHSO3Or Na2S2O5。
Application experiments on pigskin clothing leather show that the molar ratio of the self-made modifier to melamine is different in the modification process, and the application effect is different. The method is characterized in that the application experiment effect determines that the molar ratio of the self-made modifier 3-chloro-2-sodium hydroxypropanesulfonate to hydroxymethylation and sulfonated melamine is 0.5-2: 1, preferably 0.5: 1-1.8: 1, the pH value is adjusted to 8.0-10.0, preferably 8.5-9.5, the reaction temperature is controlled to be 60-100 ℃, preferably 70-90 ℃, the reaction time is controlled to be 1-6 hours, and preferably 2-5 hours.
Compared with the prior art, the modified melamine retanning filler prepared by the method is stored in a liquid form, the stability is more than 12 months, the leather after retanning is soft and plump, the leather has no color fading effect, the grain surface is smooth, and the grains are fine.
Detailed Description
Example 1:
preparation of sodium 3-chloro-2-hydroxypropanesulfonate: mixing 208.12g of NaHSO3Dissolving in 693.72g of water, adding into a three-neck flask provided with a stirrer and a condenser, dropwise adding 153.04g of epichlorohydrin at the temperature of 20-25 ℃ while stirring, and after dropwise adding, heating to 40 ℃ to react for 3 hours. And continuously heating to 70 ℃ for reaction for 2 hours to obtain 3-chloro-2-hydroxypropanesulfonic acid sodium salt, cooling and placing in a closed container for later use.
Preparation of modified melamine resin: 126.12g of melamine and 194.99g of formaldehyde (37 percent by mass) are respectively added into a three-neck flask provided with a stirrer and a condenser, borax is used as a buffering agent to adjust the pH value to be about 8.5, and the three-neck flask is reacted at 80 ℃ until the melamine is dissolved. Cooling to 70 ℃, and dripping 156.09g of NaHSO3Preparing 30% solution, adjusting pH to 8.5 with 10% NaOH water solution, adding dropwise, heating to 80 deg.C, stirring for a certain time to NaHSO3And (4) completely reacting. And then cooling to 70 ℃, dripping 861.2g of the sodium 3-chloro-2-hydroxypropanesulfonate solution, adjusting the pH value of the reactant to 8.5 by using a 10% NaOH aqueous solution, raising the temperature to 85 ℃, stirring for 2 hours, controlling the solid content of the product to be 30-40%, cooling and discharging, wherein the product is colorless transparent liquid, and the application effect is excellent.
Example 2:
preparation of sodium 3-chloro-2-hydroxypropanesulfonate: 104.06g of NaHSO3Dissolving in 346.86g of water, addinginto a three-neck flask provided with a stirrer and a condenser, dropwise adding 76.52g of epichlorohydrin at the temperature of 20-25 ℃ while stirring, and after dropwise adding, heating to 60 ℃ to react for 2 hours. And continuously heating to 90 ℃ for reaction for 1h to obtain 3-chloro-2-hydroxypropanesulfonic acid sodium salt, cooling and placing in a closed container for later use.
Preparation of modified melamine resin: 63.06g of melamine and 97.48g of formaldehyde (37 percent by mass) are respectively added into a three-neck flask provided with a stirrer and a condenser, borax is used as a buffering agent to adjust the pH value to be about 9, and the three-neck flask is reacted at 80 ℃ until the melamine is dissolved. Cooling to 70 ℃, and dripping 71.29gNa2S2O5Preparing 30% solution, adjusting pH to 9.0 with 10% NaOH water solution, adding dropwise, heating to 80 deg.C, stirring for a certain time to Na2S2O5And (4) completely reacting. And then cooling to 70 ℃, dripping 430.61g of the synthesized sodium 3-chloro-2-hydroxypropanesulfonate solution, adjusting the pH value of the reactant to 9.0 by using a 10% NaOH aqueous solution, raising the temperature to 85 ℃, stirring for 2 hours, controlling the solid content of the product to be 30% -40%, cooling and discharging, wherein the product is colorless transparent liquid and has good application effect.
Example 3:
sodium 3-chloro-2-hydroxypropanesulfonate was prepared as in example 2.
Preparation of modified melamine resin: 126.12g of melamine and 121.6g of formaldehyde (37 percent by mass) are respectively added into a three-neck flask provided with a stirrer and a condenser, borax is used as a buffering agent to adjust the pH value to be about 9, and the reaction is carried out at 80 ℃ until the melamine is dissolved. Cooling to 70 ℃, and dropwise adding 208g of NaHSO3Preparing 30% solution, using 10%Adjusting pH to 9.5 with NaOH water solution, heating to 80 deg.C after dropwise adding, and stirring for a certain time to NaHSO3And (4) completely reacting. Then cooling to 70 ℃, dropwise adding 1033g of the obtained 3-chloro-2-hydroxypropanesulfonic acid sodium solution, simultaneously adjusting the pH value of the reactant to 9.0 by using a 10% NaOH aqueous solution, keeping the temperature at 70 ℃, reacting for 5h, controlling the solid content of the product to be 30% -40%, cooling and discharging, wherein the product is colorless transparent liquid and has good application effect.
Example 4:
sodium 3-chloro-2-hydroxypropanesulfonate was prepared as in example 2.
Preparation of modified melamine resin: 126.12g of melamine and 227g of formaldehyde (the mass content is 37%) are respectively added into a three-neck flask provided with a stirrer and a condenser, borax is used as a buffering agent, the pH value is adjusted to be about 9.5, and the reaction is carried out at 80 ℃ until the melamine is dissolved. Cooling to 70 ℃, and dripping 228.8g of NaHSO3Preparing 30% solution, adjusting pH to 9.0 with 10% NaOH water solution, adding dropwise, heating to 80 deg.C, stirring for a certain time to NaHSO3And (4) completely reacting. And then cooling to 70 ℃, dripping 286.95g of the obtained 3-chloro-2-hydroxypropanesulfonic acid sodium solution, adjusting the pH value of the reactant to 9.5 by using a 10% NaOH aqueous solution, heating to 90 ℃, reacting for 2 hours, controlling the solid content of the product to be 30% -40%, cooling and discharging, wherein the product is colorless transparent liquid, and the application effect is good.
Example 5:
preparation of sodium 3-chloro-2-hydroxypropanesulfonate: 260.15g of NaHSO3Dissolving in 867.15g of water, adding into a three-neck flask provided with a stirrer and a condenser, dropwise adding 191.3g of epichlorohydrin while stirring at 20-25 ℃, after dropwise adding, heating to 70 ℃ and reacting for 1 h. And continuously heating to 100 ℃ for reaction for 0.5h to obtain 3-chloro-2-hydroxypropanesulfonic acid sodium salt, cooling, and placing in a closed container for later use.
Preparation of modified melamine resin: 126.12g of melamine and 97.3g of formaldehyde (mass content: 37%) are respectively added into a three-neck flask provided with a stirrer and a condenser, borax is used as a buffering agent, the pH value is adjusted to be about 9, and the reaction is carried out at 80 ℃ until the melamine is dissolved. Cooling to 70 ℃, and dropwise adding 208g of NaHSO3Preparing 30% solution with 1Adjusting pH to 10.0 with 0% NaOH water solution, adding dropwise, heating to 80 deg.C, stirring for a certain time to NaHSO3And (4) completely reacting. And then cooling to 70 ℃, dripping 1145.8g of the obtained 3-chloro-2-hydroxypropanesulfonic acid sodium solution, adjusting the pH value of the reactant to 8.0 by using a 10% NaOH aqueous solution, heating to 100 ℃, reacting for 1h, controlling the solid content of the product to be 30-40%, cooling and discharging, wherein the product is a primary-color transparent liquid, and the application effect is good.
Example 6:
preparation of sodium 3-chloro-2-hydroxypropanesulfonate: 52.03g of NaHSO3Dissolving in 173.43g of water, adding into a three-neck flask provided with a stirrer and a condenser, dropwise adding 38.26g of epichlorohydrin at 20-25 ℃ while stirring, and after dropwise adding, heating to 30 ℃ to react for 4 h. And continuously heating to 60 ℃ for reaction for 3h to obtain 3-chloro-2-hydroxypropanesulfonic acid sodium salt, cooling and placing in a closed container for later use.
Preparation of modified melamine resin: 126.12g of melamine and 251.4g of formaldehyde (37 percent by mass) are respectively added into a three-neck flask provided with a stirrer and a condenser, borax is used as a buffering agent, the pH value is adjusted to be about 9.5, and the reaction is carried out at 80 ℃ until the melamine is dissolved. Cooling to 70 ℃, and dripping 95gNa2S2O5Preparing 30% solution, adjusting pH to 8.0 with 10% NaOH water solution, adding dropwise, heating to 80 deg.C, stirring for a certain time to Na2S2O5And (4) completely reacting. And then cooling to 60 ℃, dripping 859.33g of the obtained 3-chloro-2-hydroxypropanesulfonic acid sodium solution, adjusting the pH value of the reactant to 10.0 by using a 10% NaOH aqueous solution, controlling the reaction temperature to be 60 ℃, reacting for 6 hours, controlling the solid content of the product to be 30% -40%, cooling and discharging, wherein the product is colorless transparent liquid, and the application effect is good.
Example 7:
sodium 3-chloro-2-hydroxypropanesulfonate was prepared as in example 6.
Preparation of modified melamine resin: 126.12g of melamine and 162.2g of formaldehyde (37 percent by mass) are respectively added into a three-neck flask provided with a stirrer and a condenser, borax is used as a buffering agent to adjust the pH value to be about 9.5, and the mixture reacts at the temperature of 80 DEG CUntil the melamine dissolves. Cooling to 70 ℃, and dripping 285gNa2S2O5Preparing 30% solution, adjusting pH to 9.0 with 10% NaOH water solution, adding dropwise, heating to 80 deg.C, stirring for a certain time to Na2S2O5And (4) completely reacting. And then cooling to 70 ℃, controlling the solid content of the product to be 30-40%, cooling and discharging, wherein the product is colorless transparent liquid with little white precipitate, and the application effect is common.
Claims (5)
1. A method for preparing modified melamine resin for leather retanning filling is characterized by comprising the following steps of modifier synthesis, hydroxymethylation and sulfonation modification and modification by a self-made modifier:
(1) and (3) synthesis of a modifier: sodium bisulfite and epoxy chloropropane are synthesized into 3-chloro-2-hydroxy sodium propane sulfonate modifier in the molar ratio of 1 to 1, and during the synthesis, the early reaction temperature is controlled at 30-70 ℃, the early reaction time is 1-4 hr, the late reaction temperature is controlled at 60-100 ℃, and the late reaction time is 0.5-3 hr;
(2) hydroxymethylation and sulfonation modification: performing addition reaction on formaldehyde and melamine at a molar ratio of 1.2-3.1: 1, adding a sulfonating agent, and further condensing to generate hydroxymethylated and sulfonated melamine, wherein the molar ratio of the sulfonating agent to the melamine is 1-3: 1 in terms of sulfonic acid groups, and adjusting the pH value to 8.0-10.0 in the condensation process;
(3) modifying by using a self-made modifier: modifying the hydroxymethylated and sulfonated melamine obtained in the step (2) by using the sodium 3-chloro-2-hydroxypropanesulfonate modifier obtained in the step (1) to obtain modified melamine resin, wherein the molar ratio of the modifier to the hydroxymethylated and sulfonated melamine is 0.5-2: 1, the pH value is adjusted to 8.0-10.0 in the modification process, the temperature is controlled to be 60-100 ℃, and the time is 1-6 hours.
2. The method for preparing modified melamine resin for leather retanning and filling according to claim 1, wherein in the step (1) of synthesizing the modifier, the early reaction temperature is controlled to be 40 ℃ to 60 ℃, the early reaction time is 2hr to 3hr, the late reaction temperature is controlled to be 70 ℃ to 90 ℃, and the late reaction time is 1hr to 2 hr.
3. The method for preparing modified melamine resin for leather retanning and filling according to claim 1 or 2, wherein in the step (2), the molar ratio of the addition reaction of formaldehyde and melamine is 1.5-2.8: 1, the molar ratio of the sulfonating agent to the further condensation of melamine in terms of sulfonic acid group is 1.5-2: 1, and the pH value is adjusted to 8.5-9.5 in the condensation process.
4. The method for preparing modified melamine resin for leather retanning filling according to claim 1 or 2, wherein the molar ratio of the hydroxymethylation to the sulfonated melamine in the step (3) is 0.5-1.8: 1 by using a sodium 3-chloro-2-hydroxypropanesulfonate modifier, the pH value is adjusted to 8.5-9.5 in the modification process, the temperature is controlled to 70-90 ℃, and the time is 2-5 hr.
5. The method for preparing modified melamine resin for leather retanning filling according to claim 3, wherein the molar ratio of the hydroxymethylation to the sulfonated melamine in the step (3) is 0.5-1.8: 1 by using a sodium 3-chloro-2-hydroxypropanesulfonate modifier, the pH value is adjusted to 8.5-9.5 in the modification process, the temperature is controlled to 70-90 ℃, and the time is 2-5 hr.
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| CN101506388B (en) * | 2006-08-23 | 2012-12-05 | 巴斯夫欧洲公司 | Compounds and their use for producing leather and as dispersants |
| CN101649362B (en) * | 2009-08-28 | 2013-06-12 | 温州大学 | Leather retanning filling agent in branched structure and preparation method thereof |
| CN101891655A (en) * | 2010-06-23 | 2010-11-24 | 程玉桥 | Method for preparing modified betaine type amphoteric surfactant used for tertiary oil recovery |
| CN102964553B (en) * | 2012-11-27 | 2013-12-18 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of modified melamine formaldehyde resin |
| CN108085435B (en) * | 2017-11-30 | 2020-10-27 | 兴业皮革科技股份有限公司 | Preparation method and application method of graphene-based protein filler |
| CN108588302B (en) * | 2018-03-06 | 2020-10-27 | 四川大学 | Preparation method of formaldehyde-free melamine resin retanning agent |
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