Cationic cyanuric chloride derivative tanning agent and preparation method thereof

Abstract

A cationic cyanuric chloride derivative tanning agent and a preparation method thereof are disclosed. The method includes: mixing 9.22-36.88 parts of cyanuric chloride, 21.35-100.31 parts of a solvent, and 7.12-33.44 parts of deionized water, all by mass, in an ice-water bath to obtain a mixture A; at a temperature of 0-5° C., adding 2.98-20.44 parts of a tertiary ammonia compound to the mixture A, and subjecting the resulting mixture to a reaction for 4-6 hours, during which its pH value is adjusted with an acid-binding agent solution to 6.0-7.0, to obtain a mixture B; filtering the mixture B, washing the filter cake, and vacuum drying for 4-6 h to obtain a solid C, and grinding to obtain the cationic cyanuric chloride derivative tanning agent.

Claims

1. A cationic cyanuric chloride derivative tanning agent, which has a structural formula of ##STR00008##

2. A method for preparing the cationic cyanuric chloride derivative tanning agent as claimed in claim 1, comprising (1) mixing 9.22-36.88 parts by mass of cyanuric chloride, 21.35-100.31 parts by mass of a solvent, and 7.12-33.44 parts by mass of deionized water in an ice-water bath, to obtain a mixture A; (2) at a temperature of 0-5° C., dropwise adding 2.98-20.44 parts of N,N-bis(3-aminopropyl)methylamine into the mixture A, and subjecting the resulting mixture to a reaction for 4-6 hours, during which a pH value of the resulting mixture is adjusted by using an acid-binding agent solution until the pH value is stabilized at 6.0-7.0, to obtain a mixture B; and (3) filtering the mixture B to obtain a filter cake, washing the filter cake, vacuum drying the washed filter cake under conditions of a vacuum degree of 0.08-0.1 MPa and a temperature of 20-25° C. for 4-6 h to obtain a solid C; grinding and crushing the solid C to obtain the cationic cyanuric chloride derivative tanning agent as a white powder.

3. The method as claimed in claim 2, wherein in step (1), the solvent is acetone or toluene.

4. The method as claimed in claim 2, wherein in step (2), an acid-binding agent in the acid-binding agent solution is sodium hydroxide or sodium carbonate.

5. The method as claimed in claim 2, wherein in step (2), the acid-binding agent solution has a mass concentration of 10-30%.

6. The method as claimed in claim 2, wherein in step (3), washing the filter cake is performed by using deionized water and/or an acetone solution with a temperature of 0-5° C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a nuclear magnetic spectrogram of the product as prepared in Example 1.

(2) FIG. 2 shows an infrared spectrogram of the product as prepared in Example 1.

(3) FIG. 3 shows a nuclear magnetic spectrogram of the product as prepared in Example 3.

(4) FIG. 4 shows an infrared spectrogram of the product as prepared in Example 3.

(5) FIG. 5 shows a nuclear magnetic spectrogram of the product as prepared in Example 5.

(6) FIG. 6 shows an infrared spectrogram of the product as prepared in Example 5.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(7) The present disclosure will be further described in detail below with conjunction with specific examples, which are explanation of the present disclosure rather than limitation.

(8) The present disclosure discloses a method for preparing a cationic cyanuric chloride derivative tanning agent, including the following steps:

(9) (1) stirring and uniformly mixing 9.22-36.88 parts by mass of cyanuric chloride, 21.35-100.31 parts by mass of a solvent, and 7.12-33.44 parts by mass of deionized water in an ice-water bath, to obtain a mixture A;

(10) (2) dropwise adding 2.98-20.44 parts of a tertiary ammonia compound into the mixture A, maintaining a temperature of 0-5° C. and reacting to obtain a mixed system; adjusting a pH of the mixed system by using an acid-binding agent solution until the pH is stabilized at 6.0-7.0, and subjecting the resulting mixture to a reaction for 4-6 hours to obtain a mixture B; and

(11) (3) filtering the mixture B to obtain a filter cake, washing the filter cake, and vacuum drying the washed filter cake under conditions of a vacuum degree of 0.08-0.1 MPa and a temperature of 20-25° C. for 4-6 h to obtain a solid C, and grinding and crushing the solid C to obtain the cationic cyanuric chloride derivative tanning agent as a white powder.

(12) The cationic cyanuric chloride derivative tanning agent prepared by the method according to the present disclosure has a structural formula of:

(13) ##STR00003##
wherein X represents O or NH; n represents 2 or 3;
Y represents CH.sub.3 or

(14) ##STR00004##

Example 1

(15) The present disclosure discloses a method for preparing a cationic cyanuric chloride derivative tanning agent. One embodiment of the method was performed according to the following procedures:

(16) 1) 9.22 g of cyanuric chloride (TCT), 25.08 g of acetone and 8.36 g of deionized water were added into a reactor equipped with a stirrer and a thermometer. The reactor was placed in an ice-water bath, and the resulting mixture therein was uniformly stirred, obtaining a mixture A.

(17) 2) At a temperature of 0° C., 5.11 g of 3-dimethylaminopropylamine was slowly dropwise added to the mixture A, and the resulting mixture was then reacted for 4 hours, during which the pH value of the reaction system was continuously adjusted with a sodium carbonate solution having a mass concentration of 10% until the pH value of the reaction system was stabilized at 6.5, obtaining a mixture B.

(18) 3) The mixture B was filtered, obtaining a filter cake. The filter cake was washed with deionized water and an acetone solution with a temperature of 3° C. respectively, with a small amount for several times. The washed filter cake was then vacuum-dried under conditions of a vacuum degree of 0.08 MPa and a temperature of 25° C. for 4 h, obtaining a solid C. The solid C was ground and crushed to obtain the cationic cyanuric chloride derivative tanning agent, as a white powder.

(19) The resultant solid was purified, and a pure product was obtained for detection.

(20) Characterization results of the product (i.e. N,N′-2-(4,6-dichloro-1,3,5-triazine-2-amino)-dimethylpropylamine, abbreviated as TAMP) synthesized from TCT and 3-dimethylaminopropylamine are as follows.

(21) ##STR00005##

(22) Analysis of nuclear magnetic spectrogram is shown in FIG. 1.

(23) Peak at δ 2.52 is a characteristic peak of a testing deuterated reagent (CD.sub.3).sub.2SO. Peak at δ 7.90 is assigned to —NH-(a). Peak at δ 3.11 is assigned to —CH.sub.2-(b). Peak at δ 2.81 is assigned to —CH.sub.2-(d). Peak at δ 1.66 is assigned to —CH.sub.2-(c). Peak at δ 2.26 is assigned to —CH.sub.3(e, e′). In connection with the aforementioned analysis, it was proved that a target product was successfully prepared.

(24) Analysis of the infrared spectrogram is shown in FIG. 2.

(25) Peak at 3207 cm.sup.−1 is ascribed to the stretching vibration of N—H. Peaks at 3026 cm.sup.−1 and 2777 cm.sup.−1 are ascribed to the stretching vibration of —CH.sub.2—. Peak at 1720 cm.sup.−1 is ascribed to the stretching vibration of C—N between C and secondary amine in a triazine ring. Peak at 1396 cm.sup.−1 is ascribed to the stretching vibration of —CH.sub.3. Peaks at 1271 cm.sup.−1 and 1051 cm.sup.−1 are ascribed to the characteristic absorption of a triazine ring skeleton. Peaks at 848 cm.sup.−1, 767 cm.sup.−1, and 705 cm.sup.−1 are ascribed to the characteristic absorption of C—Cl in a triazine compound, and it could be found that all the three absorption peaks in the TAMP spectrogram has red-shifted when compared with peaks at 1514 cm.sup.−1 and 1272 cm.sup.−1 assigned to the triazine ring skeleton in cyanuric chloride and peaks at 885 cm.sup.−1, 852 cm.sup.−1, and 796 cm.sup.−1 assigned to C—Cl characteristic absorption in cyanuric chloride. In connection with the aforementioned analysis, it could be proved that the target product TAMP was successfully prepared.

(26) TABLE-US-00001 Elemental analysis Element Theoretical value/% Test value/% C 38.40 38.79 H 5.20 5.57 Cl 28.40 27.81 N 28.00 27.83

(27) It can be seen from the elemental analysis that the measured value of each element in the synthesized compound is basically consistent with the corresponding theoretical value, which indicates that the target product is successfully prepared.

Example 2

(28) The present disclosure discloses a method for preparing a cationic cyanuric chloride derivative tanning agent. One embodiment of the method was performed according to the following procedures:

(29) 1) 36.88 g of cyanuric chloride, 100.31 g of toluene, and 33.44 g of deionized water were added into a reactor equipped with a stirrer and a thermometer. The reactor was placed in an ice-water bath, and the resulting mixture was uniformly stirred, obtaining a mixture A.

(30) 2) At a temperature of 5° C., 20.44 g of 3-dimethylaminopropylamine was slowly dropwise added to the mixture A, and the resulting mixture was reacted for 4 hours, during which the pH value of the reaction system was continuously adjusted with a sodium hydroxide solution having a mass concentration of 30% until the pH of the system was stabilized at 7.0, obtaining a mixture B.

(31) 3) The mixture B was filtered, obtaining a filter cake. The filter cake was washed with deionized water and an acetone solution with a temperature of 0° C. respectively, with a small amount for several times. The washed filter cake was then vacuum dried under conditions of a vacuum degree of 0.1 MPa and a temperature of 22° C. for 6 h, obtaining a solid C. The solid C was ground and crushed, obtaining the cationic cyanuric chloride derivative tanning agent as a white powder.

Example 3

(32) The present disclosure discloses a method for preparing a cationic cyanuric chloride derivative tanning agent. One embodiment of the method was performed according to the following procedures.

(33) 1) 9.22 g of cyanuric chloride (TCT), 21.35 g of acetone and 7.12 g of deionized water were added into a reactor equipped with a stirrer and a thermometer. The reactor was placed in an ice-water bath, and the resulting mixture was uniformly stirred, obtaining a mixture A.

(34) 2) At a temperature of 1° C., 2.98 g of N-methyldiethanolamine was slowly dropwise added to the mixture A, and the resulting mixture was then reacted for 6 hours, during which the pH value of the reaction system was continuously adjusted with a sodium carbonate solution having a mass concentration of 10% until the pH value of the system was stabilized at 7.0, obtaining a mixture B.

(35) 3) The mixture B was filtered, obtaining a filter cake. The filter cake was washed with deionized water and an acetone solution with a temperature of 2° C. respectively, with a small amount for several times. The washed filter cake was then vacuum dried under conditions of a vacuum degree of 0.09 MPa and a temperature of 24° C. for 5 h, obtaining a solid C. The solid C was ground and crushed, obtaining the cationic cyanuric chloride derivative tanning agent as a white powder.

(36) The resultant solid was purified, and a pure product was obtained for detection.

(37) Characterization results of the product (i.e. N,N′-bis-(4,6-dichloro-1,3,5-triazine-2-oxy)-diethylmethylamine, abbreviated as TYDM) synthesized from TCT and N-methyldiethanolamine are as follows.

(38) ##STR00006##

(39) Analysis of nuclear magnetic spectrogram is shown in FIG. 3.

(40) Peak at δ 2.50 is a characteristic peak of a testing deuterated reagent (CD.sub.3).sub.2SO. Peak at δ 3.93 is assigned to —CH.sub.2-(b, b′). Peak at δ 2.76 is assigned to —CH.sub.2-(c, c′). Peak at δ 2.09 is assigned to —CH.sub.3(a). In view of the above data, the target product was successfully prepared.

(41) Analysis of the infrared spectrogram is shown in FIG. 4.

(42) Peak at 2781 cm.sup.−1 is ascribed to the stretching vibration of methylene. Peaks at 1460 cm.sup.−1, 1056 cm.sup.−1, and 771 cm.sup.−1 are ascribed to the stretching vibration of a triazine ring skeleton, which have red-shifted compared with the stretching vibration peaks of the triazine ring skeleton in cyanuric chloride. Peak at 1394 cm.sup.−1 is ascribed to the stretching vibration of an ether bond. In view of the above, the target product was successfully prepared.

(43) TABLE-US-00002 Elemental analysis Element Theoretical value/% Test value/% C 31.81 31.22 H 2.65 2.95 O 7.71 8.51 Cl 34.22 33.90 N 23.61 23.42

(44) It can be seen from the elemental analysis that, the measured value of each element in the synthesized compound is basically consistent with the corresponding theoretical value, which indicates that the target product is successfully prepared.

Example 4

(45) The present disclosure discloses a method for preparing a cationic cyanuric chloride derivative tanning agent. One embodiment of the method was performed according to the following procedures.

(46) 1) 36.88 g of cyanuric chloride, 85.40 g of toluene and 28.47 g of deionized water were added into a reactor equipped with a stirrer and a thermometer. The reactor was placed in an ice-water bath, and the resulting mixture was uniformly stirred, obtaining a mixture A.

(47) 2) At a temperature of 5° C., 11.92 g of N-methyldiethanolamine was slowly dropwise added to the mixture A, and the resulting mixture was then reacted for 6 hours, during which the pH value of the reaction system was continuously adjusted with a sodium hydroxide solution having a mass concentration of 30% until the pH value of the reaction system was stabilized at 6.0, obtaining a mixture B.

(48) 3) The mixture B was filtered, obtaining a filter cake. The filter cake was washed with deionized water and an acetone solution with a temperature of 4° C. respectively, with a small amount for several times. The washed filter cake was then vacuum dried under conditions of a vacuum degree of 0.1 MPa and a temperature of 22° C. for 5 h, obtaining a solid C. The solid C was ground and crushed, obtaining the cationic cyanuric chloride derivative tanning agent as a white powder.

Example 5

(49) The present disclosure discloses a method for preparing a cationic cyanuric chloride derivative tanning agent. One embodiment of the method was performed according to the following procedures.

(50) 1) 18.44 g of cyanuric chloride (TCT), 45.00 g of acetone, and 15.00 g of deionized water were added into a reactor equipped with a stirrer and a thermometer. The reactor was placed in an ice-water bath, and the resulting mixture was uniformly stirred, obtaining a mixture A.

(51) 2) At a temperature of 5° C., 7.27 g of N,N-bis(3-aminopropyl)methylamine was slowly dropwise added to the mixture A, and the resulting mixture was then reacted for 5 hours, during which the pH value of the mixed system was continuously adjusted with a sodium hydroxide solution having a mass concentration of 30% until the pH value of the resulting system was stabilized at 6.0, obtaining a mixture B.

(52) 3) The mixture B was filtered, obtaining a filter cake. The filter cake was washed with deionized water and an acetone solution with a temperature of 4° C. respectively, with a small amount for several times. The washed filter cake was then vacuum dried under conditions of a vacuum degree of 0.1 MPa and a temperature of 20° C. for 5 h, obtaining a solid C. The solid C was ground and crushed, obtaining the cationic cyanuric chloride derivative tanning agent as a white powder.

(53) The resultant solid was purified, and a pure product was obtained for detection.

(54) Characterization results of the product (i.e. N,N′-bis-(4,6-dichloro-1,3,5-triazine-2-amino)-dipropylmethylamine, abbreviated as TADM) synthesized from TCT and N,N-bis(3-aminopropyl)methylamine are as follows.

(55) ##STR00007##

(56) Analysis of nuclear magnetic spectrogram is shown in FIG. 5.

(57) Peak at δ 2.50 is the characteristic peak of a testing deuterated reagent (CD.sub.3).sub.2SO. Peak at δ 8.17 is assigned to —NH-(e, e′). Peaks at δ 3.82 and δ 1.35 are assigned to —CH.sub.2-(c, c′). Peak at δ 3.31 is assigned to —CH.sub.2-(b, b′). Peak at δ 3.31 is assigned to —CH.sub.2-(d, d′). And peak at δ 2.09 is assigned to —CH.sub.3(a). In view of the above, the target product was successfully prepared.

(58) Analysis of the infrared spectrogram is shown in FIG. 6.

(59) Peak at 3240 cm.sup.−1 is ascribed to the stretching vibration of N—H. Peaks at 2972 cm.sup.−1 and 2788 cm.sup.−1 are ascribed to the stretching vibration of —CH.sub.2—. Peak at 1722 cm.sup.−1 is ascribed to the stretching vibration of C—N between C and secondary amine in a triazine ring. Peak at 1406 cm.sup.−1 is ascribed to the stretching vibration of —CH.sub.3. Peaks at 1232 cm.sup.1 and 1048 cm.sup.−1 are ascribed to the characteristic absorption of a triazine ring skeleton, which has red-shifted compared with the peaks at 1514 cm.sup.−1 and 1272 cm.sup.−1 assigned to the triazine ring skeleton in cyanuric chloride. In connection with the aforementioned analysis, it could be proved that the target product TAMP was successfully prepared.

(60) TABLE-US-00003 Elemental analysis Element Theoretical value/% Test value/% C 35.37 36.22 H 3.86 4.37 Cl 32.20 31.50 N 28.57 27.91

(61) It can be seen from the elemental analysis that the measured value of each element in the synthesized compound is basically consistent with the corresponding theoretical value, which indicates that the target product is successfully prepared.

Example 6

(62) The present disclosure discloses a method for preparing a cationic cyanuric chloride derivative tanning agent. One embodiment of the method was performed according to the following procedures.

(63) 1) 36.88 g of cyanuric chloride, 90.00 g of toluene and 30.00 g of deionized water were added into a reactor equipped with a stirrer and a thermometer. The reactor was placed in an ice-water bath, and the resulting mixture was uniformly stirred, obtaining a mixture A.

(64) 2) At a temperature of 4° C., 14.53 g of N,N-bis(3-aminopropyl)methylamine was slowly dropwise added to the mixture A, and the resulting mixture was then reacted for 5 hours, during which the pH value of the reaction system was continuously adjusted with a sodium carbonate solution having a mass concentration of 10% until the pH value of the reaction system was stabilized at 7.0, obtaining a mixture B.

(65) 3) The mixture B was filtered, obtaining a filter cake. The filter cake was washed with deionized water and an acetone solution with a temperature of 1° C. respectively, with a small amount for several times. The washed filter cake was then vacuum dried under conditions of a vacuum degree of 0.08 MPa and a temperature of 23° C. for 6 h, obtaining a solid C. The solid C was ground and crushed, obtaining the cationic cyanuric chloride derivative tanning agent as a white powder.

Use of the Products of Examples

(66) Salted sheep leather was subjected to a conventional processes: pre-soaking in water.fwdarw.main soaking in water.fwdarw.degreasing.fwdarw.lime-sulfide unhairing.fwdarw.weighing.fwdarw.liming.fwdarw.fleshing.fwdarw.weighing.fwdarw.deliming.fwdarw.bating.fwdarw.washing with water (the dosages of materials for the tanning experiment were calculated in terms of the weight of the limed skin; the specific tanning experiment process is shown in Table 1). The shrinkage temperature, sensory state of the white wet leather obtained after tanning, the observation results of the tanning waste fluid state are shown in Table 2. After the tanned crust leather was placed and aged for two or three days, such that the moisture content of the crust leather was maintained between 40 and 50%. The crust leather was then weighed and subjected to dyeing treatment according to the process shown in Table 3, and compared with the crust leather tanned with F-90. The dye absorption rate during dyeing and the observation results of dyeing effect are shown in Table 4.

(67) TABLE-US-00004 TABLE 1 Tanning process Dosage/ Temperature/ Time/ Operation Material % ° C. min Remarks Tanning water 200 25 Sodium chloride 10 Products of Examples 4 120 Leather Sodium Bicarbonate 1.5 45 120 Adding for 4 basifying times, pH = 6.0-6.5 Sodium Carbonate 1.0 45 120 Adding for 2 times, pH = 7.0-7.5 the drum running was stopped, and it was left to stand overnight, and rotated for 30 min on the next day, then the leather was stacked and allowed to stand, and the waste fluid was collected

(68) TABLE-US-00005 TABLE 2 Observation results of tanning waste fluid and shrinkage temperature of the white wet leather Shrinkage Chromium-free temperature/ Sensory state Color tanning agent ° C. of crust leather of waste fluid Example 1 73 White and delicate Clear Example 2 72 White and delicate Clear Example 3 75 White and delicate Milky white clear solution Example 4 76 White and delicate Milky white clear solution Example 5 76 White and delicate Relatively clear Example 6 75 White and delicate Relatively clear

(69) TABLE-US-00006 TABLE 3 Tanning and dyeing processes Dosage/ Temperature/ Time/ Operation Material % ° C. min Remarks Washing water 200 25 30 Draining with water Neutralizing water 150 Sodium bicarbonate 0.5 Sodium acetate 1.5 35 60 pH = 6.5, draining Washing water 200 25 30 pH = 6.5, draining with water Dyeing and water 150 fat liquoring Direct Red 23 3 Synthetic fat 10 50 60 liquoring agent Color Formic acid 1.0 40 60 pH = 3.5-4.0, draining fixation The waste fluid was collected, and the leather was stacked, allowed to stand and dried

(70) TABLE-US-00007 TABLE 4 Observation results of dyeing waste fluid and comparison with F-90 dyeing Dyed crust leather Color of waste fluid Dye absorptivity Example 1 Red and clear 92 Example 2 Red and clear 93 Example 3 Red and clear 93 Example 4 Red and clear 95 Example 5 Red and clear 94 Example 6 Red and clear 95 F-90 Red and relatively clear 84

(71) It can be seen from Table 2 that the cationic compound of the present disclosure, which has a core of cyanuric chloride, when used as a chrome-free tanning agent for the tanning of white wet leather, has advantage of good absorption, allows for white, flat and fine grain surface of tanned crust leather. By analysis in connection with Table 4, it can be seen that the crust leather prepared by using such tanning agent is easy to dye and has a good dyeing performance, which could provide a chrome-free tanning agent with a good performance and a feasible application process technology for the leather making industry to realize chrome-free tanning