CN103194894A - Application of tetrapyridyl pentanitrogen metal complex to low-temperature scouring and bleaching auxiliary for textiles - Google Patents

Application of tetrapyridyl pentanitrogen metal complex to low-temperature scouring and bleaching auxiliary for textiles Download PDF

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CN103194894A
CN103194894A CN2013101281949A CN201310128194A CN103194894A CN 103194894 A CN103194894 A CN 103194894A CN 2013101281949 A CN2013101281949 A CN 2013101281949A CN 201310128194 A CN201310128194 A CN 201310128194A CN 103194894 A CN103194894 A CN 103194894A
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bleaching
scouring
metal complex
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low
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毛志平
尹冲
张琳萍
徐红
钟毅
宋敏
鲁玉洁
秦新波
单宋玉
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Donghua University
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Abstract

The invention relates to application of a tetrapyridyl pentanitrogen metal complex to a low-temperature scouring and bleaching auxiliary for textiles. The low-temperature scouring and bleaching auxiliary is used for low-temperature scouring and bleaching of cotton-containing woven fabric gray cloths, knitted fabric gray cloths or gray yarns and comprises a metal complex and a scouring and bleaching auxiliary. The metal complex can improve the efficiency of the auxiliary after being added to the conventional scouring and bleaching auxiliary for textiles, is used in the pretreatment process using hydrogen peroxide as the bleaching agent, can reduce the scouring and bleaching temperature from 95-100 DEG C to 60-85 DEG C and even lower temperature, greatly reduces the production energy consumption and has good application prospect.

Description

Five application of nitrogen metal complex in the textiles low-temperature scouring and bleaching assistant of four pyridine radicals
The application is for application number is 201110379408.0, the applying date is 2011-11-24, name is called dividing an application of a kind of textiles low-temperature scouring and bleaching assistant and its preparation method and application.
Technical field
The invention belongs to textiles pre-treatment auxiliary agent Application Areas, particularly a kind of four pyridine radicals five application of nitrogen metal complex in the textiles low-temperature scouring and bleaching assistant.
Background technology
In recent years, abroad had metallic compound has been added on the precedent that increases bleaching effect in the auxiliary agent, be the hydrogen peroxide activator of OSBON such as Japanese Diaod synthetic chemical industry company number, it is used for the cold rolling heap technology of scouringing and bleaching, and can solve the uneven bleaching problem that causes because of the extraneous temperature difference and the asynchronism(-nization) of banking up.But this activator activation efficiency is not high, can not take full advantage of hydrogen peroxide, if will improve reaction efficiency, also needs to add the transition elements complex compound in activator, as manganese, copper, iron, nickel, the isoionic huge legendary turtle compound of cobalt.In solution, these complex compounds can dissociate a certain amount of metal ion, thereby play catalytic action, the decomposition rate of hydrogen peroxide is accelerated, reduce the required time of bleaching, but the metal ion that dissociates can cause very big influence to the intensity of fabric, so this activator and fail to obtain very big popularization.
Patent CN200910046259.9 discloses a kind of composition, and this composition has added manganese, zinc, the isoionic salt of aluminium, and has added the chelating agent of these metals of energy chelating, as hydrogen peroxide catalyst hydrogen peroxide bleaching.
Patent CN200810027264.0 discloses a kind of cleaning compositions that contains the metal catalytic bleach system, be a kind of the have manganese of polynary ring structure or metal complex of iron, its main application is clothes washing, main component comprises: transition metal complex, peroxide, water softener, essence, surfactant, enzyme, fluorescent whitening agent etc., the effectively spot on the clothing of place to go.
Summary of the invention
Technical problem to be solved by this invention provides five application of nitrogen metal complex in the textiles low-temperature scouring and bleaching assistant of a kind of four pyridine radicals, this scouring and bleaching assistant has added metal complex, can reduce the temperature of scouringing and bleaching, reduce energy consumption greatly, have a good application prospect.
A kind of textiles low-temperature scouring and bleaching assistant of the present invention, described low-temperature scouring and bleaching assistant comprises metal complex and scouring and bleaching assistant, the addition of metal complex is the 0.01-99.9% of gross weight.
The addition of described metal complex is the 0.01-5.0% of gross weight.
Described textiles is for containing cotton fabrics grey cloth, knit grey cloth or base yarn.
Described metal complex is N, N ', N ' '-three [salicylidene amino-ethyl] amine) metal complex, benzo four acid amides Macrocyclic metal complexes, terpyridyl metal complex, tetraazacyclododecane hexadecane metal complex, two pyridine pyrimidine metal complex, four nitrogen dicyclo tetradecane metal complexs, four pyridine radicals, five nitrogen metal complexs, Macrocyclic polyamine bridging metal complex, three pyridine radicals, four nitrogen metal complexs, 1-10 phenanthroline metal complex, bipyridyl four nitrogen metal complexs or three pyridine radicals, five nitrogen metal complexs.
Described scouring and bleaching assistant is bleaching assistant, boil and float auxiliary agent, move back to boil and float auxiliary agent, scouring agent, bleeding agent or stabilizing agent.
Described scouring and bleaching assistant is scouring agent 88-ECO, scouring enzyme DR-510, scouring agent HA-SSA, concise bleeding agent FB-18, KDN easily cotton clear, scouring agent ST-1 or stabilizing agent KDN-T.
The preparation method of a kind of textiles low-temperature scouring and bleaching assistant of the present invention comprises:
The 0.01-99.9% that metal complex is pressed the reactant gross weight adds in the scouring and bleaching assistant, stirs 15~30min, namely.
The application of a kind of textiles low-temperature scouring and bleaching assistant of the present invention, described scouring and bleaching assistant is scouringed and bleaching for the low temperature that contains cotton fabrics grey cloth, knit grey cloth or base yarn.
Beneficial effect
The metal complex that the present invention relates to adds in the conventional scouring and bleaching assistant of textiles, can increase the efficient of auxiliary agent, be used for using hydrogen peroxide as the pre-treatment process of bleaching agent, can reduce the temperature of scouringing and bleaching, the fabric temperature of scouringing and bleaching is down to 60-85 ℃ from 95-100 ℃, even can be down to more low temperature, and reduce energy consumption greatly, have a good application prospect.
Description of drawings
Fig. 1 is N, N ', N ' '-three [salicylidene amino-ethyl] amine) structural representation of metal complex; Wherein, the metal ion that M representative is different is selected from a kind of in Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Cr (I)-(II), Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III), Ni (II)-(III), Cu (I)-(II), Zn (I)-(II);
Fig. 2 is the structural representation of benzo four acid amides Macrocyclic metal complexes; Wherein, R=Me or F; X=H, Cl, NO 2, MeOOC, CH 3The metal ion that M representative is different is selected from a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Cu (I)-(II), Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Co (I)-(II)-(III);
Fig. 3 is the structural representation of terpyridyl metal complex; Wherein, R 1, R 2, R 3Independently be hydrogen, C separately 1-18Alkyl, aryl, cyano group, nitro, halogen etc.; The metal ion that M representative is different is selected from a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Cu (I)-(II), Co (I)-(II)-(III);
Fig. 4 is 5,5,7,12,12,14-hexamethyl, the structural representation of 1,4,8,11-tetraazacyclododecane hexadecane metal complex; Wherein, the metal ion that M representative is different is selected from a kind of in Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Cr (I)-(II), Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III), Ni (II)-(III), Cu (I)-(II), Zn (I)-(II);
Fig. 5 is the structural representation of two pyridine pyrimidine metal complexs; Wherein, R 1, R 2, R 3Independently be hydrogen separately, the C of replacement 1-18Alkyl or aryl, cyano group, nitro, halogen; The metal ion that M representative is different is selected from a kind of in Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Cr (I)-(II), Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III), Ni (II)-(III), Cu (I)-(II), Zn (I)-(II);
Fig. 6 is the structural representation of two pyridine pyrimidine metal complexs; Wherein, the metal ion that M representative is different, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III);
Fig. 7 is the structural representation of four pyridine radicals, five nitrogen metal complexs; Wherein, the metal ion that M representative is different, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III);
Fig. 8 is the structural representation of bridging Macrocyclic polyamine metal complexes; Wherein, the metal ion that M representative is different, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III);
Fig. 9 is the structural representation of three pyridine radicals, four nitrogen metal complexs; Wherein, the metal ion that M representative is different, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III);
Figure 10 is the structural representation of 1-10 phenanthroline metal complex; Wherein, the metal ion that M representative is different, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III); R 1, R 2, R 3, R 4Independently be hydrogen separately, the C of replacement 1-18Alkyl or aryl, cyano group, nitro, halogen etc.;
Figure 11 is the structural representation of bipyridyl four nitrogen metal complexs; Wherein, the metal ion that M representative is different, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III); R1 is methyl, ethyl; R2 is methyl, ethyl, pyridine radicals, trimethylamine groups;
Figure 12 is the structural representation of three pyridine radicals, five nitrogen metal complexs; Wherein, the metal ion that M representative is different, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III); R1, R2, R4 is selected from methyl, ethyl; R3 is selected from methyl, ethyl, hydroxyethyl, methoxy ethyl.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Take by weighing the scouring agent 88-ECO of the triumphant Chemical Manufacture of 99.8kg section, under stirring at normal temperature, evenly add the 0.2kg(mass fraction) N, N ', N ' '-three [salicylidene amino-ethyl] amine) manganese complex, interpolation finishes, and continue to stir 15min, and this scouring agent is used in the knitted fabric process of scouringing and bleaching.
The technological experiment of scouringing and bleaching: do two check experiments, 1# technology is the conventional needle fabric technology of scouringing and bleaching, and 2# technology is the low temperature that the adds metal complex catalysts technology of scouringing and bleaching.
Handle fabric: 20s cotton combing knitting single jersey, 180g/m 2
Figure BDA00003044627800031
Figure BDA00003044627800041
Table 1 result that scourings and bleaching
Figure BDA00003044627800042
Embodiment 2
Take by weighing the efficient scouring enzyme DR-510 of the flourish Chemical Manufacture of 99.9kg Wuxi moral, under stirring at normal temperature, evenly add the 0.1kg(mass fraction) the big ring iron complex of benzo four acid amides, interpolation finishes, and continues to stir 15min, obtains new auxiliary.
This example is done two check experiments, and 1# technology is the traditional woven thing technology of scouringing and bleaching, and 2# technology is the low temperature that the adds metal complex catalysts technology of scouringing and bleaching.
Handle fabric: polyester-cotton blend woven fabric T/C40 * 40*120 * 80
Figure BDA00003044627800043
Figure BDA00003044627800051
Table 2 result that scourings and bleaching
Embodiment 3
Take by weighing the multi-functional concise dose of HA-SSA that Hai'an, 49.9kg Jiangsu petrochemical plant is produced, under stirring at normal temperature, evenly add the 0.1kg(mass fraction) the terpyridyl manganese complex, interpolation finishes, and continues to stir 15min, obtains new auxiliary.This multi-functional concise dose is used in during cheese scourings and bleaching.
This example is done two check experiments, and 1# technology is traditional cheese technology of scouringing and bleaching, and 2# technology is the low temperature that the adds metal complex catalysts technology of scouringing and bleaching.
Handle fabric: textile cheese (C70S/2)
Figure BDA00003044627800053
Table 3 result that scourings and bleaching
Figure BDA00003044627800054
Embodiment 4
Take by weighing the efficient concise bleeding agent FB-18 that 49.95kg Shanghai hugeization weaving chemical science and technology research institute produces, under stirring at normal temperature, evenly add the 0.05kg(mass fraction) 5,5,7,12,12,14-vegolysen, 4,8,11-tetraazacyclododecane iron complex, interpolation finishes, continue to stir 15min, obtain new auxiliary.This infiltration scouring agent is applied in during cotton fabrics scourings and bleaching.
This example is done two check experiments, and 1# technology is the traditional cotton knitted fabric technology of scouringing and bleaching, and 2# technology is the low temperature that the adds metal complex catalysts technology of scouringing and bleaching.
Handle fabric: 20s cotton combing single jersey, 180g/m 2
Table 4 result that scourings and bleaching
Figure BDA00003044627800062
Embodiment 5
Taking by weighing 99.9kg, to go up the KDN that ground, Haikang grace biotechnology company produces easily cotton clear, evenly adds the 0.1kg(mass fraction under stirring at normal temperature) two pyridine pyrimidine radicals manganese complexes, interpolation finishes, and continues to stir 15min, obtains new auxiliary.This digesting agent is applied in the woven fabric cold bleaching.
This example is done two check experiments, and 1# technology is traditional cheese technology of scouringing and bleaching, and 2# technology is the low temperature that the adds metal complex catalysts technology of scouringing and bleaching.
Handle fabric: cotton fabrics C40 * 40*173 * 120
Figure BDA00003044627800071
Table 5 result that scourings and bleaching
Embodiment 6
Take by weighing the homemade scouring agent ST-1 of 99.9kg, add the 0.1kg(mass fraction) four nitrogen dicyclo tetradecane iron complexes, interpolation finishes, and continues to stir 15min, obtains new auxiliary.This scouring agent is used for pure cotton knitted fabric scourings and bleaching.
Table 6 self-control scouring agent ST-1 prescription
Figure BDA00003044627800073
This example is done two check experiments, and 1# technology is the conventional needle fabric technology of scouringing and bleaching, and 2# technology is the low temperature that the adds metal complex catalysts technology of scouringing and bleaching, and 3# technology is the low temperature that the does not add metal complex technology of scouringing and bleaching.
Handle fabric: 20s cotton combing single jersey, 180g/m 2
Figure BDA00003044627800081
Table 7 result that scourings and bleaching
Figure BDA00003044627800082
Embodiment 7
Take by weighing 49.94kg and go up among the stabilizing agent KDN-T that ground, Haikang grace biotechnology company produces, add the 0.06kg(mass fraction) four pyridine radicals, five nitrogen manganese complexes, this stabilizing agent is applied in cotton fabrics scourings and bleaching in the technology.
This example is done two check experiments, and 1# technology is the traditional woven thing technology of scouringing and bleaching, and 2# technology is the low temperature that the adds metal complex catalysts technology of scouringing and bleaching.
Handle fabric: cotton fabrics C40 * 40*173 * 120
Figure BDA00003044627800083
Table 8 result that scourings and bleaching
Figure BDA00003044627800092
Embodiment 8
Take by weighing the homemade scouring agent ST-1 of 99.9kg, add the 0.1kg(mass fraction) Macrocyclic polyamine bridging manganese complex, after interpolation finishes, continue to stir 15min, obtain new auxiliary, this scouring agent is used for pure cotton knitted fabric scourings and bleaching.
This example is done two check experiments, and 1# technology is the traditional woven thing technology of scouringing and bleaching, and 2# technology is the low temperature that the adds metal complex catalysts technology of scouringing and bleaching.
Handle fabric: cotton fabrics C40 * 40*173 * 120
Figure BDA00003044627800093
Figure BDA00003044627800101
Table 9 result that scourings and bleaching
Figure BDA00003044627800102
Embodiment 9
Taking by weighing 99.9kg, to go up the KDN that ground, Haikang grace biotechnology company produces easily cotton clear, evenly adds the 0.1kg(mass fraction under stirring at normal temperature) three pyridine radicals, four nitrogen manganese complexes, interpolation finishes, and continues to stir 18min, obtains new auxiliary.This digesting agent is applied in the woven fabric cold bleaching.
This example is done two check experiments, and 1# technology is traditional cheese technology of scouringing and bleaching, and 2# technology is the low temperature that the adds metal complex catalysts technology of scouringing and bleaching.
Handle fabric: cotton fabrics C40 * 40*173 * 120
Table 10 result that scourings and bleaching
Figure BDA00003044627800111
Embodiment 10
Taking by weighing 99.9kg, to go up the KDN that ground, Haikang grace biotechnology company produces easily cotton clear, evenly adds the 0.1kg(mass fraction under stirring at normal temperature) 1-10 phenanthroline manganese complex, interpolation finishes, and continues to stir 20min, obtains new auxiliary.This digesting agent is applied in the woven fabric cold bleaching.
This example is done two check experiments, and 1# technology is traditional cheese technology of scouringing and bleaching, and 2# technology is the low temperature that the adds metal complex catalysts technology of scouringing and bleaching.
Handle fabric: cotton fabrics C40 * 40*173 * 120
Figure BDA00003044627800112
Table 11 result that scourings and bleaching
Figure BDA00003044627800113
Embodiment 11
Taking by weighing 99.92kg, to go up the KDN that ground, Haikang grace biotechnology company produces easily cotton clear, evenly adds the 0.08kg(mass fraction under stirring at normal temperature) two pyridines, four nitrogen manganese complexes, interpolation finishes, and continues to stir 15min, obtains new auxiliary.This digesting agent is applied in the woven fabric cold bleaching.
This example is done two check experiments, and 1# technology is traditional cheese technology of scouringing and bleaching, and 2# technology is the low temperature that the adds metal complex catalysts technology of scouringing and bleaching.
Handle fabric: cotton fabrics C40 * 40*173 * 120
Table 12 result that scourings and bleaching
Figure BDA00003044627800122
Embodiment 12
Taking by weighing 99.9kg, to go up the KDN that ground, Haikang grace biotechnology company produces easily cotton clear, evenly adds the 0.1kg(mass fraction under stirring at normal temperature) three pyridines, five nitrogen manganese complexes, interpolation finishes, and continues to stir 15min, obtains new auxiliary.This digesting agent is applied in the woven fabric cold bleaching.
This example is done two check experiments, and 1# technology is traditional cheese technology of scouringing and bleaching, and 2# technology is the low temperature that the adds metal complex catalysts technology of scouringing and bleaching.
Handle fabric: cotton fabrics C40 * 40*173 * 120
Figure BDA00003044627800131
Table 13 result that scourings and bleaching
Figure BDA00003044627800132

Claims (2)

1. pyridine radicals five application of nitrogen metal complex in the textiles low-temperature scouring and bleaching assistant is characterized in that: described low-temperature scouring and bleaching assistant is scouringed and bleaching for the low temperature that contains cotton fabrics grey cloth, knit grey cloth or base yarn; Low-temperature scouring and bleaching assistant comprises metal complex and scouring and bleaching assistant, described four pyridine radicals, five nitrogen metal complexs, and its structure is:
Figure FDA00003044627700011
The different metal ion of M representative in the formula is selected from a kind of in Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Cr (I)-(II), Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III), Ni (II)-(III), Cu (I)-(II), Zn (I)-(II); Described scouring and bleaching assistant is scouring agent, bleeding agent or stabilizing agent; The addition of described metal complex is the 0.01-99.9% of low-temperature scouring and bleaching assistant gross weight.
2. a kind of four pyridine radicals according to claim 1 five application of nitrogen metal complex in the textiles low-temperature scouring and bleaching assistant, it is characterized in that: the addition of described metal complex is the 0.01-5% of low-temperature scouring and bleaching assistant gross weight.
CN2013101281949A 2011-11-24 2011-11-24 Application of tetrapyridyl pentanitrogen metal complex to low-temperature scouring and bleaching auxiliary for textiles Pending CN103194894A (en)

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CN1333813A (en) * 1998-11-13 2002-01-30 宝洁公司 Bleach compositions
CN1351646A (en) * 1999-04-01 2002-05-29 荷兰联合利华有限公司 Composition and method for bleaching a substrate
CN1384870A (en) * 1999-09-01 2002-12-11 荷兰联合利华有限公司 Method of bleaching stained fabrics
CN1416459A (en) * 2000-03-01 2003-05-07 荷兰联合利华有限公司 Bleaching and dye transfer inhiditing compsn. and method for stain bleaching of laundry fabrics
CN101922109A (en) * 2010-09-14 2010-12-22 东华大学 Method for low-temperature activated bleaching by using Schiff base metal complexes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1333813A (en) * 1998-11-13 2002-01-30 宝洁公司 Bleach compositions
CN1351646A (en) * 1999-04-01 2002-05-29 荷兰联合利华有限公司 Composition and method for bleaching a substrate
CN1384870A (en) * 1999-09-01 2002-12-11 荷兰联合利华有限公司 Method of bleaching stained fabrics
US20020010121A1 (en) * 2000-03-01 2002-01-24 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Bleaching and dye transfer inhibiting composition and method for laundry fabrics
CN1416459A (en) * 2000-03-01 2003-05-07 荷兰联合利华有限公司 Bleaching and dye transfer inhiditing compsn. and method for stain bleaching of laundry fabrics
CN101922109A (en) * 2010-09-14 2010-12-22 东华大学 Method for low-temperature activated bleaching by using Schiff base metal complexes

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Application publication date: 20130710