CN103194895A - Application of tetraazacyclohexadecane metal complex to low-temperature scouring and bleaching auxiliary for textiles - Google Patents

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

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CN103194895A
CN103194895A CN2013101281991A CN201310128199A CN103194895A CN 103194895 A CN103194895 A CN 103194895A CN 2013101281991 A CN2013101281991 A CN 2013101281991A CN 201310128199 A CN201310128199 A CN 201310128199A CN 103194895 A CN103194895 A CN 103194895A
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bleaching
scouring
metal complex
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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 tetraazacyclohexadecane 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

The application of tetraazacyclododecane hexadecane metal complex in the textiles low-temperature scouring and bleaching assistant
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, the particularly application of a kind of tetraazacyclododecane hexadecane 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 the application of a kind of tetraazacyclododecane hexadecane metal complex in the textiles low-temperature scouring and bleaching assistant, 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
1# tradition bleaching process
Figure BDA00003045115100031
Figure BDA00003045115100041
2# low temperature is scouringed and bleaching
Table 1 result that scourings and bleaching
Figure BDA00003045115100043
Embodiment 2
Take by weighing the efficient scouring enzyme DR-510 of the flourish Chemical Manufacture of 99.9kg Wuxi moral, evenly add the big ring iron complex of 0.1kg (mass fraction) benzo four acid amides under stirring at normal temperature, 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
1# tradition polyester-cotton blend woven fabric bleaching process
Figure BDA00003045115100044
2# low temperature is scouringed and bleaching
Figure BDA00003045115100045
Figure BDA00003045115100051
Table 2 result that scourings and bleaching
Figure BDA00003045115100052
Embodiment 3
Take by weighing the multi-functional concise dose of HA-SSA that Hai'an, 49.9kg Jiangsu petrochemical plant is produced, evenly add 0.1kg (mass fraction) terpyridyl manganese complex under stirring at normal temperature, 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)
The 1# traditional cotton cheese technology of scouringing and bleaching
Figure BDA00003045115100053
2# low temperature is scouringed and bleaching
Figure BDA00003045115100054
Table 3 result that scourings and bleaching
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 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
1# traditional cotton knitted fabric bleaching process
Figure BDA00003045115100061
2# low temperature is scouringed and bleaching
Figure BDA00003045115100062
Table 4 result that scourings and bleaching
Figure BDA00003045115100063
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 two pyridine pyrimidine radicals of 0.1kg (mass fraction) manganese complex under stirring at normal temperature, and 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
1# traditional cotton woven fabric bleaching process
Figure BDA00003045115100071
2# low temperature is scouringed and bleaching
Figure BDA00003045115100072
Table 5 result that scourings and bleaching
Figure BDA00003045115100073
Embodiment 6
Take by weighing the homemade scouring agent ST-1 of 99.9kg, add 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
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
1# traditional cotton knitted fabric bleaching process
Figure BDA00003045115100081
2# low temperature is scouringed and bleaching
Figure BDA00003045115100082
3# low temperature is scouringed and bleaching
Figure BDA00003045115100083
Table 7 result that scourings and bleaching
Figure BDA00003045115100084
Embodiment 7
Take by weighing 49.94kg and go up among the stabilizing agent KDN-T that ground, Haikang grace biotechnology company produces, add 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
1# traditional cotton woven fabric bleaching process
2# low temperature is scouringed and bleaching
Table 8 result that scourings and bleaching
Figure BDA00003045115100093
Embodiment 8
Take by weighing the homemade scouring agent ST-1 of 99.9kg, add 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
1# traditional cotton woven fabric bleaching process
Figure BDA00003045115100094
2# low temperature is scouringed and bleaching
Figure BDA00003045115100095
Figure BDA00003045115100101
Table 9 result that scourings and bleaching
Figure BDA00003045115100102
Embodiment 9
Taking by weighing 99.9kg, to go up the KDN that ground, Haikang grace biotechnology company produces easily cotton clear, evenly adds 0.1kg (mass fraction) three pyridine radicals four nitrogen manganese complexes under stirring at normal temperature, and 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
1# traditional cotton woven fabric bleaching process
2# low temperature is scouringed and bleaching
Figure BDA00003045115100104
Table 10 result that scourings and bleaching
Figure BDA00003045115100111
Embodiment 10
Taking by weighing 99.9kg, to go up the KDN that ground, Haikang grace biotechnology company produces easily cotton clear, evenly adds 0.1kg (mass fraction) 1-10 phenanthroline manganese complex under stirring at normal temperature, and 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
1# traditional cotton woven fabric bleaching process
Figure BDA00003045115100112
2# low temperature is scouringed and bleaching
Figure BDA00003045115100113
Table 11 result that scourings and bleaching
Figure BDA00003045115100114
Embodiment 11
Taking by weighing 99.92kg, to go up the KDN that ground, Haikang grace biotechnology company produces easily cotton clear, evenly adds 0.08kg (mass fraction) two pyridines four nitrogen manganese complexes under stirring at normal temperature, and 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
1# traditional cotton woven fabric bleaching process
Figure BDA00003045115100121
2# low temperature is scouringed and bleaching
Table 12 result that scourings and bleaching
Figure BDA00003045115100123
Embodiment 12
Taking by weighing 99.9kg, to go up the KDN that ground, Haikang grace biotechnology company produces easily cotton clear, evenly adds 0.1kg (mass fraction) three pyridines five nitrogen manganese complexes under stirring at normal temperature, and 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
1# traditional cotton woven fabric bleaching process
2# low temperature is scouringed and bleaching
Figure BDA00003045115100132
Table 13 result that scourings and bleaching
Figure BDA00003045115100133

Claims (2)

1. the application of a tetraazacyclododecane hexadecane 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 nitrogen dicyclo tetradecane metal complexs, and its structure is:
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. the application of a kind of tetraazacyclododecane hexadecane metal complex according to claim 1 in the textiles low-temperature scouring and bleaching assistant is characterized in that: the addition of described metal complex is the 0.01-5% of low-temperature scouring and bleaching assistant gross weight.
CN2013101281991A 2011-11-24 2011-11-24 Application of tetraazacyclohexadecane metal complex to low-temperature scouring and bleaching auxiliary for textiles Pending CN103194895A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115652627A (en) * 2022-11-01 2023-01-31 张建春 Copper ion antibacterial hemp fiber and fabric preparation method

Citations (1)

* 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

Patent Citations (1)

* 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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115652627A (en) * 2022-11-01 2023-01-31 张建春 Copper ion antibacterial hemp fiber and fabric preparation method

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Application publication date: 20130710