CN1177617A - Method of preparaing lignin dye dispersants, lignin dye dispersants produced thereby and dyetuff compositions containing same - Google Patents
Method of preparaing lignin dye dispersants, lignin dye dispersants produced thereby and dyetuff compositions containing same Download PDFInfo
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- CN1177617A CN1177617A CN 97118292 CN97118292A CN1177617A CN 1177617 A CN1177617 A CN 1177617A CN 97118292 CN97118292 CN 97118292 CN 97118292 A CN97118292 A CN 97118292A CN 1177617 A CN1177617 A CN 1177617A
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- 238000000034 method Methods 0.000 title claims abstract description 92
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 61
- 229920005610 lignin Polymers 0.000 title claims abstract description 50
- 239000000975 dye Substances 0.000 claims abstract description 124
- 238000004537 pulping Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 26
- 239000002023 wood Substances 0.000 claims abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229920001732 Lignosulfonate Polymers 0.000 claims description 59
- 235000019357 lignosulphonate Nutrition 0.000 claims description 59
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- 239000003795 chemical substances by application Substances 0.000 claims description 45
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- 239000007788 liquid Substances 0.000 claims description 21
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- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
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- 238000006243 chemical reaction Methods 0.000 claims description 11
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- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 9
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- 230000000694 effects Effects 0.000 abstract description 12
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- 239000000243 solution Substances 0.000 description 2
- ZENOXNGFMSCLLL-UHFFFAOYSA-N vanillyl alcohol Chemical compound COC1=CC(CO)=CC=C1O ZENOXNGFMSCLLL-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 241000219495 Betulaceae Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004117 Lignosulphonate Substances 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- TUXJTJITXCHUEL-UHFFFAOYSA-N disperse red 11 Chemical compound C1=CC=C2C(=O)C3=C(N)C(OC)=CC(N)=C3C(=O)C2=C1 TUXJTJITXCHUEL-UHFFFAOYSA-N 0.000 description 1
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- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Improved dyestuff compositions comprising a dye cake and a dye dispersant are disclosed wherein the dye dispersant comprises sulfonated or sulfomethylated lignin of increased activity and improved heat stability properties and which dispersants are disclosed to be prepared by substantial removal of the low molecular weight component of the sulfonated and sulfomethylated lignin. Exclusion of the low molecular weight portion of the dispersant may be accomplished by fractionation of the sulfonated or sulfomethylated lignin to remove a substantial portion of the molecules having a molecular weight below 3,000. Alternatively, in the case of lignin recovered from sulfate or soda wood pulping processes, the lignin may be fractionated to remove a substantial portion of the molecules having a molecular weight below 3,000 prior to sulfonation or sulfomethylation.
Description
The present invention relates to a kind of sulfonated lignin and a kind of activity of improvement sulfonated lignin and method of thermostability of improving that can be used as the novelty improvement of dye dispersant.
Dye composite comprises dyestuff piece (being dyestuff) and dispersion agent and/or thinner usually.These dye composites are widely used for the dyeing of natural and synthon.In dye composite, dispersion agent has three basic functions: (1) helps to reduce the particle diameter of dye granule; (2) keep dispersion medium; And (3) are as thinner.
Dye dispersant is generally one of two kinds of main kenels: (1) derives from the sulfonated lignin (through sulfurous acid pulping method or vitriol (kraft) pulping method) of pulping wood industry, wherein lignocellulosic substance (as timber, straw, cornstalk, bagasse and analogue) is handled, xylogen is separated with Mierocrystalline cellulose or paper pulp; Or (2) derive from the naphthalenesulfonate of petroleum industry.The present invention relates to the sulfonated lignin dye dispersant.Recovery obtains sulphite (or hydrosulphite) pulping wood method xylogen as Sulfite lignin from spent pulp liquors (being called " black wash liquid ").And kraft paper (or vitriol) pulping wood method xylogen is that (product of the solid company (Westvaco Corporation) of Wei Shifan, trade mark is Indulin as the xylogen sodium salt from black wash liquid
) reclaim and to obtain.(product of the solid company (Westvaco Corporation) of Wei Shifan, trade mark is Polyfon to the xylogen that reclaims as dye dispersant behind sulfonation or sulfomethylation
, Kraftsperse
And Reax
).Can make a general reference above-mentioned Sulfite lignin, sulfonated lignin or sulfomethylation xylogen at this used " sulfonated lignin " speech.
The advantage that sulfonated lignin is used as dispersion agent in the dye composite is (1) availability and (2) unique physical properties, and these physical propertiess are included in has consistency and the outstanding dispersing characteristic good with many fuel systems under room temperature and the high temperature.Yet, many shortcomings when being used as dispersion agent, xylogen are arranged also no matter be sulphite xylogen or vitriol sulfonated lignin.These negative factors comprise that used xylogen is to dyeing of fiber (because of the xylogen of dry powder is brown) and thermostability (carrying out because of dyeing course ties up under the high temperature).These unfavorable character are a difficult problem to the tinter speech, and have done many trials to overcome these shortcomings.
The development of technology has produced the novel method of many improvement sulfonated lignins, uses the unfavorable aspect of this dye dispersant material with reduction, and can not produce any important negative impact to making sulfonated lignin be suitable for the characteristic of making dye dispersant simultaneously.United States Patent (USP) 4001202 is described a kind of by making xylogen and epihalohydrins prepared in reaction have the method for the sulfonated lignin that can be used as dye dispersant of fibres modified dyeing property.United States Patent (USP) 4338091 also discloses xylogen and S-WAT and a kind of aldehyde reaction that makes improvement, and this xylogen is improved by the pre-treatment of sodium hyposulfate.
Make lignin reaction or improvement so that more suitable other embodiment that makes dye dispersant comprises United States Patent (USP) 4184845,4131564,3156520,3094515,3726850,2680113 and 3769272.Listed document has been used to show the state in present technique field, rather than wants to summarize the modification method of all xylogen.
Though above-mentioned processing and the method for preparing sulfonated lignin can provide some advantages when dyeing, do not have a kind of method to make and have the product that makes the improvement performance of product by the application's method required for protection.
In dyeing course, have only dyestuff itself to exhaust on fiber, become a tight part of fiber.Xylogen and other dyeing assistants are stayed in the liquid effluent, must handle in one-level and secondary waste reduction and disposal equipment subsequently.Though xylogen is a crude substance, but that Sulfite lignin are considered to be difficult for is biodegradable (still readily biodegradable more more than the synthetic dispersing agent that obtains from petroleum industry), when surpassing the capacity of dyehouse or municipal waste water treatment equipment, often be regarded as environmentally harmful.
One of ways of addressing this issue is to improve dye dispersant activity (the relative consumption of term " activity " required dispersion agent when being meant useful effect of xylogen dispersion agent; Used dispersion agent is fewer, and then it is active higher; And required dispersion agent the more, and then its activity is lower).Like this, increase activity and can reduce the required consumption of dyeing, thereby can alleviate an existing wastewater treatment difficult problem.
So, catalogue of the present invention be to provide sulfonated lignin with improved properties, to improve its functions of use as dye dispersant.
Specific purposes of the present invention are to improve the activity of sulfonated lignin dispersion agent.
Another object of the present invention is to provide the method for the dye formulation thermostability that a kind of raising contains sulfonated lignin.
Other purposes of the present invention, technical characterictic and advantage thereof will see following detailed description of the invention.
Find, can obviously improve the sulfonated lignin that is used as dye dispersant in the dye composite and the activity of sulfomethylation xylogen by removing most of low-molecular-weight composition in desulfonate and the sulfomethylation xylogen at least, also improve the xylogen thermostability simultaneously.Better be to remove all low-molecular-weight compositions in desulfonate and/or the sulfomethylation xylogen basically.Perhaps remove most of low-molecular-weight xylogen composition at least, then the higher xylogen composition of molecular-weight average is carried out sulfonation or sulfomethylation, also can obtain the similar improvement of dye dispersant character by from black wash liquid, reclaiming in the xylogen that obtains.Preferably remove all low-molecular-weight xylogen compositions basically, then the higher xylogen composition of the molecular-weight average of remainder is carried out sulfonation and/or sulfomethylation.
Fig. 1 is as the synoptic diagram of the thermal stability data of the xylogen composition of the different molecular weight of the dispersion agent that disperses tangerine 30 dyestuffs after the comparison sulfonation.
Fig. 2 is used as Red 167 after the comparison sulfonation: the synoptic diagram of the thermal stability data of the xylogen composition of the different molecular weight of the dispersion agent of 1 dyestuff.
Fig. 3 uses Red 167: 1 dyestuff is the synoptic diagram of the active thermal stability data of relative dye dispersant of two kinds of different molecular weight sulfonated lignin compositions and composition thereof relatively.
Fig. 4 is with disperseing tangerine 30 dyestuffs to compare the thermal stability data histogram of the relative molecular weight composition of sulfonated lignin dye dispersant and commodity sulfonated lignin dye dispersant.
Fig. 5 uses Red 167: 1 dyestuff compares the thermal stability data histogram of the relative molecular weight composition of sulfonated lignin dye dispersant and commodity sulfonated lignin dye dispersant.
Fig. 6 uses Disperse Blue-79: 1 dyestuff compares the thermal stability data histogram of the relative molecular weight composition of sulfonated lignin dye dispersant and commodity sulfonated lignin dye dispersant.
Fig. 7 is the thermal stability data histogram that compares the relative molecular weight composition of sulfonated lignin dye dispersant and commodity sulfonated lignin dye dispersant with the Disperse Blue-60 dyestuff.
Fig. 8 is a thermal stability data histogram of using the sulfonated lignin dye dispersant of the specified molecular weight that disperses tangerine 30 dyestuffs to compare commodity (separating) sulfonated lignin dye dispersant and different amounts.
Fig. 9 uses Red 167: the thermal stability data histogram of the sulfonated lignin dye dispersant of the specified molecular weight of 1 dyestuff comparison commodity (separating) sulfonated lignin dye dispersant and different amounts.
Figure 10 uses Disperse Blue-79: the thermal stability data histogram of the sulfonated lignin dye dispersant of the specified molecular weight of 1 dyestuff comparison commodity (separating) sulfonated lignin dye dispersant and different amounts.
Figure 11 is the thermal stability data histogram with the sulfonated lignin dye dispersant of the specified molecular weight of Disperse Blue-60 dyestuff comparison commodity (separating) sulfonated lignin dye dispersant and different amounts.
Lignin is the amorphous phenyl-propane polymerization that is connected with the cell wall glycan of most of higher plant Thing. Because form the randomness of lignin, the absolute three-D space structure of lignin is still unknown. By right Many plant lignins sample carries out Study on degradation, have now found that lignin polymers mainly comprise vanillyl alcohol, Tonquinol and sinapinic alcohol. They by the plant peroxidase through the free radical mechanism polymerization, just because of these Radical reaction has produced disordered structure.
Reclaiming the lignin that obtains from any known pulping wood method all can be used in the method for the present invention. But Being, better is the lignin that obtains from sulfate pulping wood method, and wherein natural lignin deposits with sodium salt . In kraft process, timber is carried out highly basic process, natural lignin is taken place in various degree Degraded is to produce the recyclable lignin (for example referring to the table 1 among the embodiment 1) of different molecular weight ranges. The lignin that reclaims in this way forms soluble sodium salt, and this sodium salt can separate with cellulose, and dissolving In paper pulp. Be decreased to insoluble the scope (～pH9-of lignin salt by the pH value with secondary stock (black wash liquid) 10), can from this black wash liquid, reclaim lignin.
The acidic materials that add carbon dioxide and so on just can easily reduce the black wash liquid that contains lignin salt PH. When adding acid and reducing pH thus in black wash liquid, ionic phenates base just transforms on the lignin molecule Become free phenols or acid type. This conversion can not be dissolved in the black wash liquid lignin, thereby is settled out wooden Plain.
Reclaiming the alkaline lignin that obtains with this intermediate processing from black wash liquid is water-fast product. With The lignin that the sulfate relevant with the present invention, soda or other alkaline methods obtain is not with sulfonated products Form reclaims, but this material and bisulfites or sulphite is reacted and with its sulfonation. Sulfonation Lignin is to contain at least the effective dose sulfonic group, thereby the slightly high aqueous solution of the subacidity of being dissolvable in water and pH Any lignin.
No matter lignin is the sulphite lignin that reclaims with lignosulphonates (seeing Table IV), still can be by sulphur The sulfate lignin (seeing Table I) of change or sulfomethylation (seeing Table II) always exists quite in the recovery lignin The lignin that the polymolecular amount is lower.
In the United States Patent (USP) case 4551151, Dilling discloses molecular weight and is about or is less than the thermostability that 5000 xylogen can influence the dye composite that contains the sulfonated lignin material, Dilling points out that the basic black slurries that will contain lignin salt are acidified to certain pH, can make all molecular weight except negligible quantity be about or be less than 5000 xylogen and not come out with the higher lignin product coprecipitation of molecular weight and still be retained in the black wash liquid.
One of problem of Dilling (U.S.4551151) method is to separate the xylogen that obtains by adding acid from black wash liquid, and is main relevant with the ionization of phenates base.When protonated, even the xylogen precipitation.Producing too high electrolyte concentration during acidifying also can cause and saltout.Suppose that protonated group number is identical, because of its size, the time that the lower xylogen of molecular weight should the xylogen bigger than molecular weight keeps in solution is longer.By regulating pH and filtration, separate the hydrophilic phenol that the low molecular weight compositions that obtains contains maximum quantity, the acidity of this hydrophilic phenol changes with the difference of adjacency functionality.So just changed solvability-pH relation greatly, therefore, this method can not only be isolated low-molecular-weight xylogen.Remove the xylogen composition of a considerable amount of intermediate molecular weight when in fact, farthest removing low-molecular weight lignin inevitably with this authorization method.Except can not obtaining the favourable contribution of this material to required dispersion agent characteristic, this separation method efficient is low-down, so economic benefit is relatively poor.
Among the present invention, as enlightening, Dilling (U.S. ' 151) from black wash liquid, do not isolate specific xylogen composition.And, separate sulfonation and sulfomethylation xylogen and do not rely on the control of pH.
Opposite with ionization precipitation principle, the present invention's separation only is as the criterion with molecular size, from following examples, can be clear that, from various sulfonation sulphite xylogen and sulfomethylation and sulfonation vitriol xylogen, not be subjected to the influence of xylogen functional group during separate low molecular amount composition; Therefore, the inventive method has greatly been improved separation method, but also a kind of sulfonated lignin dispersion agent product that has improved greatly is provided.The inventive method not only provides a kind of improved generally high reactivity dye dispersant, and can allow dispersion agent manufacturers be the specific dispersion agent of particular dye system customization.
During conventional separating lignin (as acidifying, cohesion and filtration/decant), next step that develop conventional lignin-base dye dispersant is suitably to make the xylogen sulfonation.The sulfonation degree system that should note xylogen is proportional with the viscosity of the solubleness of xylogen in the aqueous solution and this xylogen.Therefore, the solubleness of measurement sulfonated lignin is to measure a kind of method of sulfonation degree.
One of ordinary method of sulfonated lignin is by xylogen and S-WAT and formaldehyde reaction alkaline sulfomethylated lignin to be methylated.People such as E.Adler has proposed this method in United States Patent (USP) 2680113.Sulfomethylation is with-CH
2SO
3The mode of H base and this nuclear bond knot acts on the aromatic proton of lignin molecule.Alder points out that the temperature range with these sulfonated reagent processing xylogen is 50 ℃ to 200 ℃, and 80 ℃ to 170 ℃ more suitable, and 100 ℃ to 160 ℃ preferable.The consumption of sulphite (calculating with sodium sulphite anhydrous 99.3) can be about 10% to 100% of anhydrous xylogen to be changed.The consumption of aldehyde can equal the consumption of sulphite or lower, until about 1%, calculates with the quantity of anhydrous lignin substance.Handle and carry out in the basic solution more fortunately.
Also can carry out sulfomethylation to alkaline xylogen as follows, be about to alkaline xylogen and mix the formation slurry with water.In slurry, add azochlorosulfonate methyl agent, as S-WAT and formaldehyde.The proportional range of S-WAT and formaldehyde is from about 1.1: 0.1 to about 2.5: 1.0, about 1.3: 0.8 of preferable scope.Have now found that when adding, can produce the lower sulfonated lignin product of molecular weight than the excessive S-WAT of formaldehyde.
When formaldehyde mixed by stoichiometry with S-WAT, they almost formed the hydroxyl methylsulfonic acid immediately, then formed the sulfonated lignin derivative with lignin reaction.Only 90% hydroxyl methylsulfonic acid intermediate exists with required form, and 10% reactant then exists always.The problem that has 10% reactant is that formaldehyde can carry out coupled reaction with sulfomethylated xylogen.Therefore, in reaction mixture, should there be the least possible unreacting acetal.The mol ratio that changes the S-WAT PARA FORMALDEHYDE PRILLS(91,95) can be accomplished this point.The mol ratio that improves the S-WAT PARA FORMALDEHYDE PRILLS(91,95) can reduce the polymerization degree by reducing the S-WAT amount that remaining unreacting acetal produces more hydroxyl methylsulfonic acid acid intermediate and increased, and produces low-molecular-weight sulfonated lignin inevitably.
In another kind of method of sulfonating, sedimentary xylogen is carried out cleanup acid treatment, more handy sulfuric acid, dry back produces the lignin substance that pH is about 1.5-5.0.Form when 25% solid slurries are arranged approximately when xylogen mixes with water, under this pH, this xylogen exists with the precipitation attitude.If xylogen slurries pH less than 5, is increased to about 5 with sodium hydroxide with pH.At this moment, the adding S-WAT is increased to about 7 to 7.5 with the initial pH scope of reaction mixture.
Sulfonation takes place when adding formaldehyde, and it is increased to about 8.0 to 9.2 with slurries pH scope.Then with the temperature regulation of these slurries to about 130 ℃ to about 175 ℃, preferable temperature is about 140 ℃.With about 30 minutes to 12 hours of this temperature maintenance, the best was about 2 hours.
With low pH and low temperature two advantages are arranged.One is that xylogen is with this understanding compared with more difficult decomposition under the normal reaction conditions.The fact that sulfonation reaction takes place when hanging down pH means that the pH of gained sulfonated lignin product can be lower than the available value of other method.
When sulfonated lignin was used as dye dispersant, the pH scope of this xylogen was preferably about 4 to about 8.If xylogen carries out sulfonation when high pH, then the sulfonated lignin of gained has high pH.Briquetting (presscake) formulator as dispersion agent, just needs this sulfonated lignin the dyeing personnel to add people's acid in this xylogen and reduces pH, so just needs extra-pay.If sulfonated lignin when low pH only just can obtain with on a small quantity or need not be sour with regard to the applicable sulfonated lignin of making dye dispersant.
All above-mentioned sulfonation and sulfomethylation xylogen and other existing sulphite or alkali formula pulping method sulfonated lignin are all relevant with the inventive method.Basically remove molecular weight below 3000, sulfonation below 10000 and sulfomethylation xylogen composition have just produced the sulfonation or the sulfomethylation xylogen dye dispersant of improvement more fortunately.Because sulfonation or sulfomethylation have increased the molecular weight of xylogen significantly, for from sulphate process, soda process or other alkali formula pulping method, reclaiming the xylogen that obtains, remove the molecule that most of molecular weight is lower than 3000 (better being lower than 10000) by separation, high molecular xylogen composition to remainder carries out sulfonation and sulfomethylation then, also can obtain the xylogen dispersion agent of the present invention's improvement.Though remove the molecular-weight average that low-molecular-weight composition will inevitably improve the xylogen dispersion agent, composition of the present invention is not with specific average molecular weight range definition, because can improve molecular-weight average with removing low molecular weight compositions method in addition.
The method or the mode of removing (or major part is removed at least) low molecular weight compositions are not critical.Theme of the present invention only relates to the improvement sulfonated lignin dye dispersant that is substantially free of low molecular weight compositions.Because the method for multiple measurement molecular weight is arranged, they may produce different results, and improvement sulfonation that the present invention relates to or sulfomethylation xylogen dye dispersant are characterised in that being substantially free of molecular weight is lower than 3000 molecule (measuring with ultrafiltration process) (or preferably be characterised in that be substantially free of molecular weight be lower than 10000 molecule).Specifically, used ultrafiltration is with the ultrafiltration (or the most handy 10000 molecular weight films) of 3000 molecular weight films in Amicon (or similar) ultra-filtration equipment in this work.Whether exist low molecular weight compositions to measure in the sulfonated lignin dye dispersant that ultrafiltration process makes with embodiment 1 described gel permeation chromatography (GPC).Use the device of disc membrane to be applicable to laboratory scale, and use the device of spirality film to allow higher turnout, therefore be applicable to fairly large processing.
The method that merge to form low molecular weight compositions in xylogen/sulfonated lignin that the present invention improves dye composite with dyestuff is removed or removed basically to another kind is reverse osmosis.Also having a kind of method of low molecular weight compositions that reduces basically in xylogen/sulfonated lignin is that (a) makes in the xylogen low molecular weight compositions crosslinked, and then sulfonation and/or sulfomethylation, it is crosslinked that perhaps (b) makes the low molecular weight compositions in sulfonation and the sulfomethylation xylogen.Product in separating after the quantity that reduces low molecular weight compositions by precrosslink also can reduce loses.
The sulfonated lignin that makes by the present invention can be used as the dispersion agent of dye composite.This dispersion agent aequum on specific dyestuff piece, treat that coloring material and required effect decide.The greatest factor of the suitable consumption of dispersion agent when dye composite is made in decision is used concrete dyestuff piece.Generally speaking, this consumption changes with dyestuff is different.
That following only is embodiment, and should not think that the present invention only limits to these embodiment.
In order to determine the structure-characteristic-property relationship of xylogen in the related dye application, will from vitriol pulping wood method black wash liquid, reclaim the xylogen (Indulin that obtains with the low pH precipitator method with ultrafiltration process
A) be separated into the separate part (fraction) of five kinds of molecular weight.This is separated on the AmiconRA2000 ultra-filtration equipment that uses the Amicon spirality film and carries out.With pH regulator to 11, solids content is adjusted to 10% with 50%NaOH.Use 100K respectively, 30K, 10K, and the membrane filtration Indulin of 3K.Wash each separate part, till the effluent liquid clarification.The molecular weight data series of each separate part of measuring with gel infiltration chromatographic analysis (GPC) method is in Table I.
Table II ndulin
A separate part Mn
1Mw
2Mz
3Productive rate %＞100K 600 25,900 48,000 18＞30K＜100K 180 6,300 13,400 18＞10K＜30K 130 4,000 9,000 33＞3＜10K 80 1,900 4,500 11＜3K 40 1,200 3,100 20
1Intermediate value molecular weight (mean molecular weight)
2Molecular-weight average (average molecular weight)
3Maximum molecular weight
By preparation concentration is the xylogen sample of 1 mg/ml (is benchmark with %wt/wt solid in the water that flows (fine 20: 80 mixtures with the 0.1N SODIUMNITRATE of second, pH is 11.0)), each the separate part molecular-weight average shown in the meter I.Before the analysis, allow xylogen sample balance at least 8 hours, and filter with 0.45 micron filter.100 μ l aliquots containigs are injected the Waters of four balances to 40 ℃
Ultrahydragel post (1000,500,250 and 120 dust) is with the Waters that is set in 280 nanometers
486 type ultraviolet rays detector detected peaks.Produce working curve with the narrow standard substance of poly styrene sulfonate.Fitting of a curve is to have the single order match of forcing initial point.
Different separate parts is restrained sulfonation to three kind of different degree respectively according to acid point 1.1,1.5 and 2.4.As mentioned above, record solvability and can measure sulfonation degree effectively.Therefore, sulfonation degree is to begin to be settled out the required 10N sulfuric acid amount of xylogen (gram) for measuring in the solution (0.175 gram is as the criterion with solid, with distilled water diluting to 35 gram).The separate part of＜3K does not have sulfonation, may be less owing to the branched chain reaction position, but this separate part is put 1.5 by sulfomethylation to acid.After separate part was sulfonated, molecular weight is just not significant to be changed.
With hydrophobic dye (Red 167: 1) and hydrophilic dye (disperse tangerine 30) carry out a whole set of dyeing and (use Zeltex the whole series-dyeing apparatus available from Werner Mathis, promptly 1 liter/minute, 70 ℃-130 ℃, @2 ℃/minute and dye chamber pressure 2 crust), to test the thermostability of different sulfonation separate parts.The result of test as shown in Figures 1 and 2, and and Reax
The result of 85A compares (a kind of conventional sulfonated lignin dye dispersant that is considered as having high thermal stability by industry member).
With the result of two kinds of dye tests,＞10K＜30K and＞30K＜100K separate part has the highest thermostability, they and standard substance Reax
85A is identical or better.The solvability of these two kinds of separate parts is to not influence of thermostability.
According to solvability,＞100K and＞thermostability of 3K＜10K separate part is equal to or less than Reax85A.When with dispersion tangerine 30, the thermostability of＞100K separate part obviously degenerates with deliquescent increase.With the higher dyestuff of wetting ability, Red 167: 1 o'clock, then can this thing happens, the thermostability of all sulfonation degree and Reax
85A is identical.During with two kinds of dye tests,＞3K＜10K separate part thermostability reduces with deliquescent increase, but uses Red 167: this trend was clearer and more definite in 1 o'clock.
In addition, from Fig. 3, notice enjoyably 50/50 ground adding＞30K＜100K and＞that the situation of 3K＜10K separate part has is how good.Can draw as drawing a conclusion from these test-results, it is much higher that the specific activity of high molecular xylogen had before been suspected, and the low isolate of molecular weight does not participate in dyeing course.
Present embodiment relates to the Reax of different molecular weight
Relation between the xylogen thermostability during 85A separate part and dye dispersant are used.Described dye dispersant is applied to four kinds of different hydrophilics and hydrophobic dye (disperse tangerine 30, Disperse Blue-79: 1, Red 167: 1 and Disperse Blue-60).Reax
85A is a kind of sodium sulfonate xylogen that is methylated and made by the sulfomethylated lignin that recovery in the vitriol pulping wood obtains, and it is that Westvaco company is at a kind of dye dispersant of selling all over the world.Under the 60psi nitrogen pressure, one after the other remove the Reax of different amounts with the Amicon ultrafiltration groove that 50K, 10K, 3K, 1K and 500 molecular weight disc films are housed
85A.The sulfonation situation of the percentage ratio of the low molecular weight substance of being removed and rest part is listed in the Table II.
Material (%) 500 1.7 9.01K 1.6 12.83K 1.2 30.010K 0.8 38.950K 0.7 47.1 that Table II Amicon acid point (gram) is removed
Different Reax
The thermostability of 85A separate part dye dispersant is used available from a whole set of dyeing of Werner Mathis apparatus measures, 1 liter/minute of flow velocity, temperature range is 70 ℃-130 ℃, heat-up rate is 2 ℃/minute, it is 2 crust that groove is pressed, and with unsegregated Reax
The thermostability of 85A is made comparisons.The result of this comparison is illustrated in Fig. 4-7.
Fig. 4-7 shows and works as from Reax
Remove molecular weight among the 85A when the composition below 3000, obtained the high maximum temperature stability of four kinds of different dyes.Dividing potential drop area (y-axle) expression thermostability; Area is bigger, and thermostability is poorer.Table 2 shows has removed 30% low-molecular weight lignin and inorganic salt in the sepn process.Fig. 4-7 shows that also removable xylogen amount has a limit, surpasses this limit thermostability improvement and promptly begins to reduce.
Fig. 8 shows when use disperseing tangerine 30, can make the consumption of high molecular separate part reduce 40% to 45%, and still with the unsegregated Reax of commodity
The thermostability of 85A is identical.With＞3K and＞two kinds of isolates of 10K are when disperseing tangerine 30 actuating quantity researchs, though be not shown among Fig. 8 the coming to the same thing of two kinds of separate parts.
Respectively consumption is reduced to 70%, 50% and 80% more significantly when share with these dyestuffs, for Red 167: 1, Disperse Blue-79: 1 and Disperse Blue-60 (respectively in Fig. 9-11) can be observed identical trend.(Red 167: 1 and Disperse Blue-79: the 1st, hydrophobic dye, and the wetting ability of Disperse Blue-60 is higher).When finishing dyeing course, dispersant dosage is low more, needs the relatively poor xylogen amount of the biodegradability handle in one-level and secondary sewage treatment equipment just few more.
In order to determine the improvement of xylogen dye dispersant composition of the present invention, to commodity Reax to the dyestuff color fastness
85A and ultra-filtration and separation remove the Reax of molecular weight less than 3000 compositions
85A carries out thermally-stabilised boiling test, compares its relative hue fastness with present industrial standards.Used thermally-stabilised boiling test comprises that restraining dyestuff (100% is as the criterion) with 1 is dispersed in 200 ml distilled waters.With dilute acetic acid with pH regulator to 4.5.Then dispersion liquid is heated to 100 ℃ (boilings), and kept 15 minutes at 100 ℃.Under 22 inches vacuum, the dispersion liquid that had heated filters with the preweighted 11cmWhatman# 2 filter paper that is placed on the Whatman# 4 filter paper.This assessment is as the criterion with resistates on the #2 filter paper.
The results are shown in Table III.
Table III dye type standard Reax
The color fastness high molecular Reax of 85A
The color fastness of 85A
(%), (%) disperse tangerine 30 100 175 to disperse blue 79: 1 200 275 Red 167s: 1 100 200 disperse blue 60 200 300 disperse red 60s 200 264
When under the higher color fastness, (surpassing present industrial standards) when relatively thermostability is tested in boiling, all standard Reax
The 85A composite is all defective, and high molecular Reax
The 85A composite passes through heat stability test in higher color fastness.
The present embodiment explanation improves the dye composite thermostability with the lignosulfonic acid dipersant that is made by sulfite pulp black wash liquid of removing low molecular weight compositions.The sample of all tests is the commercial dye dispersion agent that Borregaard makes.Remove low molecular weight compositions in each sample with 3000 molecular weight films by the method described in the foregoing description.That measures the results are shown in following Table IV.Measured molecular weight is a molecular-weight average; Acid point 10N H
2SO
4Decision; And Hou one hurdle shows that reaching same or similar thermostability allows the usage percentage that reduces.
The MW of the precursor that Table IV sample productive rate is removed＞thermally-stabilised thermostability of 3K AP AP＞3K (precursor) is material MW precursor precursor＞3K＞3K (%)
(%) (crust ℃) (crust ℃) (crust ℃) Ufoxane-RG 49.1 50.9 11,100 13,600 10.1 5.2 58.5 49.9 56.4
(reducing 25%) DynasperseB 38.4 61.6 8,600 12,200 8.7 5.9 69.1 34.9 60.0
(reducing 75%) Vanisperse 52.1 47.9 3,200 4,200 2.0 1.4 24.4 16.4 16.6
CB (reducing 30%)
Though after removing low molecular weight compositions, only remaining with 38.4% to 52.1% the sulfonated lignin that makes by the sulfurous acid pulping wood, under same amount, also can make the thermostability raising of dye composite.Even surprisingly still can improve the thermostability of dye composite than the standard consumption reduction by 25% to 70% of precursor lignin substance.
Though think in the xylogen dye dispersant mineral acid and very low-molecular-weight xylogen composition and have neither part nor lot in or help required dye dispersant characteristic, but wondrously and beat all be, for example remove that few (this 20% is a low molecular weight compositions basically to 20% xylogen dispersion agent material, as＜3K, with＜10K is preferable) also can improve the thermal dye stability (being better than unsegregated xylogen dispersion agent) of product, and reduce the consumption of dyestuff piece.This discovery causes following possibility:
1 viewpoint from environmentalism, less consumption help a small amount of dispersion agent and enter wastewater treatment process, thereby make xylogen more help environment;
2 lower dispersant dosages can make the dye formulation that color fastness surpasses existing standard.This is particularly conducive to liquid formulations, because the xylogen consumption that reduces can be replaced by dyestuff, thereby increases the color-values of filling a prescription.Net effect is more effective packing, this for the Yan Tigao of dyestuff manufacturers turnout and reduced freight charges and textile mills have been improved the stock.
Though with reference to various concrete materials, the invention has been described for step and embodiment.But should think that the present invention is not limited to selected concrete material, combinations of substances and step.Those of skill in the art should understand the various variations that can use these details in the art.
Claims (31)
1. one kind prepares the method that improves dye composite, and described method comprises dyestuff piece and the combination of xylogen dispersion agent, it is characterized in that before dye dispersant and dyestuff agllutination close, and it is handled to remove molecular weight less than 3000 composition.
2. the method for claim 1, its feature are that also xylogen is to reclaim the Sulfite lignin that obtain in the black wash liquid that produces from sulfurous acid pulping wood process.
3. the method for claim 1, its feature are that also xylogen is to reclaim the xylogen that obtains from alkaline pulping wood process in the black wash liquid, then with S-WAT and formaldehyde reaction.
4. the method for claim 1, its feature is that also alkaline pulping wood process is selected from vitriol pulping wood process and soda pulping wood process.
5. the method for claim 1, its feature also are to select in the group that the dyestuff piece is made up of dispersed dye and vat pigment, and select in the group that wherein xylogen dispersion agent system is made up of sulfonated lignin and sulfomethylation xylogen.
6. the method for claim 1, it is according to molecular weight size separation xylogen dispersion agent less than the treatment process of 3000 composition that its feature also is to be used for to remove delignification dispersion agent molecular weight, isolates the dispersant molecule amount less than 3000 composition from all the other compositions of dispersion agent.
7. method as claimed in claim 6, its feature also are to separate by membrane ultrafiltration xylogen dispersion agent is undertaken, and described film can be removed molecular weight less than 3000 composition.
8. the method for claim 1, its feature xylogen dispersion agent are that this method is included in before xylogen dispersion agent and dyestuff agllutination close, and it is handled to remove molecular weight less than 10000 composition.
9. method as claimed in claim 6, its feature also are to separate by membrane ultrafiltration xylogen dispersion agent is undertaken, and described film can be removed molecular weight less than 10000 composition.
10. method as claimed in claim 6, its feature also are to separate by reverse osmosis xylogen dispersion agent is undertaken, to remove molecular weight less than 3000 composition.
11. also being to separate by reverse osmosis xylogen dispersion agent, method as claimed in claim 10, its feature carry out, to remove molecular weight less than 10000 composition.
12. making xylogen dispersant molecule amount before method as claimed in claim 6, its feature also are to separate carries out crosslinked less than 3000 composition.
13. making xylogen dispersant molecule amount before method as claimed in claim 12, its feature also are to separate carries out crosslinked less than 10000 composition.
14. method for preparing dye composite, it comprises combines the xylogen dispersion agent of selecting in dyestuff piece and the group of being made up of sulfonated lignin and sulfomethylation xylogen, it is characterized in that the xylogen dispersion agent is to reclaim the lignin substance that obtains by handling from the black wash liquid of alkaline pulping wood process, remove molecular weight less than 3000 composition, remaining xylogen and S-WAT and formaldehyde reaction are made.
15. method as claimed in claim 14, its feature also are to select in the group that alkaline pulping wood process is made up of soda pulping process and sulfate pulp-making process.
16. method as claimed in claim 14, its feature also are to select in the group that the dyestuff piece is made up of dispersed dye and vat pigment.
17. method as claimed in claim 14, its feature is also to be used for that to remove molecular weight be the xylogen that reclaims according to the molecular weight size separation less than the treatment process of 3000 composition from reclaiming xylogen, isolates molecular weight less than 3000 xylogen composition from all the other compositions of xylogen.
18. it is to be undertaken by the xylogen that reclaims with membrane ultrafiltration that method as claimed in claim 17, its feature also are to separate, described film can be removed molecular weight less than 3000 composition.
19. before method as claimed in claim 14, its feature were that also this method is included in xylogen dispersion agent and S-WAT and formaldehyde reaction, the xylogen that handle to reclaim was to remove molecular weight less than 10000 composition.
20. method as claimed in claim 17 is characterized in that separating by carrying out with membrane ultrafiltration xylogen dispersion agent, described film can be removed molecular weight less than 10000 composition.
21. it is that the xylogen that reclaims by reverse osmosis carries out that method as claimed in claim 17, its feature also are to separate, to remove molecular weight less than 3000 composition.
22. it is that the xylogen that reclaims by reverse osmosis carries out that method as claimed in claim 21, its feature also are to separate, to remove molecular weight less than 10000 composition.
23. make molecular weight carry out crosslinked before method as claimed in claim 17, its feature also are to separate less than 3000 recovery xylogen composition.
24. make molecular weight carry out crosslinked before method as claimed in claim 23, its feature also are to separate less than 10000 recovery xylogen composition.
25. the xylogen dye dispersant of an improvement is selected in the group that it is made up of sulfonated lignin and sulfomethylation xylogen, its feature is that also the xylogen dispersion agent is substantially free of molecular weight less than 3000 molecule.
26. a dye composite, it comprises bonded dyestuff piece and xylogen dispersion agent, it is characterized in that selecting in the group that the xylogen dispersion agent is made up of sulfonated lignin and sulfomethylation xylogen, and is substantially free of molecular weight less than 3000 molecule.
27. dye composite as claimed in claim 26, its feature be also that xylogen reclaims and obtain from the pulping wood process, select in the group that described pulping wood process is made up of sulphite pulping wood process and alkaline pulping wood process.
28. dye composite as claimed in claim 27, its feature are also that xylogen reclaims and obtain that described alkaline pulping wood process is selected from vitriol pulping wood process and soda pulping wood process from alkaline pulping wood process.
29. dye composite as claimed in claim 28, its feature also are to select in the group that the dyestuff piece is made up of dispersed dye and vat pigment.
30. dye composite as claimed in claim 29, its feature are that also the dyestuff piece is dispersed dye.
31. dye composite as claimed in claim 28, its feature are that also the xylogen dispersion agent is substantially free of molecular weight less than 10000 molecule.
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| CN 97118292 CN1177617A (en) | 1996-09-12 | 1997-09-12 | Method of preparaing lignin dye dispersants, lignin dye dispersants produced thereby and dyetuff compositions containing same |
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| CN 97118292 CN1177617A (en) | 1996-09-12 | 1997-09-12 | Method of preparaing lignin dye dispersants, lignin dye dispersants produced thereby and dyetuff compositions containing same |
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| CN102174274A (en) * | 2011-03-08 | 2011-09-07 | 延边石岘白麓纸业股份有限公司 | Method for preparing dye dispersant from waste liquid from sulphate pulping |
| CN105017539A (en) * | 2015-06-24 | 2015-11-04 | 济南圣泉集团股份有限公司 | Dye dispersant and preparation method thereof |
| CN105017337A (en) * | 2015-06-24 | 2015-11-04 | 济南圣泉集团股份有限公司 | Dye dispersant and preparation method thereof |
| CN105968381A (en) * | 2016-05-30 | 2016-09-28 | 浙江山峪染料化工有限公司 | Method for modifying lignosulfonate |
| CN105968381B (en) * | 2016-05-30 | 2019-03-05 | 浙江山峪染料化工有限公司 | A kind of method of modified lignin mahogany sulfonate |
| CN110483806A (en) * | 2018-05-15 | 2019-11-22 | 上海昶法新材料有限公司 | A kind of lignosulphonates and preparation method thereof |
| CN110483805A (en) * | 2018-05-15 | 2019-11-22 | 上海昶法新材料有限公司 | A method of preparing lignosulphonates |
| CN110922607A (en) * | 2019-12-10 | 2020-03-27 | 苏州经贸职业技术学院 | A kind of preparation method of environment-friendly dye dispersant |
| CN114044916A (en) * | 2021-10-29 | 2022-02-15 | 牡丹江恒丰纸业股份有限公司 | Method for preparing dye dispersant |
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