CN100441606C - Polyacrylonitrile resin dyeable with both cationic dye and acid dye - Google Patents
Polyacrylonitrile resin dyeable with both cationic dye and acid dye Download PDFInfo
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- CN100441606C CN100441606C CNB2005101118798A CN200510111879A CN100441606C CN 100441606 C CN100441606 C CN 100441606C CN B2005101118798 A CNB2005101118798 A CN B2005101118798A CN 200510111879 A CN200510111879 A CN 200510111879A CN 100441606 C CN100441606 C CN 100441606C
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Abstract
The polyacrylonitrile resin dyeable with both cationic dye and acid dye is mixture of copolymer A and copolymer B with viscosity average molecular weight of 20000-80000 and in the weight ratio of 1 to (0.6-1.6). The monomers for each of copolymer A and copolymer B includes the first monomer acrylonitrile, the second monomer for modifying flexibility monomer, and the third monomer for modifying dyeability. The second monomer for both copolymer A and copolymer B is conventional polyacrylonitrile flexibility monomer. The third monomer for copolymer A is compound in the structure as shown; and that for copolymer B is conventional polyacrylonitrile dyeability modifying monomer. The polyacrylonitrile fiber made with the polyacrylonitrile resin has ideal dye uptake for both cationic dye and acid dye.
Description
Technical field
The present invention relates to a kind of polyacrylonitrile resin that is used to make acrylic fiber.
Background technology
Acrylic fiber has good fluffiness and heat retention, and is soft, and performance exactly likes wool, and very superior photostabilization and radiation resistance are arranged.The application surface of acrylic fibers is very wide, take, field such as bedclothes and soft decoration all is the ideal textile raw material.The spinning material of acrylic fibers is a polyacrylonitrile resin, simple polyacrylonitrile resin dyeing behavior is very poor, so improve the second flexible comonomer except adding in the resin, also must add the 3rd comonomer that is used for dyeing, modifying, so that the seat that dyes that dyes on the dyestuff to be provided to polymer molecule.In the prior art, the 3rd monomer of plain polypropylene nitrile resin only is fit to cationic dyeing.Because the performance of acrylic fibers exactly likes wool, acrylic fibers and wool blended, the mixed fabric of knitting occupy very big ratio in acrylic fibers post-treatment product.But wool should adopt matching stain to dye, and therefore hair-nitrile blending, mixes the fabric of knitting and requires acrylic fibers and wool can carry out " with bath " to dye, and promptly requires the 3rd comonomer in the polyacrylonitrile resin can be fit to the dyeing of matching stain.The polyacrylonitrile resin of acid-dyeable or the manufacturing technology of acrylic fibers have been seen more report, open clear 56-21842, spy as the Japanese Patent spy and open the content that clear 55-8604 and the clear 48-7888 of Te Kai have all related to this respect.Although still there are obvious defects in the polyacrylonitrile resin of these existing acid-dyeables or acrylic fibers, be that reactivity ratio is on the low side in the copolymerization system that constituted of the 3rd monomer of dyeing, modifying and vinyl cyanide and flexible modification second monomer commonly used, so that easily cause dyeing saturation value can't reach ideal numerical value, but realized the acid-dyeable of acrylic fiber after all.
But the existing polyacrylonitrile resin that is used to make acrylic fibers only has singly plants dye accessible performance, or cationic dye capable of dyeing or acid-dyeable, can't accomplish that two kinds of dyestuffs all can dye.This obviously gives in the production of product sales management, the weaving processing of road, back and dyeing and finishing process of acrylic fiber and has increased difficulty in the management.
Summary of the invention
The invention provides a kind of polyacrylonitrile resin mixture that is used to make acrylic fiber, it will solve existing polyacrylonitrile resin can't accomplish that cationic dye capable of dyeing or two kinds of dyestuffs of matching stain all can dye this technical problem.No matter acrylic fiber with this polyacrylonitrile resin mixture manufacturing all has the ideal dyeing saturation value to cationic dyestuff or matching stain.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
The polyacrylonitrile resin mixture that a kind of cationic dyestuff and matching stain all can dye, it is mixed by copolymer A and multipolymer B (being designated hereinafter simply as A and B).The viscosity-average molecular weight of A and B is 20000～80000, and both weight ratios are A: B=1: (0.6～1.6).A and B are polymerized by first comonomer vinyl cyanide, second comonomer and the 3rd comonomer.In the total amount of three kinds of comonomers, second co-monomer content of A and B is 5.5～16.5wt%, and the 3rd co-monomer content of A is 3.3～12.5wt%, and the 3rd co-monomer content of B is 0.8～5.0wt%.
Wherein:
Second comonomer of A and B is respectively taken from methyl acrylate, a kind of in ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi, vinyl acetate, acrylamide, Methacrylamide, vinylbenzene, vinylchlorid or the vinylidene chloride;
The 3rd comonomer of A is for having compound in structural formula I:
Wherein n is 2～6 integer, R
1, R
2, R
3Or R
4Respectively the do for oneself alkyl of hydrogen atom or C1～C4, X is nitrate radical, sulfate radical or salt acid ion;
The 3rd comonomer of B is the compound with structural formula II, III or IV:
R wherein
1, R
2Or R
3Respectively the do for oneself alkyl of hydrogen atom or C1～C4, Y is sodium ion or potassium ion;
R wherein
1Or R
2Respectively the do for oneself alkyl of hydrogen atom or C1～C4, Y is sodium ion or potassium ion;
Wherein R is the alkyl of hydrogen atom or C1～C4, and Y is sodium ion or potassium ion.
Second comonomer of above-mentioned A and B is preferably respectively taken from methyl acrylate, a kind of in ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi or the vinyl acetate; R among the 3rd comonomer structural formula I of A
1, R
2, R
3Or R
4Be preferably hydrogen atom, methyl or ethyl separately.
Above-mentioned A and B are preferably the powdery polymer that obtains by aqueous polymerization.
Polyacrylonitrile resin provided by the invention is actually the mixture that is mixed by two kinds of polyacrylonitrile multipolymers, and wherein B is a cationic dye capable of dyeing polyacrylonitrile resin conventional in the prior art, and A then is a kind of acrylic resin of acid-dyeable.So no matter use cationic dyestuff or matching stain, this polyacrylonitrile resin mixture all has dyeability.Be understood that after A and these two kinds of multipolymers mixing of B, for a certain dyestuff (cationic dyestuff or matching stain), it and dye molecule bonded dye seat will be in the corresponding minimizing of blended ratio.Therefore no matter be A or B, should be with the wherein corresponding raising of the 3rd monomer content of dyeing, modifying, could guarantee so wherein at a certain dye molecule to dye a content constant.By prior art as can be known, known these cationic dye capable of dyeing the 3rd monomers have very high reactivity ratio in the copolymerization system that constitutes with second monomer by vinyl cyanide and flexible modification, so the raising of the 3rd monomer content is not difficult in the multipolymer.But as use those acid-dyeable the 3rd monomers of existing report can't guarantee that because of reactivity ratio is too low the 3rd monomer can be brought up to enough content in the multipolymer.One of key of the present invention is exactly that the 3rd monomer that adopts of A has higher reactivity ratio in above-described copolymerization system, this has just guaranteed that it can bring up to enough content in resin under general polymerizing condition, thereby finally makes the mixture of being made up of two kinds of multipolymers of A, B that matching stain is had the ideal dyeing saturation value equally.
It is that the suspension polymerization process of medium is made that A and B preferably adopt water, and the resin that obtains like this is pulverous, and this will help both and be mixed fully.The monomer of two kinds of multipolymers feeds intake after wishing the ratio obtain in the multipolymer separately and considering transformation efficiency, and monomer mixes with water earlier and is made into charging behind the slurry, and the monomeric concentration of total polymerization is 10～50wt% in the slurry.Temperature of reaction is 50～90 ℃, and the reaction times is 1～10 hour.
Initiator is water miscible redox system, and oxygenant can be ammonium persulphate, Potassium Persulphate, hydrogen peroxide or sodium chlorate; Reductive agent can be Sodium Pyrosulfite, sodium bisulfite, S-WAT or trolamine etc.Initiator amount is generally 0.05～5wt% in all monomer total amounts, is preferably 0.2～1.0wt%.
The chain-transfer agent that is used to regulate molecular weight is thio-alcohol or different alkanols compound, as Virahol or dodecyl mercaptans.
Two kinds of multipolymers can adopt meal mixing equipment commonly used to mix.It is the acrylic fibers wet spinning process of solvent that final polyacrylonitrile resin product can be used for sodium thiocyanate water solution or N,N-DIMETHYLACETAMIDE, is applicable to that also with organic solvents such as dimethyl formamide, dimethyl sulfoxide (DMSO) or N,N-DIMETHYLACETAMIDEs be the acrylic fibers dry-spinning technology of solvent.
Compared with prior art, the invention has the advantages that the acrylic fiber with this resin manufacture all has the ideal dye uptake to cationic dyestuff and matching stain, dyeing saturation value is all very high, has brought very big convenience for the weaving processing in road, back and dyeing and finishing processing.When carrying out the manufacturing of two-step approach acrylic fibers with this resin, the polyacrylonitrile resin of technological process and processing condition and routine is identical, and the fibrous physical property index that makes does not have any difference with conventional acrylic fibers yet.
Below will the invention will be further described by specific embodiment.In the present invention, multipolymer B, and first, second monomer and the prior art of middle A are basic identical, so embodiment will pay attention to adopting among the A different the 3rd monomeric enumerating.By what technique scheme comprised, and do not enumerate in an embodiment by the B of other kind and the polyacrylonitrile resin mixture that A formed that constitutes by other second monomer, can predict it for those of ordinary skill in the art and have identical effect.This is also easily explanation and understanding theoretically, at first, because second monomer and the 3rd monomer all are a spot of with respect to vinyl cyanide.In copolymerization system, the height of their reactivity ratios is primarily aimed at the reactivity ratio of vinyl cyanide-vinyl cyanide, and different second monomers can't constitute too much influence to the 3rd monomeric reactivity ratio.In addition, the dyeing behavior of polyacrylonitrile resin depends primarily on the 3rd monomer, so embodiment does not do too much enumerating to second monomer in the copolymer A and content thereof yet.Secondly, because the seat that dyes of cationic dyestuff and matching stain is provided by B and A respectively, and two kinds of dyestuffs can not use usually simultaneously when post-treatment, and the B that technique scheme comprised and all be known to the dyeing behavior of cationic dyestuff, so embodiment does not do too much enumerating to B yet.
Embodiment
In an embodiment:
Monomeric content is measured with the method for nucleus magnetic resonance in the multipolymer.
The measuring method of acid dyeing saturation value (the dyestuff gram number that dyes on the 100 gram polymers) is: adopt matching stain (Tectlion is red for the vapour crust, and maximum absorption wavelength is 510nm) to dye, bath raio is 1/100, PH=4.5～5.5 (acetic acid adjusting).Dyeing is 30 ℃ of initial temperatures, and heat-up rate is 1.0 ℃/min, to 100 ℃ of constant temperature dyeings 1 hour, naturally cools to room temperature then, washing.Measure the dyeing absorbancy and the absorbancy of raffinate afterwards that dyes of stoste before respectively with spectrophotometer, and obtain the dyeing saturation value S of polypropylene acrylic fibers resin according to the dyeing saturation value formula.
The measuring method of cationic dyeing saturation value (the dyestuff gram number that dyes on the 100 gram polymers) is: adopt cationic dyestuff (Victoria Green WPB, maximum absorption wavelength are 618nm) to dye, bath raio is 1: 100, PH=4～5 (regulating with acetic acid and sodium-acetate).Dyeing is that initial temperature is 70 ℃, and heat-up rate is 1 ℃/min, to 100 ℃ of constant temperature 1 hour, and cool to room temperature then, washing.Measure the dyeing absorbancy and the absorbancy of raffinate afterwards that dyes of stoste before respectively with spectrophotometer, and obtain the dyeing saturation value S of polypropylene acrylic fibers resin according to the dyeing saturation value formula.
K in the formula: the slope of standard working curve
A1: the absorbancy of stoste before the dyeing
A2: the absorbancy of raffinate after the dyeing
B: polymeric weight
[embodiment 1～3]
Multipolymer B is the multipolymer of vinyl cyanide, methyl acrylate and methylpropene sodium sulfonate.Wherein in three kinds of monomer total amounts, methyl acrylate is 8.2wt%, and methylpropene sodium sulfonate is 1.45wt%.Copolymer A is vinyl cyanide, second monomer and the 3rd monomeric multipolymer, second and third monomer and see Table 1 in the content of three kinds of monomer total amounts.The viscosity-average molecular weight of A and B is 4.8 ten thousand, and both see Table 2 at the blended weight ratio.
[embodiment 4～6]
The monomer of multipolymer B is vinyl cyanide, vinyl acetate and 2-acrylamido-2-methyl propane sulfonic acid.Wherein in three kinds of monomer total amounts, vinyl acetate is 12wt%, and 2-acrylamido-2-methyl propane sulfonic acid is 1.38wt%.The viscosity-average molecular weight of A and B is 6.4 ten thousand.All the other are with embodiment 1～3.
[embodiment 7～9]
The monomer of multipolymer B is vinyl cyanide, methyl acrylate and Sodium styrene sulfonate, and wherein in three kinds of monomer total amounts, methyl acrylate is 8wt%, and Sodium styrene sulfonate is 1.51wt%.The viscosity-average molecular weight of A and B is 6.3 ten thousand.All the other are with embodiment 1～3.
The polyacrylonitrile resin of each embodiment carries out the mensuration of cationic dyestuff and acid dyeing saturation value, the results are shown in Table 2, and wherein S1 is the cationic dyeing saturation value, and S2 is the acid dyeing saturation value.
Table 1
| Second monomer | Second monomer content (wt%) | The 3rd monomer | The 3rd monomer content (wt%) | |
| Embodiment 1 | Vinyl acetate | 12.2 | Methacrylic acid N, silomate base ethyl ester nitrate | 3.5 |
| Embodiment 2 | Vinyl acetate | 12.5 | Methacrylic acid N, silomate base ethyl ester nitrate | 7.2 |
| Embodiment 3 | Vinyl acetate | 12.1 | Methacrylic acid N, silomate base ethyl ester nitrate | 9.0 |
| Embodiment 4 | Methyl acrylate | 8.5 | Methacrylic acid N, silomate base carbethoxy hydrochloride | 5.7 |
| Embodiment 5 | Methyl acrylate | 5.5 | Methacrylic acid N, silomate base carbethoxy hydrochloride | 6.6 |
| Embodiment 6 | Methyl acrylate | 8.0 | Methacrylic acid N, silomate base carbethoxy hydrochloride | 12.5 |
| Embodiment 7 | Vinyl acetate | 12.0 | Methacrylic acid N, silomate base ethyl ester vitriol | 5.9 |
| Embodiment 8 | Vinyl acetate | 16.2 | Methacrylic acid N, silomate base ethyl ester vitriol | 7.6 |
| Embodiment 9 | Vinyl acetate | 12.0 | Methacrylic acid N, silomate base ethyl ester vitriol | 9.9 |
Table 2
| A/B (weight ratio) | S1 | S2 | |
| Embodiment 1 | 1/0.62 | 8.72 | 3.51 |
| Embodiment 2 | 1/0.78 | 9.03 | 3.48 |
| Embodiment 3 | 1/1.02 | 9.21 | 3.59 |
| Embodiment 4 | 1/0.82 | 8.17 | 3.80 |
| Embodiment 5 | 1/0.95 | 8.45 | 3.85 |
| Embodiment 6 | 1/1.60 | 9.76 | 4.03 |
| Embodiment 7 | 1/0.75 | 8.27 | 3.34 |
| Embodiment 8 | 1/0.97 | 8.54 | 3.82 |
| Embodiment 9 | 1/1.23 | 9.22 | 3.60 |
Claims (4)
1, the polyacrylonitrile resin mixture that a kind of cationic dyestuff and matching stain all can dye, it is characterized in that it is mixed by copolymer A and multipolymer B, the viscosity-average molecular weight of A and B is 20000～80000, both weight ratios are A: B=1: (0.6～1.6), A and B are by the first comonomer vinyl cyanide, second comonomer and the 3rd comonomer are polymerized, total amount in three kinds of comonomers, second co-monomer content of A and B is 5.5～16.5wt%, the 3rd co-monomer content of A is 3.3～12.5wt%, the 3rd co-monomer content of B is 0.8～5.0wt%, wherein:
Second comonomer of A and B is respectively taken from methyl acrylate, a kind of in ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi, vinyl acetate, acrylamide, Methacrylamide, vinylbenzene, vinylchlorid or the vinylidene chloride;
The 3rd comonomer of A is for having compound in structural formula I:
Wherein n is 2～6 integer, R
1, R
2, R
3Or R
4Respectively the do for oneself alkyl of hydrogen atom or C1～C4, X is nitrate radical, sulfate radical or salt acid ion;
The 3rd comonomer of B is the compound with structural formula II, III or IV:
R wherein
1, R
2Or R
3Respectively the do for oneself alkyl of hydrogen atom or C1～C4, Y is sodium ion or potassium ion,
R wherein
1Or R
2Respectively the do for oneself alkyl of hydrogen atom or C1～C4, Y is sodium ion or potassium ion,
Wherein R is the alkyl of hydrogen atom or C1～C4, and Y is sodium ion or potassium ion.
2, polyacrylonitrile resin mixture according to claim 1 is characterized in that second comonomer of described A and B is respectively taken from methyl acrylate, a kind of in ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi or the vinyl acetate.
3, polyacrylonitrile resin mixture according to claim 1 is characterized in that R among the 3rd comonomer structural formula I of described A
1, R
2, R
3Or R
4Respectively do for oneself hydrogen atom, methyl or ethyl.
4,, it is characterized in that described A and B powdery polymer for obtaining by aqueous polymerization according to claim 1,2 or 3 described polyacrylonitrile resin mixtures.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101118798A CN100441606C (en) | 2005-12-22 | 2005-12-22 | Polyacrylonitrile resin dyeable with both cationic dye and acid dye |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101118798A CN100441606C (en) | 2005-12-22 | 2005-12-22 | Polyacrylonitrile resin dyeable with both cationic dye and acid dye |
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|---|---|
| CN1986586A CN1986586A (en) | 2007-06-27 |
| CN100441606C true CN100441606C (en) | 2008-12-10 |
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| CN112082964A (en) * | 2020-09-11 | 2020-12-15 | 安徽皖维高新材料股份有限公司 | Rapid detection method for content of cationic copolyester modified monomer |
| CN115522384A (en) * | 2022-09-20 | 2022-12-27 | 阜南华翔羊毛衫有限公司 | Rapid vintage treatment method for artificial woolen sweater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS558604B2 (en) * | 1974-08-23 | 1980-03-05 | ||
| CN1275586A (en) * | 1999-03-29 | 2000-12-06 | 大日精化工业株式会社 | Resin composition and method for making non-weaving cloth outlook resin moulding article |
| CN1578864A (en) * | 2001-11-07 | 2005-02-09 | 拜尔聚合物有限责任公司 | Process for dyeing molded articles, dip-dyed articles |
-
2005
- 2005-12-22 CN CNB2005101118798A patent/CN100441606C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS558604B2 (en) * | 1974-08-23 | 1980-03-05 | ||
| CN1275586A (en) * | 1999-03-29 | 2000-12-06 | 大日精化工业株式会社 | Resin composition and method for making non-weaving cloth outlook resin moulding article |
| CN1578864A (en) * | 2001-11-07 | 2005-02-09 | 拜尔聚合物有限责任公司 | Process for dyeing molded articles, dip-dyed articles |
Non-Patent Citations (2)
| Title |
|---|
| CN 1 275 586 A 2000.12.06 |
| CN 1 578 864 A 2005.02.09 |
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