CN104610542A - Polyamide with sulfonic acid group - Google Patents
Polyamide with sulfonic acid group Download PDFInfo
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- CN104610542A CN104610542A CN201510057539.5A CN201510057539A CN104610542A CN 104610542 A CN104610542 A CN 104610542A CN 201510057539 A CN201510057539 A CN 201510057539A CN 104610542 A CN104610542 A CN 104610542A
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- sulfonic acid
- acid group
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- polyamide
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Abstract
The invention relates to a polyamide with a sulfonic acid group and a preparation method of the polyamide, and belongs to the field of high polymer material preparation. The polyamide with the sulfonic acid group is prepared by introducing a sulfonic acid group in the polyamide. The polyamide with the sulfonic acid group is characterized in that a monomer with the sulfonic acid group, a polyamide monomer, a catalyst and additives are mixed, a melt polymerization reaction is carried out, and the sulfonic acid group is introduced in the macromolecular structure of the polyamide, so that a polyamide chain is bonded with the lateral group of the sulfonic acid group, thus improving the cation binding performance and the hydrophilcity of the polymer material. The polyamide can be prepared into resin particles for spinning fibres and processing plastic products.
Description
Technical field
The present invention relates to a kind of polymeric amide with sulfonic acid group and preparation method thereof, particularly a kind ofly can produce the polymeric amide of keying action with positively charged ion.
Background technology
Tynex is the synthon containing amido linkage (-CONH-) on a kind of macromolecular chain, and because containing NH in molecular chain, easily by acid dyeing, matching stain is combined with fiber with ionic linkage.But matching stain has water-soluble, polyamide product wet colour fastness after acid dyeing is poor, and thus polymeric amide is difficult to have bright-coloured beautiful color.Cationic dyestuff is usually bright in colour, can be combined and form firmly covalent attachment, thus dyefastness by reactive group in polymkeric substance.But traditional polyamide molecule chain lacks the group that can act on mutually with cationic dyestuff, be thus difficult to by cationic dyeing, after dyeing, firmness does not ensure.Give polymeric amide cation dyeable by modification, there is feasibility, and the Application Areas of polymeric amide kind can be expanded, bring higher economic benefit.
At present, publication number is the preparation method that CN102471486A discloses a kind of modified polyamide, the method obtains the polymeric amide of modification by the modification of simple function group aromatic sulfonic acid compounds, this modified polyamide demonstrates the balance of multiple performance, reduced the molecular weight of polymeric amide by the sulfoacid compound of interpolation simple function group, and then increase its melt viscosity and do not reduce or improve its thermomechanical property and mechanical property even on the contrary.Publication number is that CN103254432A discloses the preparation method of a kind of auto-doping Electroactive polyamide acid and the application in electrochromism thereof, invention first synthesize with sulfonic acid group side chain by the mode of terpolymer on polyamic acid containing Oligoanilines; Again this polymers soln to be spin-coated on ito glass and as working electrode.Measure the electrochromism property of polymkeric substance in different pH value electrolyte solution.Compared with traditional polyaniline compound derivative, this kind of side chain type auto-doping Electroactive polyamide acid containing sulfonic acid group all maintains good electrochromic property in acidity, neutrality and weakly alkaline solution.Publication number is that CN103590129A discloses a kind of easy dyeing polypropylene fibre and preparation method thereof, this invention with to propenyl sodium sulfonate for dye seat, reacted with it by sodium allylsulfonate and maleic anhydride, be grafted on polypropylene macromolecular chain, through maleic anhydride modified sodium allylsulfonate, all contain propenyl functional group, good consistency is had with polypropylene molecular chain, and can generating portion graft copolymer, upset polypropylene fibre crystallisation process, broken ring is known clearly the orientation of macromolecular chain in polypropylene fibre and crystallization, remain this anionic functional group of sulfonic acid group simultaneously, ion-exchange can be carried out under cryogenic with cationic dyestuff, thus make cationic dyestuff enter fiber surface and inside, obtain easy dyeing polypropylene fibre.
Sulfonic acid group is introduced in polymeric amide and develop the important subject that the polyamide product with cation dyeable is macromolecule material preparation area.Utilize melt polymerization sulfonic acid group can be introduced in high-molecular polyamide by chemical bond, and then obtain the polymeric amide with sulfonic acid group.This polyamide hydrophilic with sulfonic acid group improves simultaneously, can be combined better, thus obtain the superpolymer product of quality-improving with dyestuff.
Summary of the invention
The object of the invention is for solving the group that on traditional polyamide molecule chain, shortage can act on mutually with cationic dyestuff, thus be difficult to not had guaranteed problem by firmness after cationic dyeing and dyeing, provide a kind of wetting ability high, can be combined with dyestuff better, with the preparation method of the polymeric amide of sulfonic acid group.
Polymeric amide with sulfonic acid group of the present invention is: by containing the mixing of the monomer of sulfonic acid group, monomer of polyamide, catalyzer and additive, carry out melt polymerization, be incorporated into by sulfonic acid group in polymeric amide macromolecular structure.One or more in following general formula are comprised containing sulfonic acid group monomer:
(1)
(2)
(3)
Wherein X=O or N ,-SO
3h can at the ortho position of-XH, a position or contraposition.
A kind of preparation method of the polymeric amide with sulfonic acid group is:
(1) be fully uniformly mixed containing the monomer of sulfonic acid group, monomer of polyamide, catalyzer and additive;
(2) under nitrogen protection atmosphere, heating makes said mixture melting, is heated to 90 ~ 240 DEG C of isothermal reaction 1-5 hour,
Then 240 ~ 300 DEG C of isothermal reactions 2 ~ 10 hours are progressively warming up to;
(3) polymkeric substance removes unreacted monomer through distilled water wash, and after vacuum drying oven dries 24 hours, melt pelletization obtains the polyamide resin with sulfonic acid group.
Described additive is polyvinylpyrrolidone; The addition of polyvinylpyrrolidone is 2 ~ 5% of copolymer quality.
Described catalyzer is silicon-dioxide and antimonous oxide, and the weight ratio of silicon-dioxide and antimonous oxide is 10:1 ~ 3.
The described monomer containing sulfonic acid group is 5-sulphosalicylic acid or 2-amino-5-sulfosalicylic acid.
Preferably, in step (2), described reacting by heating refers to and is heated to 90 ~ 120 DEG C of isothermal reactions 1 ~ 2 hour, reacting by heating 3 ~ 4 hours at being then progressively warming up to 260 ~ 280 DEG C.
Preferably, in step (2), described reacting by heating refers to reacting by heating to 90 DEG C, isothermal reaction 2 hours, and then progressively heating up reaches 260 DEG C, isothermal reaction 3 hours.
The preparation method of the described polymeric amide with sulfonic acid group is applicable to the preparation of the polymkeric substance such as nylon 1010, poly-11-amino undecanoic acid, poly-12 amino dodecanoic acid, poly-4-Aminobutanoicacid, nylon 46, poly-5-aminovaleric acid, polycaprolactam, polyhexamethylene adipamide, poly-hexamethylene azelamide, polyhexamethylene sebacamide, nylon 612, poly-7-aminoheptylic acid, poly(8 amino caprylic acid) and poly-9 aminononanoic acid.
The polymeric amide introducing sulfonic acid group can be prepared into resin particle, for spinned fiber and processing plastic goods.
A kind of polymeric amide with sulfonic acid group is prepared by melt polymerization, this anionic functional group of sulfonic acid group, ion-exchange can be carried out under cryogenic with cationic dyestuff, thus cationic dyestuff is entered by the fiber surface of polymer-modified preparation and inside, be conducive to improving fiber and cationic binding ability.Silicon-dioxide and adding of antimonous oxide catalyzer make the power consumption of reacting obviously reduce.Meanwhile, the additive polyvinylpyrrolidone in reaction and sulfonic acid group interact, and improve dyeing power and the wetting ability of polymeric amide further, polymeric amide is easier to by cationic dyeing and dyes rear firmness better, improving product quality.
Embodiment
Embodiment 1
Add in 40g nylon 46 by 2g 5-sulphosalicylic acid, 2.1g polyvinylpyrrolidone and catalyzer, under nitrogen protection atmosphere, heating makes its melting, and progressively heating up reaches 90 DEG C, isothermal reaction 2h.Then 260 DEG C are progressively warmed up to, isothermal reaction 3h.Polymkeric substance is poured out from reaction vessel, with enough distilled water immersions repeatedly to remove unreacted monomer.After vacuum drying oven dries 24h, melt-spinning, spinning speed is 600m/min, obtains chromatophilous fiber.The dyeing behavior of fiber is listed in table 1.
Embodiment 2
Add in 40g nylon 612 by 5g 2-amino-5-sulfosalicylic acid, 0.9g polyvinylpyrrolidone and catalyzer, under nitrogen protection atmosphere, heating makes its melting, and progressively heating up reaches 120 DEG C, isothermal reaction 1h.Then 280 DEG C are progressively warmed up to, isothermal reaction 4h.Polymkeric substance is poured out from reaction vessel, with enough distilled water immersions repeatedly to remove unreacted monomer.After vacuum drying oven dries 24h, melt-spinning, spinning speed is 600m/min, obtains chromatophilous fiber.The dyeing behavior of fiber is listed in table 1.
Embodiment 3
2g 5-sulphosalicylic acid is added, 1g polyvinylpyrrolidone and catalyzer be added in 40g 11-aminoundecanoic acid, add appropriate distilled water, under nitrogen protection atmosphere, be heated to 200 DEG C of isothermal reaction 3h.Then progressively heat up and reach 270 DEG C, isothermal reaction 6 h.Polymkeric substance is poured out from reaction vessel, with enough distilled water immersions repeatedly to remove unreacted monomer.After vacuum drying oven dries 24h, melt-spinning, spinning speed is 600m/min, obtains chromatophilous fiber.The dyeing behavior of fiber is listed in table 1.
Embodiment 4
30.34g sebacic acid, 25.85g decamethylene diamine are dissolved in 100mL ethanol respectively, are uniformly mixed after being placed in 75 DEG C of water bath with thermostatic control constant temperature.In and after salify cooling separates out, after filtration, recrystallization, drying, finally obtained nylon 1010 salt.Add in 40g nylon 1010 salt by 4g 2-amino-5-sulfosalicylic acid, 2g polyvinylpyrrolidone and catalyzer, under nitrogen protection atmosphere, heating makes its melting, and progressively heating up reaches 240 DEG C, isothermal reaction 2.5h.Then 260 DEG C are warmed up to, isothermal reaction 3h.Polymkeric substance is poured out from reaction vessel, with enough distilled water immersions repeatedly to remove unreacted monomer.After vacuum drying oven dries 24h, melt-spinning, spinning speed is 600m/min, obtains chromatophilous fiber.The dyeing behavior of fiber is listed in table 1.
Embodiment 5
The aqueous hypophosphorous acid of 1g 5-sulphosalicylic acid, 4g 6-aminocaprolc acid, 0.0015g tetra-hydration manganous chloride, 0.0043g50% is added, 1.5g polyvinylpyrrolidone and catalyzer be added in 40g hexanolactam; under nitrogen protection atmosphere; heating makes its melting, to 220 DEG C of isothermal reaction 2h.Then progressively heat up and reach 260 DEG C, isothermal reaction 4h.Polymkeric substance is poured out from reaction vessel, with enough distilled water immersions repeatedly to remove unreacted monomer.After vacuum drying oven dries 24h, melt-spinning, spinning speed is 600m/min, obtains chromatophilous fiber.The dyeing behavior of fiber is listed in table 1.
Embodiment 6
23.24g hexanodioic acid, 29.23g hexanediamine are dissolved in 100mL ethanol respectively, are uniformly mixed after being placed in 70 DEG C of water bath with thermostatic control constant temperature.In and after salify cooling separates out, after filtration, recrystallization, drying, finally obtained poly-adipoyl diamine salts.4g 2-amino-4-sulfosalicylic acid, 2g polyvinylpyrrolidone and catalyzer are added to 40g and gather adipoyl in diamine salts, under nitrogen protection atmosphere, heating makes its melting, and progressively heating up reaches 220 DEG C, isothermal reaction 1h.Then 260 DEG C are progressively warmed up to, isothermal reaction 3h.Polymkeric substance is poured out from reaction vessel, with enough distilled water immersions repeatedly to remove unreacted monomer.After vacuum drying oven dries 24h, melt-spinning, spinning speed is 600m/min, obtains chromatophilous fiber.The dyeing behavior of fiber is listed in table 1.
Embodiment 7
37.64g nonane diacid, 23.24g hexanediamine are dissolved in 100mL ethanol respectively, are uniformly mixed after being placed in 75 DEG C of water bath with thermostatic control constant temperature.In and after salify cooling separates out, after filtration, recrystallization, drying, finally obtained poly-hexamethylene azelamide salt.Adding 4g 2-amino-5-sulfosalicylic acid, 2g polyvinylpyrrolidone and catalyzer to 40g gathers in hexamethylene azelamide salt, and under nitrogen protection atmosphere, heating makes its melting, and progressively heating up reaches 180 DEG C, isothermal reaction 1h.Then 240 DEG C are warmed up to, isothermal reaction 2h.Polymkeric substance is poured out from reaction vessel, with enough distilled water immersions repeatedly to remove unreacted monomer.After vacuum drying oven dries 24h, melt-spinning, spinning speed is 600m/min, obtains chromatophilous fiber.The dyeing behavior of fiber is listed in table 1.
Embodiment 8
30.34g sebacic acid, 17.43g hexanediamine are dissolved in 100mL ethanol respectively, are uniformly mixed after being placed in 70 DEG C of water bath with thermostatic control constant temperature.In and after salify cooling separates out, after filtration, recrystallization, drying, finally obtained polyhexamethylene sebacamide salt.Add in 40g polyhexamethylene sebacamide salt by 4g 2-amino-5-sulfosalicylic acid, 1g polyvinylpyrrolidone and catalyzer, under nitrogen protection atmosphere, heating makes its melting, and progressively heating up reaches 240 DEG C, isothermal reaction 1h.Then 260 DEG C are warmed up to, isothermal reaction 4h.Polymkeric substance is poured out from reaction vessel, with enough distilled water immersions repeatedly to remove unreacted monomer.After vacuum drying oven dries 24h, melt-spinning, spinning speed is 600m/min, obtains chromatophilous fiber.The dyeing behavior of fiber is listed in table 1.
Table 1
Above to the preparation method of the polymeric amide with sulfonic acid group that the embodiment of the present invention provides, be described in detail, apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; Meanwhile, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (7)
1. the preparation method with the polymeric amide of sulfonic acid group, it is characterized in that, described polymeric amide obtains by containing the monomer of sulfonic acid group, monomer of polyamide, catalyzer and additive copolymerization, and described polymeric amide comprises at least one as the monomer containing sulfonic acid group in general formula below:
(1)
(2)
(3)
Wherein X=O or N ,-SO
3h can at the ortho position of-XH, a position or contraposition; Specifically comprise the following steps:
(1) be fully uniformly mixed containing the monomer of sulfonic acid group, monomer of polyamide, catalyzer and additive;
(2) under nitrogen protection atmosphere, heating makes said mixture melting, is heated to 90 ~ 240 DEG C of isothermal reaction 1-5 hour, is then progressively warming up to 240 ~ 300 DEG C of isothermal reactions 2 ~ 10 hours;
(3) polymkeric substance removes unreacted monomer through distilled water wash, and after vacuum drying oven dries 24 hours, melt pelletization obtains the polyamide resin with sulfonic acid group.
2. the preparation method of the polymeric amide with sulfonic acid group according to claim 1, is characterized in that, described additive is polyvinylpyrrolidone, and the addition of polyvinylpyrrolidone is 2 ~ 5% of multipolymer total mass.
3. the preparation method of the polymeric amide with sulfonic acid group according to claim 1, is characterized in that, described catalyzer is silicon-dioxide and antimonous oxide, and the weight ratio of silicon-dioxide and antimonous oxide is 10:1 ~ 3.
4. the preparation method of the polymeric amide with sulfonic acid group according to claim 1, is characterized in that, the described monomer containing sulfonic acid group is 5-sulphosalicylic acid or 2-amino-5-sulfosalicylic acid.
5. the preparation method of the polymeric amide with sulfonic acid group according to claim 1, it is characterized in that, in step (2), reacting by heating refers to and is heated to 90 ~ 120 DEG C of isothermal reactions 1 ~ 2 hour, reacting by heating 3 ~ 4 hours at being then progressively warming up to 260 ~ 280 DEG C.
6. the preparation method of the polymeric amide with sulfonic acid group according to claim 1, it is characterized in that, described preparation method is applicable to the preparation of nylon 1010, poly-11-amino undecanoic acid, poly-12 amino dodecanoic acid, poly-4-Aminobutanoicacid, nylon 46, poly-5-aminovaleric acid, polycaprolactam, polyhexamethylene adipamide, poly-hexamethylene azelamide, polyhexamethylene sebacamide, nylon 612, poly-7-aminoheptylic acid, poly(8 amino caprylic acid) and poly-9 aminononanoic acid polymkeric substance.
7. the preparation method of the polymeric amide with sulfonic acid group according to claim 1, is characterized in that, the polymeric amide introducing sulfonic acid group can be prepared into resin particle, for spinned fiber and processing plastic goods.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510057539.5A CN104610542A (en) | 2015-02-04 | 2015-02-04 | Polyamide with sulfonic acid group |
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| CN201510057539.5A CN104610542A (en) | 2015-02-04 | 2015-02-04 | Polyamide with sulfonic acid group |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329466A (en) * | 2018-03-14 | 2018-07-27 | 天津工业大学 | A kind of 6/ tetracarboxylic acid dianhydride composite material and preparation method of Flameproof polyamide |
| CN108385193A (en) * | 2018-03-06 | 2018-08-10 | 天津工业大学 | A kind of preparation method of the coloured nanofiber of polyamide 6/tetracarboxylic acid dianhydride |
| CN108465386A (en) * | 2018-05-11 | 2018-08-31 | 天津工业大学 | A kind of anion channel film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3184436A (en) * | 1959-09-04 | 1965-05-18 | Du Pont | Polycarbonamides of improved dye affinity having the benzene sulfonic acid salt moiety as an integral part of the polymer chain |
-
2015
- 2015-02-04 CN CN201510057539.5A patent/CN104610542A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3184436A (en) * | 1959-09-04 | 1965-05-18 | Du Pont | Polycarbonamides of improved dye affinity having the benzene sulfonic acid salt moiety as an integral part of the polymer chain |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108385193A (en) * | 2018-03-06 | 2018-08-10 | 天津工业大学 | A kind of preparation method of the coloured nanofiber of polyamide 6/tetracarboxylic acid dianhydride |
| CN108329466A (en) * | 2018-03-14 | 2018-07-27 | 天津工业大学 | A kind of 6/ tetracarboxylic acid dianhydride composite material and preparation method of Flameproof polyamide |
| CN108465386A (en) * | 2018-05-11 | 2018-08-31 | 天津工业大学 | A kind of anion channel film |
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Application publication date: 20150513 |
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