CN103394335A - Preparation method of carboxyl-terminated hyperbranched polyesteramide collagenous fiber adsorbing material - Google Patents
Preparation method of carboxyl-terminated hyperbranched polyesteramide collagenous fiber adsorbing material Download PDFInfo
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Abstract
The invention discloses a preparation method of a carboxyl-terminated hyperbranched polyesteramide collagenous fiber adsorbing material. The preparation method comprises the following steps of: adding carboxyl-terminated hyperbranched polyesteramide collagenous fiber into water, and stirring at normal temperature for uniform dispersion to obtain a carboxyl-terminated hyperbranched polyesteramide collagenous fiber dispersive liquid; then adjusting the pH value of glyoxylic acid aqueous solution to be 5.5-8.0, then adding the glyoxylic acid aqueous solution into the carboxyl-terminated hyperbranched polyesteramide collagenous fiber dispersive liquid, continuously reacting for 3.0-5.0 hours at the temperature of 0-40 DEG C, obtaining turbid liquid containing products, then filtering, drying and grinding a filter cake uniformly to obtain the carboxyl-terminated hyperbranched polyesteramide collagenous fiber adsorbing material. The carboxyl-terminated hyperbranched polyesteramide collagenous fiber adopted by the invention has a large amount of active groups, can be chelated with metal ions and is prepared into the carboxyl-terminated hyperbranched polyesteramide collagenous fiber adsorbing material under the action of a carboxylation reagent; and the carboxyl-terminated hyperbranched polyesteramide collagenous fiber adsorbing material has higher adsorbing performance, wider pH addition range and stronger adaptability to the change of multi-turbidity, alkalinity and the content of organic matters.
Description
Technical field
The invention belongs to water-treatment technology field, be specifically related to a kind of preparation method of end carboxyl super branched polyamide collagen fiber adsorption material.
Background technology
The greatest contamination that leather industry exists is the Cr(III that contains that produces in Chrome Tanning Process) waste water.In the tradition chrome tanning process, the absorptivity of chromium only has 65%～75%, and 25%～35% Cr(III is namely arranged) remain in useless Chrome Tanning Liquor can not by rawhide, be absorbed and fix, Cr(III in waste liquid) concentration reach 3～8g/L
-1(with Cr
2O
3Meter), cause serious environmental pollution and the waste of chromium metals resources.Cr(III) be subject to can being converted to Cr(VI under the impact of water body environment (pH, redox materials, temperature etc.)), Cr(VI) have carcinogenicly, teratogenesis, cause very big harm to the biology in human body and water body.Therefore, how effectively to process the Cr(III in leather producing chrome tanning exhausted liquid) be vital.The method of existing processing waste water containing chrome mainly contains the alkaline chemical precipitation recovery method, and adjusting suitable pH is the key of controlling chromium from waste chromium concentration, but ubiquity Cr (OH)
3Precipitation is difficult to reclaim, and need to add flocculant again, program complexity, the shortcoming such as the processing time is long, and cost is higher.
Summary of the invention
The object of the present invention is to provide the restriction of a kind of application conditions low, without the preparation method of potential safety hazard, environmental friendliness and end carboxyl super branched polyamide collagen fiber adsorption material with low cost.
For achieving the above object, the technical solution used in the present invention comprises the following steps:
1) amine-terminated hyperbrancedization polyamide collagenous fibres are added to the water, stirring at normal temperature makes to be uniformly dispersed, and obtains amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid;
2) the pH value of glyoxalic acid solution is adjusted to 5.5～8.0, then add in amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid, under 0-40 ℃, continue reaction 3.0～5.0h, obtain containing the suspension of product, the suspension that will contain product filters, the filter cake water that obtains washes away unreacted glyoxalic acid, and is then dry, obtains end carboxyl super branched polyamide collagen fiber adsorption material; Wherein, in the amino on the amino ultrabranching polyamide collagenous fibres of amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid middle-end and glyoxalic acid solution, the mol ratio of glyoxalic acid is 1:(0.5～2).
In described step 1), every amine-terminated hyperbrancedization of gram polyamide collagenous fibres add in 50～300mL water.
Described step 2) in, the mass concentration of glyoxalic acid solution is 40%.
Described step 2) drying in is at room temperature carried out.
Compared with prior art, advantage of the present invention is:
1, adsorption is high:
The present invention, take amine-terminated hyperbrancedization polyamide collagenous fibres as raw material, carries out modification by glyoxalic acid to it and has obtained end carboxyl super branched polyamide collagen fiber adsorption material.Because amine-terminated hyperbrancedization polyamide collagenous fibres are introduced ultrabranching polyamide on collagenous fibres and made.On the one hand, because ultrabranching polyamide contains a large amount of end group active function groups, on its molecular skeleton, contain a large amount of nitrogen-containing groups, can carry out chelating with metal ion, therefore, ultrabranching polyamide can carry out chelating as the metal ion in chelating agent and water body separately; Simultaneously ultrabranching polyamide has unique cavity structure and 3-D solid structure, and for its physical absorption to metal ion provides condition, but that it has is good water-soluble, and is difficult to from water body, separating after metal ion-chelant; On the other hand, amino, carboxyl and hydroxyl isoreactivity group are contained in the collagenous fibres surface, ultrabranching polyamide is introduced on collagenous fibres, can roll up the quantity of the active group on collagenous fibres surface, and because collagenous fibres are water insoluble, therefore, ultrabranching polyamide is introduced to the amine-terminated hyperbrancedization polyamide collagenous fibres that make on collagenous fibres not soluble in water, overcome ultrabranching polyamide and after chelated metal ions, be difficult to from the shortcoming of separating water body.
in addition, because the present invention adopts the terminal groups modification method, the amino on amine-terminated hyperbrancedization polyamide collagenous fibres surface is prepared into to end carboxyl super branched polyamide collagen fiber adsorption material under the effect of carboxylated reagent, therefore this end carboxyl super branched polyamide collagen fiber adsorption material is a kind of efficient, has optionally sorbing material, has higher absorption property, wider pH adds scope, to many turbidity, basicity, the variation of content of organics has stronger adaptability, after modification end carboxyl super branched polyamide collagenous fibres compared to amine-terminated hyperbrancedization polyamide collagenous fibres to Cr(III) absorption property significantly improve, so, the end carboxyl super branched polyamide collagen fiber adsorption material adsorption that the present invention makes is high, the application conditions restriction is low.
2, environmentally friendly:
The amine-terminated hyperbrancedization polyamide collagenous fibres that the present invention adopts be from the collagenous fibres that extract aboundresources, the Leather Solid Waste that nontoxic, price is cheaper as waste, therefore, environmental friendliness of the present invention and with low cost; Simultaneously, contain Cr(III after adopting end carboxyl super branched polyamide collagen fiber adsorption material that method of the present invention obtains to be applicable to process) waste water, harmful substance wherein is difficult for being leached by underground water, and environment is not had to secondary pollution, therefore, without potential safety hazard.
The accompanying drawing explanation
Fig. 1 is synthetic route chart of the present invention.
The specific embodiment
As shown in Figure 1, the present invention, take amine-terminated hyperbrancedization polyamide collagenous fibres as raw material, through the glyoxalic acid modification, makes end carboxyl super branched polyamide collagen fiber adsorption material.
Below will the present invention will be further described in detail by embodiment.
Embodiment 1:
1) prepare amine-terminated hyperbrancedization polyamide collagenous fibres (HBPN) ([1] Wang Xuechuan, Zhang Feifei, torrential by force. hyperbranched collagenous fibres adsorbent synthetic with characterize [J]. functional material, 2013,44, (4): 527～531.);
2) amine-terminated hyperbrancedization polyamide collagenous fibres are added in distilled water, stirring at normal temperature 0.5h, make to be uniformly dispersed, and obtains amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid; Every amine-terminated hyperbrancedization of gram polyamide collagenous fibres add in 50mL distilled water;
3) by mass concentration, be that the pH value of 40% glyoxalic acid solution is adjusted to 5.5, then add in amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid, under 0 ℃, continue reaction 3.0h, obtain containing the suspension of product, the suspension that will contain product filters, and the filter cake that obtains washs 3 times to wash away unreacted glyoxalic acid, then air drying with normal-temperature water, grind evenly, obtain end carboxyl super branched polyamide collagen fiber adsorption material; Wherein, in the amino on the amino ultrabranching polyamide collagenous fibres of amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid middle-end and glyoxalic acid solution, the mol ratio of glyoxalic acid is 1:0.5.
Embodiment 2:
1) prepare amine-terminated hyperbrancedization polyamide collagenous fibres (CF-HBPN) ([1] Wang Xuechuan, Zhang Feifei, torrential by force. hyperbranched collagenous fibres adsorbent synthetic with characterize [J]. functional material, 2013,44, (4): 527～531.);
2) amine-terminated hyperbrancedization polyamide collagenous fibres are added in distilled water, stirring at normal temperature 0.5h, make to be uniformly dispersed, and obtains amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid; Every amine-terminated hyperbrancedization of gram polyamide collagenous fibres add in 100mL distilled water;
3) by mass concentration, be that the pH value of 40% glyoxalic acid solution is adjusted to 6.5, then add in amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid, under 10 ℃, continue reaction 4.0h, obtain containing the suspension of product, the suspension that will contain product filters, and the filter cake that obtains washs 3 times to wash away unreacted glyoxalic acid, then air drying with normal-temperature water, grind evenly, obtain end carboxyl super branched polyamide collagen fiber adsorption material; Wherein, in the amino on the amino ultrabranching polyamide collagenous fibres of amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid middle-end and glyoxalic acid solution, the mol ratio of glyoxalic acid is 1:1.
Embodiment 3:
1) prepare amine-terminated hyperbrancedization polyamide collagenous fibres (CF-HBPN) ([1] Wang Xuechuan, Zhang Feifei, torrential by force. hyperbranched collagenous fibres adsorbent synthetic with characterize [J]. functional material, 2013,44, (4): 527～531.);
2) amine-terminated hyperbrancedization polyamide collagenous fibres are added in distilled water, stirring at normal temperature 0.5h, make to be uniformly dispersed, and obtains amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid; Every amine-terminated hyperbrancedization of gram polyamide collagenous fibres add in 150mL distilled water;
3) by mass concentration, be that the pH value of 40% glyoxalic acid solution is adjusted to 7.0, then add in amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid, under 20 ℃, continue reaction 4.0h, obtain containing the suspension of product, the suspension that will contain product filters, and the filter cake that obtains washs 3 times to wash away unreacted glyoxalic acid, then air drying with normal-temperature water, grind evenly, obtain end carboxyl super branched polyamide collagen fiber adsorption material; Wherein, in the amino on the amino ultrabranching polyamide collagenous fibres of amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid middle-end and glyoxalic acid solution, the mol ratio of glyoxalic acid is 1:1.5.
Embodiment 4:
1) prepare amine-terminated hyperbrancedization polyamide collagenous fibres (CF-HBPN) ([1] Wang Xuechuan, Zhang Feifei, torrential by force. hyperbranched collagenous fibres adsorbent synthetic with characterize [J]. functional material, 2013,44, (4): 527～531.);
2) amine-terminated hyperbrancedization polyamide collagenous fibres are added in distilled water, stirring at normal temperature 0.5h, make to be uniformly dispersed, and obtains amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid; Every amine-terminated hyperbrancedization of gram polyamide collagenous fibres add in 300mL distilled water;
3) by mass concentration, be that the pH value of 40% glyoxalic acid solution is adjusted to 8.0, then add in amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid, under 40 ℃, continue reaction 4.5h, obtain containing the suspension of product, the suspension that will contain product filters, and the filter cake that obtains washs 3 times to wash away unreacted glyoxalic acid, then air drying with normal-temperature water, grind evenly, obtain end carboxyl super branched polyamide collagen fiber adsorption material; Wherein, in the amino on the amino ultrabranching polyamide collagenous fibres of amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid middle-end and glyoxalic acid solution, the mol ratio of glyoxalic acid is 1:2.
Embodiment 5:
1) prepare amine-terminated hyperbrancedization polyamide collagenous fibres (CF-HBPN) ([1] Wang Xuechuan, Zhang Feifei, torrential by force. hyperbranched collagenous fibres adsorbent synthetic with characterize [J]. functional material, 2013,44, (4): 527～531.);
2) amine-terminated hyperbrancedization polyamide collagenous fibres are added in distilled water, stirring at normal temperature 0.5h, make to be uniformly dispersed, and obtains amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid; Every amine-terminated hyperbrancedization of gram polyamide collagenous fibres add in 250mL distilled water;
3) by mass concentration, be that the pH value of 40% glyoxalic acid solution is adjusted to 6.0, then add in amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid, under 32 ℃, continue reaction 5.0h, obtain containing the suspension of product, the suspension that will contain product filters, and the filter cake that obtains washs 3 times to wash away unreacted glyoxalic acid, then air drying with normal-temperature water, grind evenly, obtain end carboxyl super branched polyamide collagen fiber adsorption material; Wherein, in the amino on the amino ultrabranching polyamide collagenous fibres of amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid middle-end and glyoxalic acid solution, the mol ratio of glyoxalic acid is 1:1.5.
The application test of end carboxyl super branched polyamide collagenous fibres:
The collagenous fibres of 0.1g are joined to the Cr(III that contains that the 100mL initial concentration is 100mg/L) solution, obtain the collagenous fibres treatment fluid; The end carboxyl super branched polyamide collagen fiber adsorption material of 0.1g is joined to the Cr(III that contains that the 100mL initial concentration is 100mg/L) solution, obtain end carboxyl super branched polyamide collagen fiber adsorption material treatment fluid;
Collagenous fibres treatment fluid and end carboxyl super branched polyamide collagen fiber adsorption material treatment fluid are placed in respectively to the isothermal vibration device after 30 ℃ of concussion reaction 6h, measure the Cr(III of filtrate) concentration, calculate collagenous fibres and end carboxyl super branched polyamide collagen fiber adsorption material to Cr(III) clearance.Experimental result shows that end carboxyl super branched polyamide collagenous fibres are to Cr(III) clearance be that collagenous fibres are to Cr(III) 2.37 times of clearance, absorption property significantly improves.
Claims (4)
1. the preparation method of an end carboxyl super branched polyamide collagen fiber adsorption material, is characterized in that, comprises the following steps:
1) amine-terminated hyperbrancedization polyamide collagenous fibres are added to the water, stirring at normal temperature makes to be uniformly dispersed, and obtains amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid;
2) the pH value of glyoxalic acid solution is adjusted to 5.5～8.0, then add in amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid, under 0-40 ℃, continue reaction 3.0～5.0h, obtain containing the suspension of product, the suspension that will contain product filters, the filter cake water that obtains washes away unreacted glyoxalic acid, and is then dry, obtains end carboxyl super branched polyamide collagen fiber adsorption material; Wherein, in the amino on the amino ultrabranching polyamide collagenous fibres of amine-terminated hyperbrancedization polyamide collagenous fibres dispersion liquid middle-end and glyoxalic acid solution, the mol ratio of glyoxalic acid is 1:(0.5～2).
2. the preparation method of end carboxyl super branched polyamide collagen fiber adsorption material according to claim 1, it is characterized in that: in described step 1), every amine-terminated hyperbrancedization of gram polyamide collagenous fibres add in 50～300mL water.
3. the preparation method of end carboxyl super branched polyamide collagen fiber adsorption material according to claim 1 is characterized in that: described step 2), the mass concentration of glyoxalic acid solution is 40%.
4. the preparation method of end carboxyl super branched polyamide collagen fiber adsorption material according to claim 1, it is characterized in that: the drying described step 2) is at room temperature carried out.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482126A (en) * | 2015-12-31 | 2016-04-13 | 陕西科技大学 | Aldehyde group-terminated hyperbranched polymer leather retanning agent and preparation method thereof |
| CN111155315A (en) * | 2020-01-14 | 2020-05-15 | 旷达纤维科技有限公司 | Colored polyester deodorizing fiber |
| CN115467165A (en) * | 2022-08-26 | 2022-12-13 | 中国第一汽车股份有限公司 | Automobile interior odor adsorption composite finishing agent and preparation and application thereof |
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| CN102600805A (en) * | 2012-03-28 | 2012-07-25 | 陕西科技大学 | Preparation method of modified collagen fiber adsorbing material |
| CN102744043A (en) * | 2012-07-02 | 2012-10-24 | 陕西科技大学 | Synthesis method of carboxylation modified collagen fiber adsorbent |
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Patent Citations (2)
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| CN102600805A (en) * | 2012-03-28 | 2012-07-25 | 陕西科技大学 | Preparation method of modified collagen fiber adsorbing material |
| CN102744043A (en) * | 2012-07-02 | 2012-10-24 | 陕西科技大学 | Synthesis method of carboxylation modified collagen fiber adsorbent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482126A (en) * | 2015-12-31 | 2016-04-13 | 陕西科技大学 | Aldehyde group-terminated hyperbranched polymer leather retanning agent and preparation method thereof |
| CN105482126B (en) * | 2015-12-31 | 2018-04-20 | 陕西科技大学 | A kind of terminal aldehyde hyper branched polymer leather retanning agent and preparation method thereof |
| CN111155315A (en) * | 2020-01-14 | 2020-05-15 | 旷达纤维科技有限公司 | Colored polyester deodorizing fiber |
| CN111155315B (en) * | 2020-01-14 | 2022-03-25 | 旷达纤维科技有限公司 | Colored polyester deodorizing fiber |
| CN115467165A (en) * | 2022-08-26 | 2022-12-13 | 中国第一汽车股份有限公司 | Automobile interior odor adsorption composite finishing agent and preparation and application thereof |
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