CN1314846C - Spinning stoste of cellulose derivative and its preparation and use - Google Patents
Spinning stoste of cellulose derivative and its preparation and use Download PDFInfo
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- CN1314846C CN1314846C CNB2005100408844A CN200510040884A CN1314846C CN 1314846 C CN1314846 C CN 1314846C CN B2005100408844 A CNB2005100408844 A CN B2005100408844A CN 200510040884 A CN200510040884 A CN 200510040884A CN 1314846 C CN1314846 C CN 1314846C
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Abstract
The present invention discloses a spinning solution of cellulose derivatives, a preparation method thereof and an application thereof, and the spinning solution is prepared from adding surface activity additives into CAB, CAP, HEC and HPC as raw materials and acetic acids, formic acids, etc. as solvents after sufficient stir, standing and deaeration. The spinning solution is used in electrostatic spinning, and can be made into ultra-fine fibers with the diameter of 200 to 1000 nm; additionally, the ultra-fine fibers not only have characteristics of good absorptivity, strong filtering, etc., but also have characteristics of favorable biocompatibility, good biodegradability, excellent ultraviolet light resistance, good cold hardiness, etc. The present invention effectively solves the problems of spinnability of the class of solutions, relieves the phenomenon of blocked spinning jets in the process of electrostatic spinning and decreases the formation of bead joints of fibers, and prepared ultra-fine fibers have uniform thickness in diameter; the quality of products is enhanced, the present invention also adds new varieties into fiber products, and meanwhile the present invention opens up new applications of material of cellulose derivatives.
Description
Technical field
The present invention relates to spinning solution and preparation and the application of cellulose derivative, the particularly spinning solution of cellulose ether and ester and preparation thereof and application belongs to spinning solution preparation and applied technical field.
Background technology
Cellulose ether and ester all are the natural polymer derivatives, have excellent biological compatibility and biodegradability, have character such as good ultraviolet resistance, cold-resistant, pliable and tough, transparent and electric insulation simultaneously, therefore, this class raw material is mainly used in coating and fields such as leather gloss agent and other industrial auxiliary agent.At present, cellulose derivative is used for spinning, particularly prepare superfine fibre with electrospinning process, remove and use acetyl cellulose, sodium carboxymethylcellulose and cyano group cellulose are having outside the report of raw material, other as relevant cellulose acetate-butyrate (CAB), cellulose acetate propionate (CAP), hydroxyethylcellulose (HEC) and hydroxypropyl cellulose cellulose derivatives such as (HPC) are used to prepare the technology of superfine fibre, so far do not see yet both at home and abroad report is arranged, this is owing to the decision of material self character, because, CAB, substituting group types such as CAP are many, the substituting group size is bigger, these materials all are non-fibre-grades, usually spinning moulding is relatively more difficult, and especially electrostatic spinning is more difficult.Electrospinning process is directly and the simply method of preparation high molecular superfine fiber, and the fibre diameter that obtains can hang down and reach nanoscale, and fiber has great specific area.But electrostatic spinning has the superfine fibre that spinning nozzle easily stops up, obtains and " pearl joint " occur through regular meeting, and the unequal shortcoming of fibre diameter thickness that obtains with a kind of spinning solution has a negative impact to the spinning moulding and the structural behaviour of fiber.Therefore, use existing electrospinning process, can't make various level and smooth and plain ether of true fibre and ester superfine fibres such as cellulose acetate-butyrate, cellulose acetate propionate.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of spinning solution of cellulose-derived raw material and method of preparation and application thereof of containing is provided.
For achieving the above object, the technical solution used in the present invention is: the spinning solution of a kind of cellulose derivative, contain raw material and solvent, and also contain surfactant additive in the described spinning solution; Described raw material is selected from cellulose acetate-butyrate, cellulose acetate propionate, hydroxyethylcellulose and hydroxypropyl cellulose or their combination; Described solvent is a kind of in water, acetic acid, formic acid, propionic acid, acetone, butanone, pentanone, the cyclohexanone or their mixture.
Described surfactant additive is a kind of in anionic surfactant, cationic surface active agent, amphoteric surfactant and the nonionic surface active agent or their composition.
The preparation method of spinning dope of a kind of cellulose derivative of the present invention is, earlier powder shaped raw material, surfactant additive is dissolved in the solvent, and material content is 1.0～70wt%, and surfactant additive content is 0.1～20wt%; Under 20～80 ℃ temperature conditions, fully stir again, obtain uniform spinning solution after the standing and defoaming.
The application of the spinning solution of a kind of cellulose derivative of the present invention, it is characterized in that: described spinning solution is applied to electrostatic spinning, spinning temperature is 15～100 ℃, the output voltage of high voltage source is 3～50KV, distance between receiving screen and the spinning nozzle is 5～35cm, and making diameter is the cellulose ether of 200～1000nm and the superfine fibre of ester.
Advantage of the present invention is:
1. the present invention has added surfactant additive in the stoste of preparation spinning, solved the spinnability of CAB, CAP, HEC and HPC solution effectively, alleviated spinning nozzle phenomenon of blocking in the electrostatic spinning process, reduced the formation of fiber " pearl joint ", the superfine fibre diameter thickness that makes is even, has improved the quality of product.
2. the CAB that makes with electrospinning process, CAP, HEC and HPC superfine fibre nonwoven cloth, except strong adsorptivity that common superfine fibre nonwoven cloth had, strong filter etc., also because the material behavior of CAB, CAP, HEC and HPC itself, product has excellent biological compatibility and biodegradability and good ultraviolet resistance, character such as cold-resistant, can satisfy some special application requirements, widen the Application Areas of superfine fibre nonwoven cloth.
3. utilize CAB, CAP, HEC and HPC spinning solution, filled up the blank of domestic and international this product of nothing, opened up the new purposes of the plain derivative raw material of this fibrid as superfine fibre, simultaneously, for the fiber-like product has added new kind.CAB, CAP, HEC and HPC powder wide material sources, cheap, the electrostatic spinning production process is pollution-free, and the superfine fibre nonwoven cloth product purpose is extensive, and therefore, this technology has broad prospect for its application.
Description of drawings
Fig. 1 is that the spinning solution of the cellulose derivative in the embodiment of the invention is applied to electrostatic spinning, the principle schematic of its device for spinning.
Wherein: the 1st, high voltage source; The 2nd, former liquid container; The 3rd, spinning nozzle; The 4th, nozzle; The 5th, receiving screen.
The specific embodiment
Embodiment one:
With cellulose acetate-butyrate (CAB) is raw material, prepare the CAB spinning solution earlier, solvent is the mixed solvent of acetic acid and acetone, acetic acid: acetone=1: 2 (volume ratio), cationic surface active agent are softex kw (CTAB), wherein, the CAB powder content is 50wt%, ctab surface activating agent addition is 1wt%, stirs under 25 ℃ temperature conditions, obtains uniform CAB spinning solution after the standing and defoaming.
Referring to accompanying drawing 1, the CAB spinning solution that makes is injected in the former liquid container 2, spinning temperature is about 25 ℃, and the output voltage of high voltage source 1 is 10KV, and the distance between receiving screen 5 and the spinning nozzle 3 is 20cm, and receiving screen is an aluminium foil.Take off the CAB superfine fibre of collecting on the receiving screen, its diameter is 500 ± 50nm, and level and smooth, even thickness.
Embodiment two:
With cellulose acetate propionate (CAP) is raw material, prepare the CAP spinning solution earlier, solvent is an acetone, nonionic surface active agent is polyethylene glycol (PEG), and wherein, the CAB powder content is 40wt%, the PEG degree of polymerization is 20000, addition is 2wt%, stirs under 50 ℃ temperature conditions, obtains uniform CAP spinning solution after the standing and defoaming.
Referring to accompanying drawing 1, the CAP spinning solution that makes is injected in the former liquid container 2, spinning temperature is about 80 ℃, and the output voltage of high voltage source 1 is 25KV, and receiving screen 5 is 30cm with the distance of asking of spinning nozzle 3, and receiving screen is a copper mesh.Take off the CAP superfine fibre of collecting on the receiving screen, its diameter is 600 ± 50nm, and level and smooth, even thickness.
Embodiment three:
With hydroxyethylcellulose (HEC) is raw material, prepare the HEC spinning solution earlier, solvent is a water, anionic surfactant is a dodecyl sodium sulfate, wherein the HEC powder content is 30wt%, the surfactant addition is 2.5wt%, stirs on magnetic stirrer under 30 ℃, obtains uniform HEC spinning solution after the standing and defoaming.
Referring to accompanying drawing 1, the HEC spinning solution that makes is injected in the former liquid container 2, spinning temperature is about 20 ℃, and the output voltage of high voltage source 1 is 30KV, and the distance between receiving screen 5 and the spinning nozzle 3 is 10cm, and receiving screen is a copper mesh.Take off the HEC superfine fibre of collecting on the receiving screen, its diameter is 300 ± 50nm, and level and smooth, even thickness.
Embodiment four:
With hydroxypropyl cellulose (HPC) is raw material, prepare the HPC spinning solution earlier, solvent is a water, additive is the amphoteric surfactant phosphatid ylcholine, wherein the HPC powder content is 15wt%, the surfactant addition is 0.5wt%, stirs on magnetic stirrer under 25 ℃, obtains uniform HPC spinning solution after the standing and defoaming.
Referring to accompanying drawing 1, the HPC spinning solution that makes is injected in the former liquid container 2, spinning temperature is about 35 ℃, and the output voltage of high voltage source 1 is 40KV, and the distance between receiving screen 5 and the spinning nozzle 3 is 35cm, and receiving screen is a copper mesh.Take off the HPC superfine fibre of collecting on the receiving screen, its diameter is 400 ± 50nm, and level and smooth, even thickness.
CAB, the CAP, HEC and the HPC superfine fibre that make by technical solutions of above embodiments can be used as medical material, as extensive uses such as wound dressing, timbering material and drug sustained release systems.
Claims (4)
1, the spinning solution of a kind of cellulose derivative contains raw material and solvent, it is characterized in that: also contain surfactant additive in the described spinning solution; Described raw material is selected from cellulose acetate-butyrate, cellulose acetate propionate, hydroxyethylcellulose and hydroxypropyl cellulose or their combination; Described solvent is a kind of in water, acetic acid, formic acid, propionic acid, acetone, butanone, pentanone, the cyclohexanone or their mixture.
2, the spinning solution of a kind of cellulose derivative according to claim 1 is characterized in that: described surfactant additive is a kind of in anionic surfactant, cationic surface active agent, amphoteric surfactant and the nonionic surface active agent or their composition.
3, the preparation method of spinning dope of a kind of cellulose derivative as claimed in claim 1, it is characterized in that: earlier powder shaped raw material, surfactant additive are dissolved in the solvent, material content is 1.0～70wt%, and surfactant additive content is 0.1～20wt%; Under 20～80 ℃ temperature conditions, fully stir again, obtain uniform spinning solution after the standing and defoaming.
4, the application of the spinning solution of a kind of cellulose derivative as claimed in claim 1, it is characterized in that: described spinning solution is applied to electrostatic spinning, spinning temperature is 15～100 ℃, the output voltage of high voltage source is 3～50KV, distance between receiving screen and the spinning nozzle is 5～35cm, and making diameter is the cellulose ether of 200～1000nm and the nanofiber of ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100408844A CN1314846C (en) | 2005-06-29 | 2005-06-29 | Spinning stoste of cellulose derivative and its preparation and use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100408844A CN1314846C (en) | 2005-06-29 | 2005-06-29 | Spinning stoste of cellulose derivative and its preparation and use |
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| Publication Number | Publication Date |
|---|---|
| CN1710158A CN1710158A (en) | 2005-12-21 |
| CN1314846C true CN1314846C (en) | 2007-05-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100408844A Expired - Fee Related CN1314846C (en) | 2005-06-29 | 2005-06-29 | Spinning stoste of cellulose derivative and its preparation and use |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146594A (en) * | 2011-05-09 | 2011-08-10 | 张家港耐尔纳米科技有限公司 | Oxidized cellulose nanofibers and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277642B (en) * | 2011-07-04 | 2013-01-09 | 西南科技大学 | Method for preparing fibers by thermoplastic carboxymethylcellulose derivatives through electrostatic spinning |
| CN104911738B (en) * | 2015-05-19 | 2017-03-15 | 南京林业大学 | A kind of preparation method of PU/CAP core sheath structure fibers |
| CN110656390B (en) * | 2019-09-27 | 2022-06-24 | 武汉轻工大学 | Cellulose derivative fiber, preparation method thereof and application thereof in processing edible oil |
| CN111139541B (en) * | 2020-03-10 | 2023-06-30 | 苏州大学 | Stirring type large-batch free liquid level electrostatic spinning device and method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS523011B1 (en) * | 1968-12-03 | 1977-01-25 |
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2005
- 2005-06-29 CN CNB2005100408844A patent/CN1314846C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS523011B1 (en) * | 1968-12-03 | 1977-01-25 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146594A (en) * | 2011-05-09 | 2011-08-10 | 张家港耐尔纳米科技有限公司 | Oxidized cellulose nanofibers and preparation method thereof |
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| CN1710158A (en) | 2005-12-21 |
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