CN101165236B - High hydrolytic resistance polylactic acid fibre products - Google Patents
High hydrolytic resistance polylactic acid fibre products Download PDFInfo
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- CN101165236B CN101165236B CN2006100969434A CN200610096943A CN101165236B CN 101165236 B CN101165236 B CN 101165236B CN 2006100969434 A CN2006100969434 A CN 2006100969434A CN 200610096943 A CN200610096943 A CN 200610096943A CN 101165236 B CN101165236 B CN 101165236B
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- polylactic acid
- polylactic
- acid
- acid fiber
- fiber
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Abstract
The present invention discloses one kind of polylactic acid fiber product with high hydrolysis resistance, and over 60 % of the polylactic acid molecule chains have terminal carboxyl group in closed form. The polylactic acid fiber product is finished with finishing fluid containing water soluble cross-linking agent so as to have high hydrolysis resistance and high strength holding rate. The polylactic acid fiber product has wide use, and is suitable for use in clothing and in various industries.
Description
Technical field:
The present invention relates to the polylactic acid fibre production and processing method.
Background technology:
Acid fiber by polylactic PLA is a kind of novel ecological, environmental protective fiber type, it is raw material with the cornstarch, earlier its fermentation is made lactic acid, then through condensation, polymerisation is made PLA, and the higher molecular weight PLA that utilizes couplant to make again to have good mechanical passes through chemical modification at last, its intensity, water-retaining property are promoted and with its fibration, form through reeling off raw silk from cocoons then.The PLA fiber has the performance of a lot of excellences as the new generation of environment protection polyethylene terephthalate, as snugness of fit, elasticity, and drapability, hygroscopicity, gas permeability, heat resistance and anti-ultraviolet function, the PLA fiber has favorable biological degradability simultaneously.These excellent properties that acid fiber by polylactic has make it have broad application prospects in textile industry.Acid fiber by polylactic can be used for woven, knitting and non-weaving cloth.Acid fiber by polylactic can also be used for various fashionable dresses, leisure wear, sports goods, amenities etc.
But acid fiber by polylactic exists a very big problem as weaving and industry with fiber, because acid fiber by polylactic contains a lot of end carboxyls, is easy to hydrolysis under hot and humid condition.When acid fiber by polylactic uses as dress materials, all need to carry out back processed such as concise, typing, dyeing, the acid fiber by polylactic hydrolysis is very serious in process, molecular weight of polymer is descended significantly, the intensity of fibre sharply reduces, and does not satisfy the requirement of strength of actual use.
In addition, necessarily require good strength retention, but degraded is being carried out too because acid fiber by polylactic (comprises storage and transportation) in environment for use, and significantly reduced the service life of product as industry purposes material.
Summary of the invention:
The object of the present invention is to provide the good high hydrolytic resistance polylactic acid fibre of a kind of anti-hydrolytic performance.
Technical solution of the present invention is:
A kind of high hydrolytic resistance polylactic acid fibre is characterized in that: the terminal carboxyl group in the polylactic acid molecule chain is closing form, and it is structure shown in the formula 1 that the molecular end structure more than 60% is wherein arranged:
(formula 1)
Wherein R, R ' are alkyl, aliphatic group.
The content of carboxyl is at 20mol/10 in the acid fiber by polylactic structure
6Below the g.
The molecular weight of acid fiber by polylactic strand is between 80000～200000.
Production method is: polylactic acid fibre is put into the dressing liquid immersion treatment of following composition by weight, obtain these goods through curing then:
Water-soluble cross-linker 0.1%～20%
Other auxiliary agent 0%～10%
Soft water 70%～99.9%
Immersion treatment is handled for exhausting in bathing, and exhausts under 20～100 ℃ condition and handles 1～30min, and preliminary drying was handled 2～15 minutes under 60～120 ℃ condition then, baked to handle 2～10 minutes under 100～160 ℃ condition again.Water-soluble cross-linker is the aziridines water-soluble cross-linker.Other auxiliary agent is one or more in catalyst, pH value conditioning agent, the surfactant.Catalyst is organic amine compound or metal salt compound, as trimethylamine, triethylbenzene ammonium chloride, Sodium Benzoate, zinc acetate, potassium fluoborate, fluoboric acid magnesium, zinc fluoroborate etc.The pH value conditioning agent is diammonium hydrogen phosphate, acetic acid, hydrochloric acid or sulfuric acid.Glass or plastic containers such as poly alkyl alcohol ethylene oxide ether, alkyl phenol polyethylene glycol oxide ether etc., anion surfactant such as sodium alkyl sulfonate etc.
Reaction principle of the present invention is shown in following reaction, and these goods are after water-soluble cross-linker is handled
Polylactic acid fibre with molecular structure shown in following (A) formula.
Wherein R, R ' are alkyl, aliphatic group etc.
The present invention carries out processing and sorting by the processing and sorting liquid that use contains water-soluble crosslinking agent to polylactic acid fibre, can react by the end group of water-soluble cross-linker and fiber, thereby reduce the content of carboxyl end group of acid fiber by polylactic, make polylactic acid fibre have the high hydrolysis resistance performance, have good strength retention.And it is, of many uses by all kinds of polylactic acid articles that the present invention obtains.High hydrolytic resistance polylactic acid fibre of the present invention is applicable to clothes and various industry purposes, has very big economic benefit.This hydrolytic resistance polylactic acid fibre that the present invention makes has good dyeability, the intensity of fiber is protected than rough after 110～120 ℃ of disperse dyeings significantly raising, fibre strength is greater than 1.2CN/dtex, and the relative molecular mass conservation rate of acid fiber by polylactic also has significant improvement than rough.
The invention will be further described below in conjunction with embodiment.
The assay method that is adopted in the illustrative experiment at first
A. TENSILE STRENGTH
Use the instron of INTEC company, under the condition of constant speed elongation, measure, draw the TENSILE STRENGTH of sample by load-deformation curve.
B. the strength retention after the hot water treatment
In pressure vessel, add a certain amount of sample and water, under different temperatures and time condition, carry out hot water treatment.Measure its intensity then,, measure its strength retention according to the intensity after fiber and the fabric hot water treatment and its green strength.Intensity * 100% before intensity/hot water treatment after strength retention=hot water treatment.
C. the mensuration of relative molecular mass
Accurately take by weighing a certain amount of testing sample, make the dissolution with solvents sample, use gel permeation chrommatograph, measure the relative molecular mass of acid fiber by polylactic and fabric with oxolane.
The specific embodiment:
Embodiment 1:
1. the component with following weight fraction is mixed into processing and sorting liquid:
Aziridine water-soluble cross-linker 4%
Other auxiliary agent 0.5%
Soft water 95.5%
2. exhaust processing in the processing and sorting liquid of making being bathed acid fiber by polylactic (or PLA fabric), cure processing then.
The time that exhausts processing in the bath is 1～30 minute, and preferably 10 minutes, temperature was 20～100 ℃.Cure when handling, at first preliminary drying was handled 5 minutes under 60～120 ℃ of temperature conditions, and then baked under 100～130 ℃ temperature conditions 3 minutes.
Wherein the aziridine water-soluble cross-linker is an aliphatic aziridine water-soluble cross-linker, other auxiliary agent is a pH value conditioning agent diammonium hydrogen phosphate, catalyst is organic amine compound or metal salt compound, as trimethylamine, triethylbenzene ammonium chloride, Sodium Benzoate, zinc acetate, potassium fluoborate, fluoboric acid magnesium, zinc fluoroborate etc.
Reaction equation is:
Wherein R, R ' are alkyl, aliphatic group etc.
The end group that obtains the polylactic acid molecule chain through said process is the acid fiber by polylactic (or PLA fabric) of closing form, and it is structure shown in the formula 1 that the molecular end structure more than 60% is wherein arranged:
(formula 1)
Wherein R, R ' are alkyl, aliphatic group etc.
The content of carboxyl is at 20mol/10 in the acid fiber by polylactic structure
6Below the g.The molecular weight of acid fiber by polylactic strand is between 80000～200000.
Sample before and after processing is carried out hot water treatment experiment and carboxyl-content mensuration, by the Strength Changes of sample and the anti-hydrolytic performance of carboxyl-content variation evaluation fabric.
Concrete outcome is as shown in the table:
Claims (2)
1. high hydrolytic resistance polylactic acid fibre, it is characterized in that: the terminal carboxyl group in the polylactic acid molecule chain is closing form, and it is structure shown in the formula 1 that the molecular end structure more than 60% is wherein arranged:
Wherein R, R ' are alkyl, aliphatic group, and the molecular weight of acid fiber by polylactic strand is between 80000～200000.
2. a kind of high hydrolytic resistance polylactic acid fibre according to claim 1 is characterized in that: the content of carboxyl is at 20mol/10 in the acid fiber by polylactic structure
6Below the g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100969434A CN101165236B (en) | 2006-10-20 | 2006-10-20 | High hydrolytic resistance polylactic acid fibre products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100969434A CN101165236B (en) | 2006-10-20 | 2006-10-20 | High hydrolytic resistance polylactic acid fibre products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101165236A CN101165236A (en) | 2008-04-23 |
| CN101165236B true CN101165236B (en) | 2011-07-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100969434A Expired - Fee Related CN101165236B (en) | 2006-10-20 | 2006-10-20 | High hydrolytic resistance polylactic acid fibre products |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106638028B (en) * | 2016-11-28 | 2018-11-27 | 苏州大学 | Method for improving bioactivity of viscose and chitin blend fiber |
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2006
- 2006-10-20 CN CN2006100969434A patent/CN101165236B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| JP特开2005-200775A 2005.07.28 |
| seong lhl woo etc..Polymerization of aqueous lactic acid to prepare high molecular weight poly(lactic acid) by chain-extending with hexamethylene diisocyanate.《Polymer Bulletin》.1995,第35卷415-420. * |
| 赵京波等.合成生物降解性聚酯研究的进展.《高分子通报》.1997,(第2期),11-15. * |
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| CN101165236A (en) | 2008-04-23 |
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Granted publication date: 20110727 Termination date: 20111020 |