CN105463624B - The preparation method of the vertical structure rate polylactic acid stereoscopic composite of height - Google Patents
The preparation method of the vertical structure rate polylactic acid stereoscopic composite of height Download PDFInfo
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- CN105463624B CN105463624B CN201511005350.8A CN201511005350A CN105463624B CN 105463624 B CN105463624 B CN 105463624B CN 201511005350 A CN201511005350 A CN 201511005350A CN 105463624 B CN105463624 B CN 105463624B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
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Abstract
The invention discloses a kind of preparation method of high vertical structure rate polylactic acid stereoscopic composite, comprise the following steps：(1) by described PLLA and the dissolving of dextrorotation PLA, then solvent is removed in volatilization in a solvent, the pre- vertical structure thing of PLA for the solid-state that step (1) is obtained 170~230 DEG C temperature, tension force be 0.3~0.6cN/dtex under the vertical 0~120min of structure of heat, finally it is cooled to room temperature, rate of temperature fall is 1~20 DEG C/min, during being somebody's turn to do, pre- vertical structure thing keeps solid forms, obtains described height and founds structure rate polylactic acid stereoscopic composite.The polylactic acid stereoscopic composite of vertical structure rate 100% prepared by the inventive method has single melting peak, and melting temperature is more than 200 DEG C.Its softening temperature is 125~165 DEG C, far above common PLA fibers (60~120 DEG C).It is 65%~95% that the polylactic acid stereoscopic composite hydrolyzes 1h post-tensioning strength retention in 130 DEG C, pH5 solution, far above common PLA products.
Description
Technical field
The present invention relates to the preparation method of polylactic acid stereoscopic composite.
Background technology
The problem of non-renewable and non-degradable of petroleum based material is not present in poly-lactic acid material, is expected to take in many fields
For traditional non-renewable petroleum base high polymer material (such as polypropylene, polyamide, polyester).PLA is with natural reproducible resource
(such as corn, wheat) is raw material, it is fermented, polymerization and obtain, can be with degradable into dioxy when discarded without the use of petroleum resources
Change carbon and water, environmental pollution will not be caused.The advantages of based on more than PLA, PLA has broad application prospects.
But the relatively low softening temperature of PLA and facile hydrolysis limit its large-scale commercial application.It is such as poly-
Lactic acid, which cannot be used for preparing, the packing containers such as lunch box, the cup of heat resistant requirements, can not also be used as engineering plastics in automobile, electricity
Sub- electrical component etc. is applied.High temperature facile hydrolysis limits application of the acid fiber by polylactic in textile industry.Due to poly-
Acid fiber easily hydrolyzes, and is acutely hydrolyzed when higher temperature dyes, and fibrous mechanical property is impaired serious, so acid fiber by polylactic
Relatively low temperature can only be used to dye, cause the dye-uptake of dyestuff low, fabric can only obtain shallower color.
Ikada etc. is in document Macromolecules 1987,20:Reported first in 904-906 and pass through PLLA
(PLLA) and the blending of dextrorotation PLA (PDLA) can form the crystallization of vertical structure, and the stereoscopic composite fusing point is higher than common PLA
30~60 DEG C.Therefore Many researchers are want to improve the performance of PLA by forming polylactic acid stereoscopic crystallization.
Presently disclosed most of polylactic acid stereoscopic spinning process are, it is necessary to use nucleator.Publication number CN 101805941A
Report a kind of method that polylactic acid fiber with high melting point is prepared using PLLA and PDLA blend melt spinnings.This method adds
0.01wt%~5wt% nucleator, prepared acid fiber by polylactic fusing point are 209 DEG C；CN 102409432A disclose it is a kind of with
Alkyl fatty race salt carries out the method that PLLA, PDLA blend melt spinning prepare high heat-proof polylactic acid fiber as nucleator.Should
Fibers melt temperature has ironability more than 190 DEG C, and at 170 DEG C；CN 101528994A disclose one kind with phosphate
Metal salt carries out the method that PLLA, PDLA blend melt spinning prepare acid fiber by polylactic, the heat resistance of the fiber as nucleator
It is excellent with thermal shrinkage.It is configured to however, the addition of nucleator is stood in promotion, is often dropped while improving material thermal resistance
The mechanical property of low material.CN 1400343A report a kind of vertical structure fiber of PLLA and PDLA blending, and the fiber is below 90 DEG C
Intensity be 0.8cN/dtex.But the preparation of the fiber needs very high spinning speed, and complicated hot gas spring condition.It is above-mentioned
Complexity of the method due to technique or the high request to equipment, are all difficult to industrialization promotion.
Vertical structure rate is higher, and the heat resistance and hydrolytic resistance of polylactic acid stereoscopic composite are better.When PLLA and PDLA is mixed
Vertical structure crystallization is readily formed, while can also form homogeneous crystallization.Therefore, simple mixing is extremely difficult to 100% vertical structure
Rate.Therefore, the height for developing a kind of easy large-scale promotion of high-efficient simple founds structure rate (vertical structure rate refers to vertical structure crystallization and accounts for total crystallization
Ratio) the preparation method of polylactic acid stereoscopic composite have great importance.
The content of the invention
It is existing to overcome present invention aims at a kind of preparation method of high vertical structure rate polylactic acid stereoscopic composite of offer
The defects of technology is present, meet the needs of people.
Described height founds the preparation method of structure rate polylactic acid stereoscopic composite, comprises the following steps：
(1) pre- vertical structure：Described PLLA (PLLA) and dextrorotation PLA (PDLA) are dissolved in a solvent respectively,
Then two kinds of solution are mixed, the pre- vertical structure thing of PLA of solvent acquisition solid-state is removed in then volatilization；Or will be described left-handed poly-
In a solvent, solvent is removed in then volatilization for lactic acid (PLLA) and dextrorotation PLA (PDLA) co-dissolve, obtains PLLA/PDLA mixing
Material, the pre- vertical structure thing of PLA of as solid-state, the pre- vertical structure thing of PLA of the solid-state can be plastics, film, fiber or
Using PLA as matrix or the composite of reinforcement；
Preferably, the weight ratio of described PLLA (PLLA) and dextrorotation PLA (PDLA) is 10:90~90:
10；
Preferably, the weight average molecular weight of described PLLA (PLLA) and dextrorotation PLA (PDLA) is 50,000~35
Ten thousand；
Preferably, the weight average molecular weight ratio of described PLLA (PLLA) and dextrorotation PLA (PDLA) is 1：6 arrive
6：1；
Term " the ratio between weight average molecular weight " refers to the ratio between PLLA and PDLA molecular size range, if PLLA is that 300,000, PDLA is
100000, the ratio between weight average molecular weight is 3:1；
Described solvent in the organic solvents such as chloroform, tetrahydrofuran, dioxane, hexafluoroisopropanol it is a kind of with
On；
(2) structure is found entirely：By temperature of the pre- vertical structure thing of PLA of the solid-state of step (1) acquisition at 170~230 DEG C, tension force
For the vertical 0~120min of structure of heat under 0.3~0.6cN/dtex, room temperature is finally cooled to, rate of temperature fall is 1~20 DEG C/min, the mistake
Cheng Zhong, pre- vertical structure thing keep solid forms, obtain described height and found structure rate polylactic acid stereoscopic composite；
Further, preparation method of the invention, comprises the following steps：
(1) PLLA (PLLA) and dextrorotation PLA (PDLA) are dissolved in solvent respectively, it is then molten by two kinds again
Liquid mixes, and is paved into film, and volatilization removes solvent, obtains PLLA/PDLA compounds, then injects described PLLA/PDLA compounds
Melting extrusion in extruder, collection obtain as-spun fibre, 2.5~3.5 times of the drawing-off at 100 DEG C~120 DEG C by as-spun fibre, so
Afterwards by the product after drawing-off, 20~120 DEG C, preferably 20~30 DEG C are cooled to, rate of temperature fall is 1~20 DEG C/min, obtains drawing-off
The acid fiber by polylactic of cooling afterwards, it is the pre- vertical structure thing of PLA of solid-state；
Wherein：Screw rod area temperature is 175~240 DEG C, and spinneret temperature is 230 DEG C~235 DEG C, spinning speed 800m/
min；
Preferably, the weight ratio of described PLLA (PLLA) and dextrorotation PLA (PDLA) is 10:90~90:
10；
Preferably, the weight average molecular weight of described PLLA (PLLA) and dextrorotation PLA (PDLA) is 50,000~35
Ten thousand；
Preferably, the weight average molecular weight ratio of described PLLA (PLLA) and dextrorotation PLA (PDLA) is 1：6 arrive
6：1；
Term " the ratio between weight average molecular weight " refers to the ratio between PLLA and PDLA molecular size range, if PLLA is that 300,000, PDLA is
100000, the ratio between weight average molecular weight is 3:1；
Described solvent in the organic solvents such as chloroform, tetrahydrofuran, dioxane, hexafluoroisopropanol it is a kind of with
On；
(2) by the acid fiber by polylactic after drawing-off at 170~230 DEG C, preferably 190~205 DEG C, tension force is 0.3~0.6cN/
0~120min, preferably 40~60min are kept under dtex, carries out secondary vertical structure, described height is obtained and founds structure rate polylactic acid stereoscopic
Compound, for a kind of high vertical structure rate polylactic acid stereoscopic fiber；
Term " tension force " is defined as follows：When object under tension acts on, it is present in inside it and perpendicular to two adjacent parts
Mutual tractive force on contact surface；
Described height founds structure rate polylactic acid stereoscopic composite, when being measured with differential scanning calorimeter, has single
Melting peak, and the melting peak temperature be more than 200 DEG C, it is preferred that when being measured with differential scanning calorimeter, have it is single
Melting peak, and the melting peak temperature be 218~228 DEG C；With XRD determining only have diffraction maximum that vertical structure crystallizes (2 θ=12 °,
21 °, 24 °), without the diffraction maximum (2 θ=16 °) homogeneously crystallized；Crystallinity is 30~60%, and preferably crystallinity is 48~53%；
Softening temperature is 125~165 DEG C, preferably 149~153 DEG C；Fusing point be 200~240 DEG C, preferably 218~224
℃；
After hydrolyzing 1h in 130 DEG C, pH 5 solution, stretching strength retentivity is 65%~95%, preferably 87%
~92%；
By described height stand structure rate polylactic acid stereoscopic fiber using method well known in the art carry out woven, knitting or
It is non-woven, you can the height for obtaining other forms founds structure rate polylactic acid stereoscopic composite, available for clothes, home textile product, women and children
Amenities and industrial nonwoven cloth etc.；
For the present invention without using any nucleator and other additives, products obtained therefrom is 100% polylactic acid article, and technique is simple
It is single, it is adapted to large-scale production.The vertical structure rate that described height founds structure rate polylactic acid stereoscopic composite is 100%, and heat resistance is excellent
It is good.In addition, it is 65%~95% that the product hydrolyzes 1h post-tensioning strength retention in 130 DEG C, pH 5 solution, hydrolytic resistance
It is excellent.
The polylactic acid stereoscopic composite of vertical structure rate 100% prepared by the inventive method has single melting peak, and molten
Melt temperature more than 200 DEG C.Its softening temperature is 125~165 DEG C, far above common PLA fibers (60~120 DEG C).The poly- breast
It is 65%~95% that sour stereoscopic composite hydrolyzes 1h post-tensioning strength retention in 130 DEG C, pH 5 solution, far above common
PLA products.
Brief description of the drawings
Fig. 1 is the result that the differential scanning calorimeter of embodiment 1 measures.
Fig. 2 is the XRD test results of embodiment 1.
Fig. 3 is the result that the differential scanning calorimeter of embodiment 2 measures.
Fig. 4 is the XRD test results of embodiment 2.
Fig. 5 is the result that the differential scanning calorimeter of embodiment 3 measures.
Fig. 6 is the XRD test results of embodiment 3.
Embodiment
Technical scheme and effect are further described with reference to embodiment.These embodiments are only used for
Illustrate the present invention rather than limitation the scope of the present invention.
Embodiment 1
The PLLA of weight average molecular weight 250,000 and weight average molecular weight 80,000 PDLA are dried；Take dried PLLA and
Each 50g of PDLA are dissolved in 500ml chloroform respectively, are fully dissolved by 20h, then the even solution of both of which is mixed into 5h, so
Mixed solution is paved into film afterwards, volatilized by solvent, obtains PLLA/PDLA compounds.
Inject a mixture into single screw extrusion machine and melt, extruded through measuring pump and spinneret orifice, collection obtains as-spun fibre.
Wherein screw rod area temperature is 240 DEG C, and spinneret temperature is 235 DEG C, spinning speed 800m/min.As-spun fibre is at 100 DEG C
2.5 times of drawing-off.Pre- vertical structure of the whole spinning process equivalent to the inventive method above.
By the acid fiber by polylactic after drawing-off at 190 DEG C, tension force is to handle 45min under 0.4cN/dtex to carry out secondary vertical structure.
The fiber is measured with differential scanning calorimeter and only a melting peak nearby occurs at 228 DEG C, illustrates only vertical structure knot in the fiber
Crystalline substance, and without homogeneous crystallization, found structure rate 100%.Tested through XRD, the crystallinity of the fiber is 51%.The acid fiber by polylactic it is soft
It is 154 DEG C to change temperature, and it is 91% that 1h post-tensioning strength retention is hydrolyzed in 130 DEG C, pH 5 solution.
Embodiment 2
PLLA and PDLA that weight average molecular weight is 150,000 are dried；Take dried each 30g of PLLA and PDLA points
It is not dissolved in 300ml chloroform, is fully dissolved by 20h, then the even solution of both of which is mixed into 5h, then by mixed solution
Film is paved into, is volatilized by solvent, obtains PLLA/PDLA blend films.Above solution mixed process is pre- equivalent to the inventive method
Vertical structure.
PLLA/PDLA blend films are handled into 30min at 205 DEG C and carry out secondary vertical structure.Measured with differential scanning calorimeter
Only nearby there is a melting peak at 226 DEG C in the film, illustrates only vertical structure crystallization in the film, and without homogeneous crystallization, found structure rate
100%.Tested through XRD, the crystallinity of the film is 56%.The softening temperature of the polylactic acid membrane is 156 DEG C, at 130 DEG C, pH's 5
It is 94% that 1h post-tensioning strength retention is hydrolyzed in solution.
Embodiment 3
The PLLA of weight average molecular weight 250,000 and weight average molecular weight 80,000 PDLA are dried；Take dried PLLA and
Each 30g of PDLA are dissolved in 300ml chloroform respectively, are fully dissolved by 20h, then the even solution of both of which is mixed into 5h, so
Mixed solution is paved into film afterwards, volatilized by solvent, obtains PLLA/PDLA blend films.Above solution mixed process is equivalent to this
The pre- vertical structure of inventive method.
PLLA/PDLA blend films are handled into 30min at 205 DEG C and carry out secondary vertical structure.Measured with differential scanning calorimeter
Only nearby there is a melting peak at 224 DEG C in the film, illustrates only vertical structure crystallization in the film, and without homogeneous crystallization, found structure rate
100%.Tested through XRD, the crystallinity of the film is 53%.The softening temperature of the polylactic acid membrane is 152 DEG C, at 130 DEG C, pH's 5
It is 91% that 1h post-tensioning strength retention is hydrolyzed in solution.
Comparative example 4
The PLLA of weight average molecular weight 150,000 is dried；Take dried PLLA 60g to be dissolved in 600ml chloroform, pass through
Cross 20h fully to dissolve, solution is then paved into film, volatilized by solvent, obtain PLLA films.This is measured with differential scanning calorimeter
Only nearby there is a melting peak at 168 DEG C in film, illustrates only homogeneous crystallization in the film.Tested through XRD, homogeneous crystal in the film
Crystallinity be 31%.The softening temperature of the polylactic acid membrane is 68 DEG C, and it is strong that 1h post-tensioning is hydrolyzed in 130 DEG C, pH 5 solution
It is 15% to spend conservation rate.
Claims (3)
1. the preparation method of the vertical structure rate polylactic acid stereoscopic composite of height, it is characterised in that comprise the following steps：
(1) pre- vertical structure：PLLA (PLLA) and dextrorotation PLA (PDLA) are dissolved in a solvent respectively, then by two kinds
Solution mixes, and the pre- vertical structure thing of PLA of solvent acquisition solid-state is removed in then volatilization；Or by PLLA (PLLA) and dextrorotation
In a solvent, solvent is removed in then volatilization to PLA (PDLA) co-dissolve, obtains the pre- vertical structure thing of PLA of solid-state；
(2) structure is found entirely：By temperature of the pre- vertical structure thing of PLA of the solid-state of step (1) acquisition at 170~230 DEG C, tension force 0.3
0~120min of the vertical structure of heat, is finally cooled to room temperature under~0.6cN/dtex, and rate of temperature fall is 1~20 DEG C/min, during being somebody's turn to do,
Pre- vertical structure thing keeps solid forms, obtains described height and founds structure rate polylactic acid stereoscopic composite, described PLLA
(PLLA) and dextrorotation PLA (PDLA) weight ratio be 10:90~90:10, described PLLA (PLLA) and dextrorotation gather
The weight average molecular weight of lactic acid (PDLA) is 50,000~350,000；
Described PLLA (PLLA) and the weight average molecular weight ratio of dextrorotation PLA (PDLA) are 1：6 to 6：1.
2. the preparation method of the vertical structure rate polylactic acid stereoscopic composite of height, it is characterised in that comprise the following steps：
(1) PLLA (PLLA) and dextrorotation PLA (PDLA) are dissolved in solvent respectively, then again mixed two kinds of solution
Close, be paved into film, solvent is removed in volatilization, obtains compound, or PLLA (PLLA) and dextrorotation PLA (PDLA) is common
In a solvent, solvent is removed in then volatilization, obtains the pre- vertical structure thing of PLA of solid-state for dissolving；Then described compound is injected and squeezed
Go out melting extrusion in machine, collection obtains as-spun fibre, 2.5~3.5 times of the drawing-off at 100 DEG C~120 DEG C by as-spun fibre, then
By the product after drawing-off, 20~120 DEG C are cooled to, obtains the pre- vertical structure thing of PLA of solid-state；
(2) by the acid fiber by polylactic after drawing-off at 170~230 DEG C, tension force is that 0~120min is kept under 0.3~0.6cN/dtex,
Secondary vertical structure is carried out, described height is obtained and founds structure rate polylactic acid stereoscopic composite, for a kind of high vertical structure rate polylactic acid stereoscopic
Fiber, in step (1), rate of temperature fall is 1~20 DEG C/min, and screw rod area temperature is 175~240 DEG C, and spinneret temperature is 230 DEG C
~235 DEG C, spinning speed 800m/min, the weight ratio of described PLLA (PLLA) and dextrorotation PLA (PDLA) is
10:90~90:10, the weight average molecular weight of described PLLA (PLLA) and dextrorotation PLA (PDLA) is 50,000~350,000；
Described PLLA (PLLA) and the weight average molecular weight ratio of dextrorotation PLA (PDLA) are 1：6 to 6：1.
3. according to the method described in any one of claim 1~2, it is characterised in that described height founds structure rate polylactic acid stereoscopic
Compound, when being measured with differential scanning calorimeter, there is single melting peak, and the melting peak temperature is more than 200 DEG C,
There was only diffraction maximum that vertical structure crystallizes (2 θ=12 °, 21 °, 24 °) with XRD determining, without the diffraction maximum (2 θ=16 °) homogeneously crystallized；Knot
Brilliant degree is 30~60%；Softening temperature is 125~165 DEG C, and fusing point is 200~240 DEG C, is hydrolyzed in 130 DEG C, pH 5 solution
After 1h, stretching strength retentivity is 65%~95%.
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| CN109337308B (en) * | 2018-08-30 | 2020-08-28 | 北京服装学院 | High-stereospecificity composite polylactic acid material and preparation method thereof |
| CN112626638B (en) * | 2020-12-15 | 2023-03-03 | 中国纺织科学研究院有限公司 | All-stereo composite polylactic acid fiber, preparation method, crystallization behavior testing method, device, computer-readable storage medium and equipment |
| CN113279085B (en) * | 2021-03-17 | 2023-02-24 | 中国纺织科学研究院有限公司 | Stock solution coloring fully-stereo composite polylactic acid fiber, preparation method, crystallization behavior testing method, device, storage medium and equipment |
| TW202248481A (en) * | 2021-06-01 | 2022-12-16 | 南亞塑膠工業股份有限公司 | Polylactic acid fibre |
| CN113604017B (en) * | 2021-08-27 | 2023-08-22 | 成都荷风智能科技有限公司 | Completely degradable self nanofiber reinforced polylactic acid composite material and preparation thereof |
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| CN102532837A (en) * | 2012-01-06 | 2012-07-04 | 四川大学 | Preparation method for high molecular weight polylactic acid steric composite |
| CN103467941A (en) * | 2013-09-02 | 2013-12-25 | 东华大学 | Transparent high-toughness polylactic acid membrane and preparation method thereof |
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Effective date of registration: 20230421 Address after: 102600 1803a, building 6, yard 2, Ronghua South Road, Beijing Economic and Technological Development Zone, Daxing District, Beijing Patentee after: Beijing Langjing Huiming Biotechnology Co.,Ltd. Patentee after: Shandong Langjing New Material Technology Co.,Ltd. Address before: 801-8150, 8 / F, building 2, a 5 Rongchang East Street, Beijing Economic and Technological Development Zone, Daxing District, Beijing, 100176 Patentee before: Beijing Langjing Huiming Biotechnology Co.,Ltd. |
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