CN111593437A - Preparation method of polyester blending modified polylactic acid elastic fiber - Google Patents
Preparation method of polyester blending modified polylactic acid elastic fiber Download PDFInfo
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- CN111593437A CN111593437A CN202010606683.0A CN202010606683A CN111593437A CN 111593437 A CN111593437 A CN 111593437A CN 202010606683 A CN202010606683 A CN 202010606683A CN 111593437 A CN111593437 A CN 111593437A
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 112
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 109
- 229920000728 polyester Polymers 0.000 title claims abstract description 62
- 210000004177 elastic tissue Anatomy 0.000 title claims abstract description 46
- 238000002156 mixing Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 78
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000002074 melt spinning Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims description 25
- 239000004593 Epoxy Substances 0.000 claims description 23
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- 230000008569 process Effects 0.000 claims description 15
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 238000004804 winding Methods 0.000 claims description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 239000004632 polycaprolactone Substances 0.000 claims description 8
- IUPHTVOTTBREAV-UHFFFAOYSA-N 3-hydroxybutanoic acid;3-hydroxypentanoic acid Chemical compound CC(O)CC(O)=O.CCC(O)CC(O)=O IUPHTVOTTBREAV-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 4
- 238000004043 dyeing Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
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- 230000000052 comparative effect Effects 0.000 description 14
- 238000000113 differential scanning calorimetry Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
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- 238000001125 extrusion Methods 0.000 description 9
- 238000005469 granulation Methods 0.000 description 9
- 230000003179 granulation Effects 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- 239000004970 Chain extender Substances 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
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- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
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- 238000012805 post-processing Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
- D01D1/00—Treatment of filament-forming or like material
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- 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
-
- 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
- D01D5/12—Stretch-spinning methods
-
- 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
- D01D7/00—Collecting the newly-spun products
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- Physics & Mathematics (AREA)
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Abstract
A preparation method of polyester blending modified polylactic acid elastic fiber relates to the field of polylactic acid fiber preparation. The method comprises the following steps: preparing a blended fiber master batch, adding a compatibilizer into pre-dried polylactic acid and polyester polymer, and performing melt blending in a double-screw extruder to obtain the blended fiber master batch; and (3) preparing a finished product, namely drying the obtained blend fiber master batch, then carrying out melt spinning, and controlling the technological parameters of the melt spinning to obtain the polyester blend modified polylactic acid elastic fiber. The compatibility of PLA and polyester polymer is improved through the reaction of the epoxy group in the compatibilizer and the special functional group in the polyester, and a PLA/polyester blending system is formed; polyester polymers can increase the toughness of PLA; the compatibility between PLA and polyester polymer components can be obviously improved; the processing performance of the blending system is improved; the dyeing property of the fiber can be increased, and the application range is enlarged; has environment-friendly performance and good application prospect.
Description
Technical Field
The invention relates to the field of polylactic acid fiber preparation, in particular to a preparation method of polyester blending modified polylactic acid elastic fiber.
Background
Polylactic acid (PLA) fiber mainly uses natural renewable resources as raw materials, reduces the dependence on non-renewable resources such as petroleum, and has excellent mechanical properties and degradability. With the increasing attention of people to the environment, the scale and cost reduction of PLA synthesis and the continuous expansion of the application field, the PLA fiber is bound to become one of important fiber varieties and is expected to replace the traditional chemical fiber materials such as polypropylene fiber, terylene, chinlon and the like in many fields.
Although polylactic acid itself is excellent in mechanical properties, it is easily degraded in an environment with moisture, and thus its mechanical properties are degraded during melt processing. In the production and commercialization processes of the fiber, certain requirements are required for the softness and elasticity of the fiber, and the polylactic acid fiber is characterized by high strength but poor toughness, so that blending modification needs to be carried out on the polylactic acid fiber.
Chinese patent application publication No. CN1687497A discloses a method for preparing polylactic acid blend polymer fiber, which comprises dissolving polylactic acid slices in chloroform solvent, stirring to obtain slurry with a concentration of 6-12%, coagulating the slurry in a spinning channel to form filaments, and stretching and heat setting in hot air (see page 2 of the specification of the patent). As is well known, chloroform (also known as "chloroform") is toxic and not suitable for the fields of food packaging and disposable sanitary materials, and is difficult to recover and costly, and is not environment-friendly.
The invention patent publication No. CN102660797B recommends "a preparation method of hydrolysis-resistant modified polylactic acid fiber", which uses low molecular weight polyester (1000-30000) and adipic acid polyester as plasticizer, and multifunctional polycarbodiimide is used to improve the water resistance of polylactic acid and the acting force between the low molecular weight polyester and the polylactic acid. Although the polylactic acid fiber prepared by the method has good hand feeling and softness, the polycarbodiimide can generate irritant gas in the spinning process, thereby not only influencing the environment of a spinning place, but also causing harm to human bodies.
Disclosure of Invention
The invention aims to provide a preparation method of polyester blending modified polylactic acid elastic fiber, which is beneficial to obviously improving the compatibility of PLA and polyester polymers, increasing the toughness of the PLA fiber, increasing the thermal stability of a blending system to improve the processing performance of the blending system, and is convenient for the fiber to reflect good dyeing performance and ensure the environment-friendly performance of the fiber.
The task of the invention is completed by the following steps:
A) preparing a blended fiber master batch, adding a compatibilizer into pre-dried polylactic acid and polyester polymer to perform melt blending in a double-screw extruder to obtain the blended fiber master batch;
B) drying the blended fiber master batch obtained in the step A), then carrying out melt spinning, and controlling the technological parameters of the melt spinning to obtain the polyester blended modified polylactic acid elastic fiber.
In a specific embodiment of the present invention, the weight parts of the polylactic acid, the polyester-based polymer and the compatibilizer in the blended fiber masterbatch are as follows:
70-90 parts of polylactic acid (PLA);
10-30 parts of polyester polymer;
0.5-1 part of a compatibilizer;
the weight-average molecular weight of the polylactic acid (PLA) is 100000-150000 g/mol;
the weight average molecular weight of the polyester polymer is 80000-100000 g/mol.
In another specific embodiment of the present invention, the polyester-based polymer is Polycaprolactone (PCL), polybutylene adipate terephthalate (PBAT), or poly 3-hydroxybutyrate-3-hydroxyvalerate (PHBV).
In yet another specific embodiment of the present invention, the compatibilizer is an epoxy acrylic compatibilizer.
In another specific embodiment of the present invention, the epoxy acrylic compatibilizer is one or both of an acrylic copolymer containing epoxy functional groups and styrene or glycidyl methacrylate.
In yet another specific embodiment of the present invention, the epoxy value of the epoxy acrylic compatibilizer is 350-480 g/mol.
In a more specific embodiment of the present invention, the temperature of each zone of the twin-screw in the melt blending in the twin-screw extruder is 160-200 ℃, the rotation speed of the twin-screw is 60-80rpm and the pelletizing speed is 300-400 m/min.
In a further specific embodiment of the present invention, the drying process of the pre-dried polylactic acid is: vacuum drying at 110-120 ℃ for 16-24 h; the drying process of the pre-dried polyester polymer comprises the following steps: vacuum drying at 55-90 deg.C for 16-24 hr; the drying temperature of the blended fiber master batch is 100-110 ℃, and the drying time is 16-24 h.
In a more specific embodiment of the present invention, the melt spinning process parameters are controlled to 200-.
In yet another specific embodiment of the invention, the polyester blended and modified polylactic acid elastic fiber has a monofilament linear density of 1.8-4.1dtex, a breaking strength of 2.1-3.9CN/dtex, and an elongation at break of 41-82%.
The technical scheme provided by the invention has the technical effects that: compared with the prior art, the compatibility of PLA and polyester polymer is improved by the reaction of the epoxy group in the compatibilizer and the specific functional group in the polyester, so that a PLA/polyester blending system is formed; because the raw material components and the process parameters are reasonably selected, the polyester polymer can increase the toughness of PLA, and the loss of strength is small; the compatibility between PLA and polyester polymer components can be obviously improved by adding the compatibilizer; the addition of the polyester polymer can increase the thermal stability of the blending system and improve the processing performance of the blending system; because benzene rings exist in molecules of a certain preferable polymer, the dyeing property of the fiber can be effectively improved, and the application range is enlarged; because the selected polyester polymers are all biodegradable materials, the fiber prepared by the method also has environment-friendly performance and good application prospect.
Drawings
FIG. 1 is a diagram of a finished product of the polyester blend modified polylactic acid elastic fiber prepared by the method of the invention.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms "comprises" or "comprising," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
Approximating language, as used herein in the specification and claims, may be applied to modify a quantity, such that the invention is not limited to the specific value, but includes equivalents thereof, as modified in response to specific variations thereof without departing from the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The present invention will be described in detail with reference to specific comparative examples and examples.
The invention uses the following raw material sources: polylactic acid (Natureworks, USA, with the designation 6202D), polyester polymers (different varieties are respectively purchased from Germany BASF, Guanghua Wei materials, Inc. of Shenzhen, Guangdong province, China), and compatibilizers (different varieties are respectively purchased from Germany BASF and New materials, Inc. of Hangzhou, Zhejiang province);
comparative example 1:
vacuum drying the polylactic acid slices at 110 ℃ for 16h, then adding the dried slices into a spinning machine, wherein the spinning temperature is 230 ℃, and the winding speed is 1800 m/min; the drafting temperature is set to be 100 ℃, and the drafting multiple is 4 times, so that the polylactic acid fiber is finally obtained.
The obtained polylactic acid fiber monofilament has the linear density of 1.5dtex, the breaking strength of 4.2cN/dtex and the elongation at break of 6.1 percent; the fiber has obvious melting peak near 180 ℃ measured by Differential Scanning Calorimetry (DSC). Comparative example 1 is some properties of the pure polylactic acid fiber, which can be compared with the following comparative examples.
Comparative example 2:
vacuum drying the polylactic acid slices at 110 ℃ for 16h, vacuum drying the polybutylene adipate-butylene terephthalate slices at 90 ℃ for 16h, adding 70 parts of polylactic acid, 30 parts of polybutylene adipate-butylene terephthalate and 0.5 part of glycidyl methacrylate into a double-screw extruder, setting the temperature of each zone to be 160-inch glass and 190 ℃, and extruding and granulating to obtain the modified blending master batch.
Drying the modified blended master batch at 110 ℃ for 16h, and adding the dried modified blended master batch into a spinning machine, wherein the spinning temperature is 220 ℃, and the winding speed is 1000 m/min; the drafting temperature is set to be 90 ℃, and the drafting multiple is 2 times, so that the polyester blending modified polylactic acid elastic fiber is finally obtained.
The obtained blended modified polylactic acid elastic fiber has the monofilament line density of 4dtex, the breaking strength of 2.2 cN/dtex and the elongation at break of 67 percent; and more broken filaments appear during the drawing process. The fiber has an obvious melting peak near 160 ℃ measured by Differential Scanning Calorimetry (DSC), the surface of the fiber is very rough and the section appearance is not uniform measured by a scanning electron microscope, which fully indicates that the addition of the compatibilizer does not play a good role, possibly caused by excessive PBAT components.
Comparative example 3:
and (2) carrying out vacuum drying on the polylactic acid slices at 110 ℃ for 20h, carrying out vacuum drying on the polybutylene adipate-butylene terephthalate slices at 95 ℃ for 20h, adding 75 parts of polylactic acid, 25 parts of polybutylene adipate-butylene terephthalate and 0.5 part of epoxy acrylic acid and styrene copolymer into a double-screw extruder, setting the temperature of each zone to be 160-grade and 190 ℃, and carrying out extrusion granulation to obtain the modified blending master batch.
Drying the modified blended master batch at 110 ℃ for 20h, and then adding the dried modified blended master batch into a spinning machine, wherein the spinning temperature is 215 ℃, and the winding speed is 1200 m/min; the drafting temperature is set to be 90 ℃, and the drafting multiple is 2.3 times, so that the polyester blending modified polylactic acid elastic fiber is finally obtained.
The obtained blended modified polylactic acid elastic fiber monofilament has the linear density of 3.7dtex, the breaking strength of 2.4 cN/dtex and the elongation at break of 62 percent; and more broken filaments appear during the drawing process. The fiber has an obvious melting peak near 163 ℃ measured by Differential Scanning Calorimetry (DSC), the surface of the fiber is very rough and the section appearance is not uniform measured by a scanning electron microscope, which fully indicates that the addition of the compatibilizer does not play a good role, possibly caused by excessive PBAT components.
It can be seen from comparison of comparative example 2 with comparative example 3 that increasing the drying time and replacing another compatibilizer did not effectively improve the yarn breakage, and comparison of comparative examples 1, 2 and 3 revealed that post-processing of the fiber was difficult due to the addition of PBAT, and the maximum draw-down times reached only about 2 times.
Example 1:
A) preparing a blended fiber master batch, carrying out vacuum drying on polylactic acid slices (PLA slices) at 110 ℃ for 20h, carrying out vacuum drying on polybutylene adipate-butylene terephthalate slices (PBAT slices) at 90 ℃ for 20h, adding 80 parts of polylactic acid with the weight-average molecular weight of 150000g/mol, 20 parts of polybutylene adipate-butylene terephthalate with the weight-average molecular weight of 80000g/mol and 0.8 part of glycidyl methacrylate with the epoxy value of 350g/mol into a double-screw extruder, setting the temperature of each zone to be 160-inch cake, setting the rotating speed of the double screws to be 80rpm and the grain cutting speed to be 400m/min, and carrying out extrusion granulation to obtain the modified blended master batch;
B) drying the modified blended master batch at 110 ℃ for 20 hours, and then adding the dried modified blended master batch into a spinning machine, wherein the spinning temperature is 225 ℃, and the winding speed is 1100 m/min; the drafting temperature is set to 90 ℃ and the drafting multiple is 2.8 times, and the finished product of the polyester blending modified polylactic acid elastic fiber shown in figure 1 is obtained.
The obtained blended modified polylactic acid elastic fiber monofilament has the linear density of 3.1dtex, the breaking strength of 2.9 cN/dtex and the elongation at break of 60 percent; the broken filaments are reduced in the drawing process. The fiber has an obvious melting peak near 166 ℃ measured by Differential Scanning Calorimetry (DSC), the surface and the section appearance of the fiber are improved measured under a scanning electron microscope, and the comparison of the example 1 and a comparative example shows that the compatibility between PLA and PBAT can be improved by properly reducing the addition amount of PBAT and increasing the amount of compatibilizer, so that the post-treatment and the fiber performance of the fiber are improved.
Example 2:
A) preparing a blended fiber master batch, carrying out vacuum drying on a polylactic acid slice (PLA slice) at 110 ℃ for 24h, carrying out vacuum drying on a polybutylene adipate-butylene terephthalate slice (PBAT slice) at 80 ℃ for 24h, adding 85 parts of polylactic acid with the weight-average molecular weight of 100000g/mol, 15 parts of polybutylene adipate-butylene terephthalate with the weight-average molecular weight of 100000g/mol and 0.8 part of glycidyl methacrylate with the epoxy value of 480g/mol into a double-screw extruder, setting the temperature of each zone to 160-plus-material 195 ℃, setting the rotating speed of the double screws to 60rpm and the grain cutting speed to 300m/min, and carrying out extrusion granulation to obtain the modified blended master batch;
B) drying the modified blended master batch at 110 ℃ for 20 hours, and then adding the dried modified blended master batch into a spinning machine, wherein the spinning temperature is 230 ℃, and the winding speed is 1400 m/min; the drafting temperature is set to 95 ℃ and the drafting multiple is 3.1 times, and the finished product of the polyester blending modified polylactic acid elastic fiber shown in figure 1 is obtained.
The obtained blended modified polylactic acid elastic fiber monofilament has the linear density of 2.6dtex, the breaking strength of 3.2 cN/dtex and the elongation at break of 51 percent; the yarn breaking phenomenon hardly occurs in the drawing process. The fiber has an obvious melting peak near 170 ℃ measured by Differential Scanning Calorimetry (DSC), the surface and the section appearance of the fiber are uniform and smooth measured under a scanning electron microscope, and the comparison between the example 1 and the example 2 shows that the phase separation degree of a blending system is reduced along with the reduction of the adding amount of PBAT, the reduction of the strength of the fiber is less along with the increase of compatibility, the toughness and the toughness are obviously increased, and the modified elastic fiber with excellent performance can be obtained by only adjusting the formula ratio subsequently.
Example 3:
A) preparing a blended fiber master batch, carrying out vacuum drying on polylactic acid slices (PLA slices) at 120 ℃ for 24h, carrying out vacuum drying on polybutylene adipate-butylene terephthalate slices (PBAT slices) at 90 ℃ for 16h, adding 90 parts of polylactic acid with the weight-average molecular weight of 105000g/mol, 10 parts of polybutylene adipate-butylene terephthalate with the weight-average molecular weight of 90000g/mol and 0.5 part of glycidyl methacrylate with the epoxy value of 360g/mol into a double-screw extruder, setting the temperature of each zone to be 160-inch-fluid-pressure 200 ℃, setting the rotating speed of the double screws to be 70rpm and the grain-cutting speed to be 350m/min, and carrying out extrusion granulation to obtain the modified blended master batch;
B) drying the modified blended master batch at 110 ℃ for 24h, and adding the dried modified blended master batch into a spinning machine, wherein the spinning temperature is 235 ℃, and the winding speed is 1500 m/min; the drafting temperature is set to 100 ℃, and the drafting multiple is 3.5 times, so that the polyester blending modified polylactic acid elastic fiber finished product shown in figure 1 is obtained.
The obtained blended modified polylactic acid elastic fiber monofilament has the linear density of 2.1dtex, the breaking strength of 3.6 cN/dtex and the elongation at break of 48 percent; the yarn breaking phenomenon hardly occurs in the drawing process. The fiber has an obvious melting peak near 175 ℃ measured by Differential Scanning Calorimetry (DSC), and the surface and the profile of the fiber are uniform and smooth measured by a scanning electron microscope, and are nearly as smooth as those of the fiber in the comparative example 1. As can be seen from the comparison between example 3 and example 2, with the further decrease of the amount of PBAT, the compatibility of the two components of the blending system is further increased, the strength and toughness of the fiber are correspondingly changed, and the modified elastic fiber with the corresponding index can be obtained by only adjusting the formula ratio.
Example 4:
A) preparing blended fiber master batches, carrying out vacuum drying on polylactic acid slices (PLA slices) at 120 ℃ for 16h, carrying out vacuum drying on polybutylene adipate-butylene terephthalate slices (PBAT slices) at 90 ℃ for 24h, adding 90 parts of polylactic acid with the weight-average molecular weight of 110000g/mol, 10 parts of polybutylene adipate-butylene terephthalate with the weight-average molecular weight of 85000g/mol and 0.5 part of acrylic acid and styrene copolymer containing epoxy functional groups and having the epoxy value of 370g/mol into a double-screw extruder, setting the temperature of each zone to be 160-DEG-plus-200 ℃, setting the rotating speed of the double screws to be 65rpm and the grain cutting speed to be 370m/min, and carrying out extrusion granulation to obtain modified blended master batches;
B) drying the modified blended master batch at 110 ℃ for 16h, and adding the dried modified blended master batch into a spinning machine, wherein the spinning temperature is 235 ℃, and the winding speed is 1600 m/min; the drafting temperature is set to be 100 ℃, and the drafting multiple is 3.9 times, so as to obtain the polyester blending modified polylactic acid elastic fiber finished product.
The obtained blended modified polylactic acid elastic fiber monofilament has the linear density of 1.8dtex, the breaking strength of 3.8 cN/dtex and the elongation at break of 46 percent; the yarn breaking phenomenon hardly occurs in the drawing process. The fiber has an obvious melting peak near 175 ℃ measured by Differential Scanning Calorimetry (DSC), and the surface and the profile of the fiber are uniform and smooth measured by a scanning electron microscope, and are nearly as smooth as those of the fiber in the comparative example 1. As can be seen from the comparison between example 4 and example 3, the compatibility of the two components of the blending system is relatively good by changing the components of the compatibilizer, which indicates that the two compatibilizers have good effects. The strength and the toughness of the fiber are correspondingly changed, and the modified elastic fiber with corresponding indexes can be obtained by only adjusting the formula ratio.
Example 5:
A) preparing blended fiber master batches, carrying out vacuum drying on polylactic acid slices (PLA slices) at 110 ℃ for 20h, carrying out vacuum drying on polycaprolactone slices (PCL slices) at 55 ℃ for 20h, adding 80 parts of polylactic acid with the weight-average molecular weight of 145000g/mol, 20 parts of polycaprolactone with the weight-average molecular weight of 98000g/mol and 0.8 part of glycidyl methacrylate with the epoxy value of 475g/mol into a double-screw extruder, setting the temperature of each zone to 160-190 ℃, setting the rotating speed of the double screws to 75rpm and the grain cutting speed to 380m/min, and carrying out extrusion granulation to obtain modified blended master batches;
B) drying the modified blended master batch at 100 ℃ for 20 hours, and then adding the dried modified blended master batch into a spinning machine, wherein the spinning temperature is 225 ℃, and the winding speed is 1200 m/min; the drafting temperature is set to be 90 ℃, and the drafting multiple is 2.5 times, so as to obtain the polyester blending modified polylactic acid elastic fiber finished product.
The obtained blended modified polylactic acid elastic fiber monofilament has the linear density of 4.1dtex, the breaking strength of 2.1 cN/dtex and the elongation at break of 82 percent; the broken filaments are more in the drafting process. The fiber has an obvious melting peak near 160 ℃ measured by Differential Scanning Calorimetry (DSC), and the surface and section appearance of the fiber are rough and the surface defects are more measured under a scanning electron microscope.
Example 6:
A) preparing blended fiber master batches, carrying out vacuum drying on polylactic acid slices (PLA slices) at 110 ℃ for 24 hours, carrying out vacuum drying on poly 3-hydroxybutyrate-3-hydroxyvalerate slices (PHBV slices) at 70 ℃ for 24 hours, adding 85 parts of polylactic acid with the weight-average molecular weight of 120000g/mol, 15 parts of poly 3-hydroxybutyrate-3-hydroxyvalerate with the weight-average molecular weight of 80000g/mol and 1.0 part of glycidyl methacrylate with the epoxy value of 470g/mol into a double-screw extruder, setting the temperature of each zone to be 160-185 ℃, setting the rotating speed of the double screws to be 65rpm and the grain cutting speed to be 325m/min, and carrying out extrusion granulation to obtain the modified blended master batches;
B) drying the modified blended master batch at 110 ℃ for 20 hours, and then adding the dried modified blended master batch into a spinning machine, wherein the spinning temperature is 200 ℃, and the winding speed is 1000 m/min; the drafting temperature is set to be 120 ℃, and the drafting multiple is 4 times, so as to obtain the polyester blending modified polylactic acid elastic fiber finished product.
The obtained blended modified polylactic acid elastic fiber monofilament has the linear density of 2.4dtex, the breaking strength of 3.2 cN/dtex and the elongation at break of 50 percent; the yarn breaking phenomenon hardly occurs in the drawing process. The fiber has an obvious melting peak near 170 ℃ measured by Differential Scanning Calorimetry (DSC), the surface and section appearance of the fiber are uniform and smooth measured by a scanning electron microscope, and the comparison between the example 6 and the example 5 shows that the surface appearance of the fiber is greatly improved after PCL is replaced by PHBV, so that the PHBV is more suitable for blended master batch spinning processing than PCL.
Example 7:
A) preparing blended fiber master batches, carrying out vacuum drying on polylactic acid slices (PLA slices) at 115 ℃ for 22h, carrying out vacuum drying on poly-3-hydroxybutyrate-3-hydroxyvalerate slices (PHBV slices) at 50 ℃ for 22h, adding 70 parts of polylactic acid with the weight-average molecular weight of 135000g/mol, 30 parts of poly-3-hydroxybutyrate-3-hydroxyvalerate with the weight-average molecular weight of 95000g/mol, 0.25 part of glycidyl methacrylate with the epoxy value of 400g/mol and 0.35 part of acrylic acid and styrene copolymer containing epoxy functional groups into a double-screw extruder, setting the temperature of each zone to be 160-200 ℃, setting the rotating speed of the double screws to be 75rpm and the grain cutting speed to be 375m/min, and carrying out extrusion granulation to obtain modified blended master batches;
B) drying the modified blended master batch at 105 ℃ for 18h, and then adding the dried modified blended master batch into a spinning machine, wherein the spinning temperature is 215 ℃, and the winding speed is 1350 m/min; the drafting temperature is set to be 100 ℃, and the drafting multiple is 3.5 times, so as to obtain the polyester blending modified polylactic acid elastic fiber finished product.
The obtained blended modified polylactic acid elastic fiber monofilament has the linear density of 2.0dtex, the breaking strength of 3.8 cN/dtex and the elongation at break of 45 percent; the yarn breaking phenomenon hardly occurs in the drawing process. The fiber has an obvious melting peak near 172 ℃ measured by Differential Scanning Calorimetry (DSC), and the surface and the profile of the fiber are uniform and smooth measured by a scanning electron microscope and are nearly as smooth as those of the fiber in the comparative example 1.
Example 8:
A) preparing blended fiber master batches, carrying out vacuum drying on polylactic acid slices (PLA slices) at 115 ℃ for 18h, carrying out vacuum drying on poly 3-hydroxybutyrate-3-hydroxyvalerate slices (PHBV slices) at 65 ℃ for 18h, adding 75 parts of polylactic acid with the weight-average molecular weight of 130000g/mol, 25 parts of poly 3-hydroxybutyrate-3-hydroxyvalerate with the weight-average molecular weight of 89000g/mol and 0.7 part of epoxy acrylic acid and styrene copolymer with the epoxy value of 440g/mol into a double-screw extruder, setting the temperature of each zone to be 160-200 ℃, setting the rotating speed of the double screws to be 80rpm and the grain cutting speed to be 400m/min, and carrying out extrusion granulation to obtain modified blended master batches;
B) drying the modified blended master batch at 108 ℃ for 23h, and adding the dried modified blended master batch into a spinning machine, wherein the spinning temperature is 215 ℃, and the winding speed is 1400 m/min; the drafting temperature is set to be 100 ℃, and the drafting multiple is 3.7 times, so as to obtain a finished product, namely the polyester blending modified polylactic acid elastic fiber.
The obtained blended modified polylactic acid elastic fiber monofilament has the linear density of 1.9dtex, the breaking strength of 3.9cN/dtex and the elongation at break of 41 percent; the yarn breaking phenomenon hardly occurs in the drawing process. The fiber has an obvious melting peak near 172 ℃ measured by Differential Scanning Calorimetry (DSC), and the surface and the profile of the fiber are uniform and smooth measured by a scanning electron microscope and are nearly as smooth as those of the fiber in the comparative example 1.
The polyester blend modified polylactic acid elastic fiber obtained in the above examples 1 to 8 increases the flexibility of the polylactic acid fiber, and increases the thermal stability of the polylactic acid to a certain extent, while not changing the advantage of biodegradability thereof.
Firstly, blending polylactic acid and polybutylene adipate-butylene terephthalate, adding an epoxy acrylic chain extender into a blending system to increase the compatibility of the two components, and increasing the elongation at break of the polylactic acid through the excellent toughness of the polybutylene adipate-butylene terephthalate compared with the polylactic acid; finally, the blended master batches are subjected to melt spinning to prepare the modified elastic fiber, and compared with the polylactic acid fiber, the fiber prepared by the optimized formula has tensile strength close to that of the polylactic acid fiber, and the elongation at break is increased by 7-8 times.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are intended to illustrate the principles of the invention, but rather that various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of polyester blending modified polylactic acid elastic fiber is characterized by comprising the following steps:
A) preparing a blended fiber master batch, adding a compatibilizer into pre-dried polylactic acid and polyester polymer to perform melt blending in a double-screw extruder to obtain the blended fiber master batch;
B) drying the blended fiber master batch obtained in the step A), then carrying out melt spinning, and controlling the technological parameters of the melt spinning to obtain the polyester blended modified polylactic acid elastic fiber.
2. The method for preparing the polyester blending modified polylactic acid elastic fiber according to claim 1, wherein the weight parts of the polylactic acid, the polyester polymer and the compatibilizer in the blending fiber master batch are as follows:
70-90 parts of polylactic acid;
10-30 parts of polyester polymer;
0.5-1 part of a compatibilizer;
the weight-average molecular weight of the polylactic acid is 100000-150000 g/mol;
the weight average molecular weight of the polyester polymer is 80000-100000 g/mol.
3. The method for preparing a polyester blend modified polylactic acid elastic fiber according to claim 1 or 2, wherein the polyester polymer is polycaprolactone, polybutylene adipate-terephthalate or poly 3-hydroxybutyrate-3-hydroxyvalerate.
4. The method for preparing the polyester blending modified polylactic acid elastic fiber according to claim 1 or 2, wherein the compatibilizer is an epoxy acrylic compatibilizer.
5. The method for preparing the polyester blending modified polylactic acid elastic fiber according to claim 4, wherein the epoxy acrylic compatibilizer is one or two of a copolymer of acrylic acid and styrene containing epoxy functional groups or glycidyl methacrylate.
6. The method for preparing polyester blending modified polylactic acid elastic fiber according to claim 4, wherein the epoxy value of the epoxy acrylic compatibilizer is 350-480 g/mol.
7. The method for preparing the polyester blending modified polylactic acid elastic fiber according to claim 1, wherein the temperature of each zone of the twin-screw in the melt blending in the twin-screw extruder is 160-200 ℃, the rotating speed of the twin-screw is 60-80rpm, and the pelletizing speed is 300-400 m/min.
8. The method for preparing the polyester blended and modified polylactic acid elastic fiber according to claim 1, wherein the drying process of the pre-dried polylactic acid is as follows: vacuum drying at 110-120 ℃ for 16-24 h; the drying process of the pre-dried polyester polymer comprises the following steps: vacuum drying at 55-90 deg.C for 16-24 hr; the drying temperature of the blended fiber master batch is 100-110 ℃, and the drying time is 16-24 h.
9. The method for preparing polyester blend modified polylactic acid elastic fiber according to claim 1, wherein the process parameters for controlling the melt spinning are controlling the melt spinning temperature at 200-235 ℃, the winding speed at 1000-1600m/min, the hot drawing temperature at 90-120 ℃ and the drawing multiple at 2.5-4 times.
10. The method for preparing the polyester blended and modified polylactic acid elastic fiber according to claim 1, wherein the monofilament linear density of the polyester blended and modified polylactic acid elastic fiber is 1.8-4.1dtex, the breaking strength is 2.1-3.9CN/dtex, and the elongation at break is 41-82%.
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