CN118029011A - PLA-PHA parallel composite elastic fiber and preparation method thereof - Google Patents
PLA-PHA parallel composite elastic fiber and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 210000004177 elastic tissue Anatomy 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 42
- 238000009987 spinning Methods 0.000 claims abstract description 25
- -1 siloxane chain Chemical group 0.000 claims abstract description 21
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims abstract description 9
- 239000004593 Epoxy Substances 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
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- 229920000747 poly(lactic acid) Polymers 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 21
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 10
- AUWTYYWCSSZUKQ-UHFFFAOYSA-N [bis(2-methylpropyl)-[tris(2-methylpropyl)silyl]silyl]-hydroxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](O)(CC(C)C)[Si](CC(C)C)(CC(C)C)[Si](CC(C)C)(CC(C)C)CC(C)C AUWTYYWCSSZUKQ-UHFFFAOYSA-N 0.000 claims description 7
- FHUDZSGRYLAEKR-UHFFFAOYSA-N 3-hydroxybutanoic acid;4-hydroxybutanoic acid Chemical compound CC(O)CC(O)=O.OCCCC(O)=O FHUDZSGRYLAEKR-UHFFFAOYSA-N 0.000 claims description 5
- UQOXIKVRXYCUMT-UHFFFAOYSA-N [dimethyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silyl]oxy-dimethyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1CC2OC2CC1CC[Si](C)(C)O[Si](C)(C)CCC1CC2OC2CC1 UQOXIKVRXYCUMT-UHFFFAOYSA-N 0.000 claims description 5
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 5
- RRWWOSSPAGCJFO-UHFFFAOYSA-N 3-hydroxybutanoic acid;3-hydroxyhexanoic acid Chemical compound CC(O)CC(O)=O.CCCC(O)CC(O)=O RRWWOSSPAGCJFO-UHFFFAOYSA-N 0.000 claims description 4
- SZKKRCSOSQAJDE-UHFFFAOYSA-N Schradan Chemical group CN(C)P(=O)(N(C)C)OP(=O)(N(C)C)N(C)C SZKKRCSOSQAJDE-UHFFFAOYSA-N 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
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- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 35
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- GVYJNBPRFDRDPE-UHFFFAOYSA-N bis[[dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silyl]oxy]-methyl-phenylsilane Chemical compound C1OC1COCCC[Si](C)(C)O[Si](C)(C=1C=CC=CC=1)O[Si](C)(C)CCCOCC1CO1 GVYJNBPRFDRDPE-UHFFFAOYSA-N 0.000 description 4
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Abstract
The invention discloses a PLA-PHA parallel composite elastic fiber and a preparation method thereof, belonging to the field of composite elastic fibers; the preparation method comprises the following steps: firstly, melting, extruding and granulating PLA and polysilsesquioxane in a double-screw extruder to obtain master batches, and then melting and mixing the master batches and the PLA to obtain a component A; the PHA is subjected to chain extension modification by double-end epoxy siloxane and then is fused and mixed with PLA to obtain a component B; the component A and the component B are subjected to composite spinning to prepare parallel composite elastic fibers; after the PHA is subjected to chain extension by the double-end epoxy siloxane, the relative molecular mass of the PHA can be increased, and the melt strength is improved; meanwhile, the siloxane chain segment can play a role of internal lubrication to improve the fluidity of the melt, reduce the processing temperature of the melt, further reduce the thermal degradation of PHA and ensure the necessary spinnability. In addition, polysilsesquioxane is introduced into the component A to improve the fluidity of PLA melt, reduce the viscosity difference between the component A and the component B, ensure that the composite fiber forms a good interface structure, and lay a macrostructure foundation for fiber curl formation; meanwhile, the polysilsesquioxane in the component A can promote nucleation and crystallization of PLA, and the blend of the PLA and the chain extension modified PHA component in the component B can construct a gradient distribution structure through heterogeneous flow control, so that the difference of radial microstructures in the composite fiber is increased, and the formation of fiber curl is promoted.
Description
Technical Field
The invention belongs to the field of composite elastic fibers, and particularly relates to a PLA-PHA parallel composite elastic fiber and a preparation method thereof.
Background
The bicomponent side-by-side type composite elastic fiber is a fiber composed of two polymers which are good in compatibility and large in difference in heat shrinkage performance. After the fiber is heated, a permanent spiral three-dimensional curling structure is formed due to the difference of the heat shrinkage rates of the two components, so that the fiber is endowed with good curling elasticity and elastic recovery performance, the requirements of most fabrics in the aspects of comfort, dyeing property, weaving property and the like are met, the problems that the traditional spandex is difficult to dye, the elasticity is excessive, the weaving is complex, the ageing is easy to occur in the using process and the like are solved, and the fiber can be directly woven on a machine without core-spun yarn treatment.
At present, in the development process of the parallel composite elastic fiber, different petroleum-based materials such as polyethylene terephthalate (PET)/polytrimethylene terephthalate (PTT), high-low viscosity polyester, polypropylene/polyamide 6, polypropylene/ethylene octene copolymer and the like are mainly combined. However, petroleum-based polymers present certain challenges in terms of resource utilization, environmental protection, and the like.
In recent years, green low carbon function is a mainstream trend of development of fiber materials. Polylactic acid (PLA) and Polyhydroxyalkanoate (PHA) materials have incomparable advantages in designing parallel composite elastic fibers due to their bio-based sources, biodegradability and other characteristics. The glass transition temperature of polylactic acid is usually about 55-60 ℃, the glass transition temperature of polyhydroxyalkanoate is usually about-20-10 ℃, the glass transition temperature of the two polymers is large, the heat shrinkage performance of the composite fiber can be obviously different after heat treatment, and the fiber is theoretically conducive to forming a good curled structure. However, the polyhydroxyalkanoate polymer has a narrow thermal processing window, is easily degraded by heat in the processing process, and causes the reduction of melt strength, and the phenomena of broken spinning and broken filaments are serious. Meanwhile, the polylactic acid and the polyhydroxyalkanoate are not completely thermodynamically miscible materials, so that the bonding force between two component interfaces of the composite fiber can be reduced to a certain extent, the asymmetric stress transfer among the components is affected, and the fiber crimping performance is reduced.
Therefore, further strengthening the formation of curl in PLA-PHA composite fibers is a technical problem to be solved if the forming performance of the PLA-PHA composite fibers is improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a PLA-PHA parallel composite elastic fiber and a preparation method thereof, which solve the problems in the prior art.
The aim of the invention can be achieved by the following technical scheme:
A preparation method of PLA-PHA parallel composite elastic fiber comprises the following steps:
PLA and polysilsesquioxane are firstly mixed according to the following steps (7-8): (2-3) carrying out melt extrusion granulation in a double-screw extruder to obtain master batches, and then carrying out melt mixing on the master batches and PLA to obtain a component A;
The PHA is subjected to chain extension modification by double-end epoxy siloxane and then is fused and mixed with PLA to obtain a component B;
and (3) carrying out composite spinning on the component A and the component B to obtain the parallel composite elastic fiber.
Further, in the component A, the mass ratio of PLA to polysilsesquioxane is (97-99.5): (0.5-3).
Further, in the component B, the mass ratio of PHA and PLA after chain extension modification is as follows: (25-75): (25-75).
Further, in the chain-extended modified PHA, the mass ratio of PHA to double-end epoxysiloxane is (97.5-99.5): (0.5-2.5).
Further, in the composite spinning process, the mass ratio of the component A to the component B is (20-80): (20-80).
Further, the number average molecular weight of the PLA is 200000-300000 g/mol, and the number average molecular weight of the PHA is 150000-300000 g/mol.
Further, the polysilsesquioxane is: one or more of heptaisobutyl trisilanol cage polysilsesquioxane, heptaoctyl trisilanol cage polysilsesquioxane, heptadecadialkyl trisilanol cage polysilsesquioxane, octamethyl cage polysilsesquioxane and octa (isobutyl silsesquioxane).
Further, the PHA is one of poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-3-hydroxyvalerate), poly (3-hydroxybutyrate-3-hydroxyhexanoate), and poly (3-hydroxybutyrate-4-hydroxybutyrate).
Further, the double-ended epoxysiloxane is one or more of bis [2- (3, 4-epoxycyclohexyl) ethyl ] hexamethyltrisiloxane, 1, 3-tetramethyl-1, 3-bis [3- (epoxyethylmethoxy) propyl ] disiloxane, 1, 3-bis [2- (3, 4-epoxycyclohexyl) ethyl ] tetramethyldisiloxane, 1, 5-bis (epoxypropoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane.
The PLA-PHA parallel composite elastic fiber is prepared by the preparation method of the PLA-PHA parallel composite elastic fiber.
The invention has the beneficial effects that:
1. The double-end epoxy siloxane adopted by the invention expands the PHA, and on the one hand, the degraded molecular chain in the PHA granulating process is dynamically repaired, so that the melt strength of the PHA is improved; meanwhile, in the spinning melting process, the siloxane chain segment can play a role of internal lubrication to improve the fluidity of the melt, reduce the processing temperature of the melt, further reduce the thermal degradation of PHA and ensure the necessary spinnability.
2. The invention adopts PLA and chain extension modified PHA component to blend and constructs a gradient distribution structure through heterogeneous flow control, while the polysilsesquioxane is introduced into the polylactic acid component in the other component to improve the melt fluidity of the polylactic acid component and promote nucleation and crystallization in fiber formation. The structure is not only beneficial to the formation of a good macroscopic interface structure of the composite fiber, but also can increase the difference of microstructures among components, increase the radial asymmetric stress of the composite fiber and promote the fiber curl.
3. The PLA/PHA parallel composite fiber has the characteristics of biological base and biodegradability, has good elasticity, mechanical property and the like, is simple and convenient in preparation method, meets the development requirement of green low-carbon fiber, and has wide application prospect in the fields of clothing, home textiles and the like.
Detailed Description
The technical solutions will be clearly and completely described in connection with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The process of preparing PLA-PHA side-by-side composite elastic fibers is illustrated by the following examples;
In the following examples, the raw materials are respectively:
Poly (3-hydroxybutyrate) (PHB) was purchased from Zhuhai wheat, inc. of the genetics sciences Co., ltd;
poly (3-hydroxybutyrate-4-hydroxybutyrate) (P34 HB) was purchased from Zhuhai's Makino extract technologies Co., ltd;
Poly (3-hydroxybutyrate-3-hydroxyvalerate) (PHBV) was purchased from Shanghai Cheng Quan plasticization Co., ltd;
the amount fraction of poly (3-hydroxybutyrate-3-hydroxycaproate) (PHBHHx) HH material was 11%, kaneka corporation, japan.
Polylactic acid (PLA) is purchased from dadaceae, pyn;
heptaisobutyl trisilanols cage polysilsesquioxane was purchased from New technology Co., guangzhou;
Heptadeca-dialkyl trisilanol polyhedral oligomeric silsesquioxanes are available from new technology, inc., guangzhou;
Octamethyl cage polysilsesquioxane was purchased from new technology limited, guangzhou;
eight (isobutyl silsesquioxane) CAS number: 221326-46-1;
heptaoctyl trisilanol cage polysilsesquioxane is available from new technology limited, guangzhou;
Bis [2- (3, 4-epoxycyclohexyl) ethyl ] hexamethyltrisiloxane, prepared according to the synthetic method reported in literature (Shen Han. Synthesis of bis [2- (3, 4-epoxycyclohexyl) ethyl ] hexamethyltrisiloxane, study of uv-curing properties [ D ]. University of south-chang, 2023.);
1, 3-tetramethyl-1, 3 bis [3- (epoxyethylmethoxy) propyl ] disiloxane CAS No.: 126-80-7;
1, 3-bis [2- (3, 4-epoxycyclohexyl) ethyl ] tetramethyldisiloxane CAS number: 18724-32-8;
1, 5-bis (glycidoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane CAS number: 865811-59-2.
Example 1
The preparation method of the PLA-PHA parallel composite elastic fiber comprises the following steps:
S1, melt blending PLA and PLA-polysilsesquioxane master batches to obtain a component A melt;
The method comprises the following steps:
1) The PLA-heptaisobutyl trisilyl cage-shaped polysilsesquioxane master batch is prepared by melt extrusion granulation of a double screw extruder, wherein the temperatures of a region I, a region II, a region III, a region IV, a region V, a region VI and a region VII of the double screw extruder are 155 ℃, 168 ℃, 165 ℃, 162 ℃ and 162 ℃ respectively, and the content of the heptaisobutyl trisilyl cage-shaped polysilsesquioxane in the master batch is 20 wt percent.
2) Adopting a masterbatch adding method, carrying out melt blending on PLA slices and PLA-heptaisobutyl trisilyl cage-shaped polysilsesquioxane masterbatch through a composite spinning machine screw at 195 ℃ to obtain a component A melt, and controlling the adding amount of the masterbatch to ensure that the mass ratio of PLA to heptaisobutyl trisilyl cage-shaped polysilsesquioxane in the component A is 99.5:0.5.
S2, melting and blending PHA with PLA after chain extension of double-end epoxy siloxane to obtain a component B melt;
The method comprises the following steps:
1) Poly (3-hydroxybutyrate) and bis [2- (3, 4-epoxycyclohexyl) ethyl ] hexamethyltrisiloxane were reacted according to 99.5: chain extension reaction is carried out in a mass ratio of 0.5 to obtain a chain extension product, the chain extension reaction is carried out in a double-screw extruder, the chain extension extrusion temperature is 165 ℃, the negative pressure is minus 0.05MPa, and the time is 3min;
2) The chain extension product was then combined with PLA according to 25:75 mass ratio, and carrying out melt blending at 185 ℃ through a composite spinning machine screw to obtain a component B melt; the zero-cut viscosity of the polylactic acid is 200 Pa.S higher than that of poly (3-hydroxybutyrate) after chain extension of bis [2- (3, 4-epoxycyclohexyl) ethyl ] hexamethyltrisiloxane under the condition of extrusion temperature;
wherein the PLA has a number average molecular weight of 200000g/mol and the poly (3-hydroxybutyrate) has a number average molecular weight of 150000g/mol.
S3, preparing the parallel composite elastic fiber by composite spinning of the component A and the component B;
the main process of composite spinning comprises the following steps: respectively extruding the component A and the component B through a spinning hole by adopting a compound spinning machine, cooling, hot stretching and overfeeding winding;
Melting the component A and the component B in a double-screw extruder respectively, wherein the temperature of the melt of the component A is 195 ℃ and the temperature of the melt of the component B is 185 ℃; then, metering the materials respectively through metering pumps, extruding the materials into a spinning assembly through a spinning hole, wherein the spinning temperature is 188 ℃; the rotational speed of the metering pump of the component A and the component B is regulated so that the mass ratio of the component A to the component B is 20:80. in the spinneret extrusion process, the shear rate of the melt at the spinneret was 3500S -1. The cooling mode in the cooling procedure is side blowing, the component B faces the blowing direction, the component A faces away from the blowing direction, and the blowing temperature is 12 ℃. The hot stretching temperature is 105 ℃, and the stretching multiplying power is 1.5 times. The overfeed rate of the overfeed winding is 5%.
Example 2
The preparation method of the PLA-PHA parallel composite elastic fiber comprises the following steps:
S1, melt blending PLA and PLA-polysilsesquioxane master batches to obtain a component A melt;
The method comprises the following steps:
1) The PLA-heptaisobutyl trisilyl cage-shaped polysilsesquioxane master batch is prepared by melt extrusion granulation of a double screw extruder, wherein the temperatures of a region I, a region II, a region III, a region IV, a region V, a region VI and a region VII of the double screw extruder are 155 ℃, 168 ℃, 165 ℃, 162 ℃ and 162 ℃ respectively, and the content of the heptaisobutyl trisilyl cage-shaped polysilsesquioxane in the master batch is 30 wt percent.
2) Adopting a masterbatch adding method, carrying out melt blending on PLA slices and PLA-heptaisobutyl trisilyl cage-shaped polysilsesquioxane masterbatch through a composite spinning machine screw at 185 ℃ to obtain a component A melt, and controlling the adding amount of the masterbatch to ensure that the mass ratio of PLA to heptaisobutyl trisilyl cage-shaped polysilsesquioxane in the component A is 97: 3.
S2, melting and blending PHA with PLA after chain extension of double-end epoxy siloxane to obtain a component B melt;
The method comprises the following steps:
1) Poly (3-hydroxybutyrate) and bis [2- (3, 4-epoxycyclohexyl) ethyl ] hexamethyltrisiloxane were reacted in accordance with 97.5:2.5, carrying out chain extension reaction to obtain a chain extension product, wherein the chain extension reaction is carried out in a double-screw extruder, the chain extension extrusion temperature is 175 ℃, the negative pressure is-0.1 MPa, and the time is 6min;
2) The chain extension product was then combined with PLA according to 75:25 by mass ratio, blending the materials at 165 ℃ through a composite spinning machine screw to obtain a component B melt; the zero-cut viscosity of the polylactic acid is 350 Pa.S higher than that of poly (3-hydroxybutyrate) after chain extension of bis [2- (3, 4-epoxycyclohexyl) ethyl ] hexamethyltrisiloxane under the condition of extrusion temperature;
wherein the PLA has a number average molecular weight of 300000g/mol and the poly (3-hydroxybutyrate) has a number average molecular weight of 300000g/mol.
S3, preparing the parallel composite elastic fiber by composite spinning of the component A and the component B;
the main process of composite spinning comprises the following steps: respectively extruding the component A and the component B through a spinning hole by adopting a compound spinning machine, cooling, hot stretching and overfeeding winding;
Melting the component A and the component B in a double-screw extruder respectively, wherein the temperature of the melt of the component A is 185 ℃ and the temperature of the melt of the component B is 165 ℃; then, metering the materials by metering pumps respectively, extruding the materials into a spinning assembly through a spinneret orifice, wherein the spinning temperature is 175 ℃; the rotational speed of the metering pumps of the component A and the component B is regulated so that the mass ratio of the component A to the component B is 80:20. in the spinneret extrusion process, the shear rate at the spinneret was 5000S -1. The cooling mode in the cooling procedure is side blowing, the component B faces the blowing direction, the component A faces away from the blowing direction, and the blowing temperature is 22 ℃. The hot stretching is carried out at a stretching temperature of 150 ℃ and a stretching multiplying power of 6 times. The overfeed rate of the overfeed winding is 30%.
Example 3
This embodiment differs from embodiment 1 only in that:
In S1, polysilsesquioxane is heptaoctyl trisilanol cage polysilsesquioxane;
in S2, PHA is poly (3-hydroxybutyrate-3-hydroxyvalerate), and the double-end epoxysiloxane is 1, 3-tetramethyl-1, 3 bis [3- (epoxyethylmethoxy) propyl ] disiloxane.
Example 4
This embodiment differs from embodiment 1 only in that:
in S1, polysilsesquioxane is heptadecadialkyltrisilanol cage-shaped polysilsesquioxane;
In S2, PHA is poly (3-hydroxybutyrate-3-hydroxycaproate), and the double-end epoxysiloxane is 1, 3-bis [2- (3, 4-epoxycyclohexyl) ethyl ] tetramethyl disiloxane.
Example 5
This embodiment differs from embodiment 2 only in that:
In S1, polysilsesquioxane is octamethyl cage-shaped polysilsesquioxane;
In S2, PHA is poly (3-hydroxybutyrate-4-hydroxybutyrate), and the double-ended epoxysiloxane is 1, 5-bis (glycidoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane.
Example 6
This embodiment differs from embodiment 2 only in that:
in S1, the polysilsesquioxane is eight (isobutyl silsesquioxane);
In S2, PHA is poly (3-hydroxybutyrate-4-hydroxybutyrate), and the double-ended epoxysiloxane is 1, 5-bis (glycidoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane.
Comparative example 1
The preparation method of PLA-PHA parallel composite elastic fiber is basically the same as that of example 1, and the only difference is that: component A consists of PLA and component B consists of PLA and poly (3-hydroxybutyrate).
And (3) testing and verifying:
Test verification was performed on the composite elastic fibers obtained in examples 1 to 6 and comparative example 1;
the following are performance test criteria:
Curl, curl recovery, according to GB/T14338-2022 test;
tensile breaking strength according to GB/T14344-1993 standard.
The experimental results are shown in table 1 below:
TABLE 1 test data for the performance of composite elastic fibers obtained in examples 1-6 and comparative examples
From the above table, it can be seen that:
in comparative example 1, no heptaisobutyl trisilanol cage-like polysilsesquioxane is added to the component A, so that the melt viscosity of the component A is high, the fluidity is poor, the viscosity difference between the component A and the component B is increased, the interface structure of the composite fiber is deformed, and the curl formation is affected; meanwhile, in the component ratio B, poly (3-hydroxybutyrate) is directly melt-blended with PLA, the poly (3-hydroxybutyrate) is severely thermally degraded, and the PLA is induced to be thermally degraded, so that the fiber spinnability is deteriorated.
In the embodiment 1, the heptaisobutyl trisilanol cage-shaped polysilsesquioxane is added into the component A, so that the fluidity of the component A is improved, the viscosity difference between the component A and the component B is reduced, the composite fiber is facilitated to form a good interface structure, and a macrostructure foundation formed by curling is laid; meanwhile, after the poly (3-hydroxybutyrate) in the component B is subjected to chain extension of bis [2- (3, 4-epoxycyclohexyl) ethyl ] hexamethyltrisiloxane, the molecular weight of the poly (3-hydroxybutyrate) is improved, the spinning forming stability is ensured, and meanwhile, the effect of 'internal lubrication' is exerted after a siloxane chain segment is introduced, so that the poly (3-hydroxybutyrate) is promoted to diffuse to the outside of the fiber in the component B, and a gradient distribution phase structure is formed. In addition, the heptaisobutyl trisilanol cage-shaped polysilsesquioxane in the component A can be used as a nucleating agent to promote PLA crystallization, further aggravate the difference of radial structures in the composite fiber and is beneficial to the formation of fiber curl.
Example 2 compared with example 1, the radial structural difference of the composite fiber is enhanced by increasing the content of the heptaisobutyl trisilanol cage-like polysilsesquioxane in the component A and the mass ratio of PHA after chain extension of the double-end epoxy siloxane in the component B, so that larger asymmetric stress is formed inside the composite fiber, and the crimping rate of the fiber is remarkably improved.
In examples 3 to 6, it was found that by properly changing the raw materials, parallel composite elastic fibers having good crimping performance could be obtained.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. The preparation method of the PLA-PHA parallel composite elastic fiber is characterized by comprising the following steps:
PLA and polysilsesquioxane are firstly mixed according to the following steps (7-8): (2-3) carrying out melt extrusion granulation in a double-screw extruder to obtain master batches, and then carrying out melt mixing on the master batches and PLA to obtain a component A;
The PHA is subjected to chain extension modification by double-end epoxy siloxane and then is fused and mixed with PLA to obtain a component B;
and (3) carrying out composite spinning on the component A and the component B to obtain the parallel composite elastic fiber.
2. The method for preparing the PLA-PHA side-by-side composite elastic fiber according to claim 1, wherein in the component A, the mass ratio of PLA to polysilsesquioxane is (97-99.5): (0.5-3).
3. The method for preparing the PLA-PHA parallel composite elastic fiber according to claim 1, wherein in the component B, the mass ratio of the chain-extended modified PHA to the PLA is as follows: (25-75): (25-75).
4. The method for producing a PLA-PHA side-by-side composite elastic fiber according to claim 3, wherein the mass ratio of PHA to double-ended epoxysiloxane in the chain-extended modified PHA is (97.5-99.5): (0.5-2.5).
5. The method for producing a PLA-PHA side-by-side composite elastic fiber according to claim 1, wherein in the composite spinning process, the mass ratio of the component a to the component B is (20-80): (20-80).
6. The method for producing a side-by-side composite elastic fiber of PLA-PHA according to claim 1, wherein the number average molecular weight of PLA is 200000 to 300000g/mol and the number average molecular weight of PHA is 150000 to 300000g/mol.
7. The method for producing a PLA-PHA side-by-side composite elastic fiber according to claim 1, wherein said polysilsesquioxane is: one or more of heptaisobutyl trisilanol cage polysilsesquioxane, heptaoctyl trisilanol cage polysilsesquioxane, heptadecadialkyl trisilanol cage polysilsesquioxane, octamethyl cage polysilsesquioxane and octa (isobutyl silsesquioxane).
8. The method of producing side-by-side composite elastic PLA-PHA of claim 1, wherein said PHA is one of poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-3-hydroxyvalerate), poly (3-hydroxybutyrate-3-hydroxyhexanoate) and poly (3-hydroxybutyrate-4-hydroxybutyrate).
9. The method of producing a PLA-PHA side-by-side composite elastic fiber according to claim 1, wherein said double-ended epoxysiloxane is one or more of bis [2- (3, 4-epoxycyclohexyl) ethyl ] hexamethyltrisiloxane, 1, 3-tetramethyl-1, 3 bis [3- (epoxyethylmethoxy) propyl ] disiloxane, 1, 3-bis [2- (3, 4-epoxycyclohexyl) ethyl ] tetramethyldisiloxane, 1, 5-bis (epoxypropoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane.
10. A PLA-PHA side-by-side composite elastic fiber, characterized in that it is produced using the method for producing a PLA-PHA side-by-side composite elastic fiber as defined in any one of claims 1 to 9.
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