CN117026418A - Full-biodegradable sheath-core composite fiber and preparation method thereof - Google Patents
Full-biodegradable sheath-core composite fiber and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 229920008262 Thermoplastic starch Polymers 0.000 claims abstract description 71
- 239000004628 starch-based polymer Substances 0.000 claims abstract description 71
- 229920000229 biodegradable polyester Polymers 0.000 claims abstract description 59
- 239000004622 biodegradable polyester Substances 0.000 claims abstract description 59
- 239000010410 layer Substances 0.000 claims abstract description 42
- 238000009987 spinning Methods 0.000 claims abstract description 37
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 35
- 239000012792 core layer Substances 0.000 claims abstract description 33
- 239000004626 polylactic acid Substances 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 238000002844 melting Methods 0.000 claims description 24
- 239000000155 melt Substances 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 20
- -1 polybutylene succinate Polymers 0.000 claims description 16
- 229920002961 polybutylene succinate Polymers 0.000 claims description 14
- 239000004631 polybutylene succinate Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000009264 composting Methods 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 abstract description 10
- 230000008025 crystallization Effects 0.000 abstract description 10
- 229920000728 polyester Polymers 0.000 description 35
- 239000000047 product Substances 0.000 description 12
- 239000000306 component Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
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- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 description 4
- 239000002667 nucleating agent Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- 229920004933 Terylene® Polymers 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 3
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
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- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
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- 239000000945 filler Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 102100021669 Stromal cell-derived factor 1 Human genes 0.000 description 1
- 101710088580 Stromal cell-derived factor 1 Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 description 1
- 229920005586 poly(adipic acid) Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Multicomponent Fibers (AREA)
Abstract
The application relates to a full-biological degradable sheath-core composite fiber and a preparation method thereof, and the preparation method comprises the following steps: taking biodegradable polyester mixed with thermoplastic starch as a skin layer raw material and polylactic acid as a core layer raw material, and preparing the full-biodegradable skin-core composite fiber according to a skin-core composite spinning process; the product is as follows: the skin layer is biodegradable polyester, thermoplastic starch is mixed in the biodegradable polyester, and the core layer is polylactic acid; the thermoplastic starch content of the biodegradable polyester is not more than 2wt%. The application takes the biodegradable polyester with excellent flexibility as the skin layer and polylactic acid as the core layer, fully exerts the low-melting-point adhesiveness of the skin layer components and the framework supporting function of the core layer, introduces thermoplastic starch into the skin layer to promote the crystallization performance of the skin layer biodegradable polyester and improve the processability; the full-biodegradable sheath-core composite fiber spun by the application has skin-friendly softness and good hot air adhesion, and realizes the unification of application performance and biodegradability.
Description
Technical Field
The application belongs to the technical field of biodegradable fibers, and relates to a full-biodegradable sheath-core composite fiber and a preparation method thereof.
Background
Along with the improvement of living standard and the rapid expansion of non-woven industry, the filling gasket material has been in the updating stage, and the traditional polyurethane foaming material has obviously limited the application in the field with high safety and comfort requirements due to the defects of poor ventilation and heat dissipation, easy aging, burning to generate hydrogen cyanide highly toxic gas and the like. In recent years, the appearance of a polyester three-dimensional non-woven material (also called upright cotton) provides better choices for people, generally, polyester fibers and low-melting-point fibers are used as raw materials, a multi-gap three-dimensional structure is formed by hot air fusion bonding processing after vertical lapping through mixed carding, the fiber aggregate can show resilience and compression resistance similar to sponge, the problem of poor water permeability and air permeability caused by poor gap connectivity of polyurethane foaming sponge can be effectively solved, and meanwhile, the bulk, unit weight, ageing resistance, product safety and environmental protection performance, production cleanliness and the like are comprehensively improved. At present, the fields of home textiles, automotive interiors, underwear, sports goods, medical sanitation and the like are all widely started to replace polyurethane foam materials by polyester upright cotton, and the market prospect is wide.
The low-melting-point fiber is a core raw material for preparing the polyester upright cotton, plays a decisive role in rebound and air permeability of the product, and is also a hot spot for developing new chemical fiber products at present. The analysis of the sheath-core composite low-melting-point fiber shows that the sheath layer of the composite fiber mainly plays a role in bonding in application, the core layer plays a role in mechanical support, and the composite fiber is ensured to have certain mechanical strength. The sheath-core composite low-melting-point fiber is applied to hot air processing and depends on contact bonding between the fiber and a fiber sheath layer so as to realize the three-dimensional structure of a macroscopic product. The bonding properties, in particular the bond strength, between fibers have a very large influence on the three-dimensional nonwoven product.
The Chinese patent No. 112981610A discloses an environment-friendly hydrophilic low-melting PET composite short fiber which is of a sheath-core structure, wherein the sheath layer is a modified environment-friendly hydrophilic low-melting PET, and the core layer is an environment-friendly polyester chip, so that the composite short fiber has good water absorption performance and bonding performance. The bonding characteristics between fibers are mainly dependent on the fact that the composite fibers are all based on polyester, and have good thermodynamic compatibility properties.
Chinese patent No. 114262954A relates to a preparation method of low-melting-point polyester fiber and application thereof in natural fiber adhesion, in order to realize good adhesion strength between the low-melting-point polyester fiber and the natural fiber, aluminum oxide is added into the low-melting-point polyester as a heat-conducting filler, which is beneficial to improving the heat conductivity coefficient of the low-melting-point fiber. When the mass addition amount of the alumina is 2-3%, the heat conductivity coefficient of the low-melting-point fiber can be improved by 8-10%, and the heating speed of the low-melting-point fiber during hot baking can be improved to a certain extent due to the improvement of the heat conductivity coefficient, so that the melting amount is increased, and the bonding effect of the low-melting-point fiber is improved.
Chinese patent CN114775105a discloses a method for preparing homogeneous heterogeneous polyester sheath-core composite fiber, which comprises spinning low-melting polyester and block polyester sheath-core to obtain composite fiber, wherein the sheath layer of the composite fiber comprises low-melting polyester and preactivated polymer, and the core layer is block polyester; activating the composite fiber to prepare the homogeneous heterogeneous polyester sheath-core composite fiber; and carrying out hot air forming on the homogeneous heterogeneous polyester sheath-core composite fiber. The main components of the skin layer and the core layer are polyester, and the interface compatibility is good. The composite fiber is activated by a certain alkaline aqueous solution, and the surface of the activated composite fiber forms a microporous structure with the diameter of 0.1-1.0 micrometers and rich reactive groups. In the hot air bonding process of the homogeneous heterogeneous polyester sheath-core composite fiber, the contact area between the fibers is increased, and meanwhile, the reactive groups further react with the surfaces of the fibers, so that the bonding strength is comprehensively improved, and the application of the homogeneous heterogeneous polyester sheath-core composite fiber to the high-resilience textiles for non-woven fabrics can be realized.
With the development of the age, attention is paid to environmental problems, interest is generated in green environment-friendly fibers, and development of composite fibers with biodegradable properties is an important direction.
Chinese patent No. CN115094541a discloses a low-adhesion biodegradable sheath-core composite copolyester fiber, and its preparation method, the low-adhesion biodegradable sheath-core composite copolyester fiber has a sheath-core composite structure; cortex is PLA, PBS, PVA, PCL, PGA or PHA; the core layer is PBAT, PBST, PBSF or PBAF; the difference of melt index MI of the skin layer and the core layer at the same temperature is not more than 15g/min; the biodegradable sheath-core composite copolyester fiber with low adhesiveness is prepared, but the biodegradable fiber sacrifices the adhesiveness of the sheath layer, and limits the application range.
Chinese patent No. CN111979605B discloses a method for processing a composite fiber using a multicomponent degradable polymer, wherein the sheath group is selected from 50% low melting amorphous polylactic acid COPLA, 30% polycaprolactone PCL and 20% polybutylene succinate PBS; the core component is selected from 70% high melting point polylactic acid PLA, 20% polyhydroxyalkanoate PHA/B and 10% polybutylene terephthalate-adipate PBAT. According to the application, the sheath-core type composite fiber is processed by taking the mixed and melted multi-component degradable polymer as the sheath-core raw material, the defects of single component are overcome by mutual mixing by utilizing the compatibility of the polymer of each component, and the degradable composite fiber with better performance is prepared, however, the interface compatibility is improved by blending a plurality of components, the components are complex, the thermal degradation phenomenon is easy to occur by high shearing of double screws, the crystallization rate and the stretching orientation of each component are different in the spinning and stretching processes, the broken yarn is easy to occur, the fiber strength is easy to be reduced, and the mechanical property of the final product is influenced.
Therefore, the full-biodegradable sheath-core composite fiber and the preparation method thereof are researched to have excellent mechanical property, biodegradability, excellent adhesive property and better compatibility, and have very important significance.
Disclosure of Invention
The application aims to solve the problems in the prior art and provides a full-biodegradable sheath-core composite fiber and a preparation method thereof.
In order to achieve the above purpose, the application adopts the following technical scheme:
the fully biodegradable sheath-core composite fiber has a sheath layer of biodegradable polyester mixed with thermoplastic starch (TPS) and a core layer of polylactic acid; polylactic acid has biodegradability and excellent mechanical strength and plays a role in supporting a core layer; the polyhydroxy structure of the sheath TPS forms a hydrogen bond with carbonyl in the core polylactic acid to generate physical crosslinking, so that intermolecular acting force exists at the sheath-core interface, and the interface bonding acting force between the sheath and the core is improved; and, the polyhydroxy structure of the thermoplastic starch added in the cortex and the carbonyl structure of the bonded polyester form a hydrogen bond, and physical adsorption is improved through the intermolecular interaction, so that the bonding performance of the cortex is improved;
the content of the thermoplastic starch in the biodegradable polyester is not more than 2wt%; when the TPS content is increased to more than 2wt%, hydrogen bonds among TPS molecules are more easily formed, agglomeration can occur, microphase separation occurs, and the TPS is not easy to form a hydrogen bond with polyester to generate a physical crosslinking structure; when TPS is added in a trace amount, the TPS is uniformly dispersed in the biodegradable polyester and does not generate obvious agglomeration phenomenon, the effect of a nucleating agent can be exerted in the cooling crystallization process, the crystallization performance of the biodegradable polyester is improved, the agglomeration phenomenon of the TPS is obvious as the content of the TPS is increased to more than 2wt%, and the TPS and the biodegradable polyester are subjected to microphase separation, so that the effect of the nucleating agent cannot be effectively exerted;
the fineness of the full-biodegradable sheath-core composite fiber is 0.5-5.5 dtex, the composting biological decomposition rate is more than or equal to 60%, the disintegration degree is more than or equal to 90%, the breaking strength is more than or equal to 2.0cN/dtex, the fiber modulus is 40-80 cN/dtex, the fiber compression rebound resilience is excellent, and the elastic recovery rate is more than or equal to 80%; the sheath bonding strength of the fully biodegradable sheath-core composite fiber is improved by 20-50% compared with a comparison sample, and the comparison sample is basically the same as the fully biodegradable sheath-core composite fiber, except that the biodegradable polyester does not contain thermoplastic starch.
As a preferable technical scheme:
the fully biodegradable sheath-core composite fiber has the content of thermoplastic starch in the biodegradable polyester of 0.2-2 wt%.
The full-biodegradable sheath-core composite fiber has the melting point of thermoplastic starch of 120-130 ℃ and the melt index of 10-20 g/10min under the condition of 190 ℃/2.16 kg.
The full-biodegradable sheath-core composite fiber has the intrinsic viscosity of 0.80-1.20 dL/g and the melt index of 15-30 g/10min under the condition of 190 ℃/2.16 kg.
A fully biodegradable sheath-core composite fiber as described above, the biodegradable polyester is polybutylene succinate (PBS), polybutylene adipate/terephthalate (PBAT) or polybutylene succinate terephthalate (PBST).
The full-biodegradable sheath-core composite fiber has the melting point of polylactic acid of 125-180 ℃ and the melt index of 15-25 g/10min under the condition of 190 ℃/2.16 kg.
The full-biodegradable sheath-core composite fiber has the mass ratio of the sheath layer to the core layer of 4:6-6:4.
The application also provides a preparation method of the full-biodegradable sheath-core composite fiber, which is characterized in that the full-biodegradable sheath-core composite fiber is prepared by taking biodegradable polyester mixed with thermoplastic starch as a sheath raw material and polylactic acid as a core raw material according to a sheath-core composite spinning process.
As a preferable technical scheme:
the preparation method of the full-biodegradable sheath-core composite fiber comprises the following spinning process parameters: the spinning temperature is 190-210 ℃, the spinning speed is 500-2000 m/min, and the total draft ratio is 3.5-6.0 times.
Principle of the application
The application adopts biodegradable polybutylene succinate (PBS), poly adipic acid/butylene terephthalate (PBAT) or poly butylene succinate/terephthalate (PBST) as a skin layer, polylactic acid as a core layer, respectively dries, extrudes and melts into a melt in respective screw extruders, and then prepares the bicomponent sheath-core structural fiber through spinning, circular blowing cooling, winding and forming. The skin layer is polyester with biodegradability, is more flexible than conventional PET polyester or polylactic acid, and the corresponding fiber material is more fit and comfortable to the human body. PBS, PBAT or PBST is taken as a cortex, so that the skin affinity of the spun fiber in the process of contacting with a human body can be remarkably improved; the core layer polylactic acid plays a role of framework support, and the composite fiber is ensured to have good mechanical strength.
PBS, PBAT or PBST has many advantages as the sheath layer, but the problems existing in the spinning of the sheath-core composite fiber are mainly concentrated on the problems that the crystallization performance of the biodegradable polyester is weaker, the sheath-core composite fiber can not realize coaxial stretching of the inner and outer layers in the processing process due to the fact that the thermodynamic property difference is larger when the biodegradable polyester is compounded with polylactic acid, the fiber spinnability is reduced, the mechanical strength of the fiber is low, and the like. The present application introduces trace amount of thermoplastic starch into the biodegradable polyester. Thermoplastic starch has been largely demonstrated to have very excellent degradability, including hydrolysis and biodegradability, etc., and incorporation into the skin layer does not adversely affect the degradation of the biodegradable polyester. The thermoplastic starch is introduced into the skin layer to serve as a heterogeneous component, plays a role of a nucleating agent in the cooling crystallization process, and improves the crystallization performance of the biodegradable polyester. Meanwhile, the thermoplastic starch has a branched structure of polyhydroxy functional groups, has stronger molecular chain hydrogen bonding action, improves the interface bonding acting force of the skin layer and the core layer, and further realizes the improvement of the performance of the skin-core composite fiber. In the post-processing hot air forming process of the spun sheath-core composite fiber, the sheath layer is bonded with low-melting-point characteristics, meanwhile, the thermoplastic starch contained in the sheath layer further strengthens the bonding strength, the fiber is not easy to be scattered in the preparation process of the processed fiber, and the performance is more excellent.
In the prior art, thermoplastic starch is usually used as a filler of a film or a plastic product and is added into polyester in a content of more than 10wt% (usually 30-50%) so as to reduce the application cost of biodegradable polyester while keeping the biodegradation rate, but most of the prior art focuses on modification of TPS due to incompatibility of TPS and polyester so as to improve the interfacial compatibility of TPS and polyester, prevent microphase separation phenomenon, and improve the mechanical property of biodegradable polyester while reducing the production cost. In addition, improvement of mechanical properties of the biodegradable polyester can be achieved only after TPS is modified, and cannot be achieved by simply adding high-content TPS.
The application introduces a trace amount (less than or equal to 2 wt%) of thermoplastic starch into the biodegradable polyester, firstly, because the polyhydroxy structure of TPS can form hydrogen bond with carbonyl of the polyester to generate a physical crosslinking structure, the action force between molecular chains is increased, the thermal degradation of the polyester in the high-temperature processing process is inhibited, the molecular weight of the blend is increased, the molecular weight distribution is narrowed, the processing thermal stability of the polyester is improved, and the spinnability of PBAT is improved. Secondly, TPS can be used as a nucleating agent of PBAT, so that the crystallization temperature and crystallization rate of the PBAT are improved, and the mechanical properties of the PBAT are improved. Unlike available technology, which has hydrophobic polyester and hydrophilic TPS, and thus has no excellent compatibility, the present application has no obvious microphase separation during trace addition of TPS, and the addition of TPS in high content results in lowered mechanical performance and spinnability of the mixture.
The beneficial effects are that:
(1) According to the full-biodegradable sheath-core composite fiber, biodegradable polyester with excellent flexibility is taken as a sheath layer, polylactic acid is taken as a core layer, and the low-melting-point adhesiveness of the sheath layer components and the framework supporting function of the core layer are fully exerted;
(2) According to the fully biodegradable sheath-core composite fiber, the thermoplastic starch is introduced into the sheath to promote the crystallization performance of the sheath biodegradable polyester, so that the processability is improved, and the degradation performance of the biodegradable polyester is not adversely affected; the thermoplastic starch has a branched structure of polyhydroxy functional groups, has stronger molecular chain hydrogen bonding action, improves the bonding force of a composite interface of the skin layer and the core layer, realizes synchronous stretching of skin-core components under the same process, and ensures that the full-biodegradable skin-core composite fiber has good mechanical properties;
(3) The full-biodegradable sheath-core composite fiber has skin-friendly softness and good hot air adhesion, and realizes unification of application performance and biodegradability;
(4) According to the preparation method of the full-biodegradable sheath-core composite fiber, the thermoplastic starch contained in the sheath layer strengthens the bonding strength while the spinnability is not damaged, and the related application performance of the fiber in the disposable sanitary textile processed after hot air forming is improved.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The test standard/test method related to the application is as follows:
composting biological decomposition rate: according to GB/T19277.1-2011 test;
degree of disintegration: according to GB/T19811-2005 test;
breaking strength: according to GB/T14344-2022 test;
fiber modulus: according to GB/T14344-2022 test;
elastic recovery: tested according to FZT 50007-2012;
adhesive strength: evaluating the bonding strength of the full-biodegradable sheath-core composite fiber by referring to GB7124-1986, cutting a terylene cloth spline, wherein the specification of the terylene cloth spline is 10mm x 2.5mm, and weighing a 20mg fiber sample; taking two cut polyester fabric strips, placing one of the two cut polyester fabric strips on a heat table and heating to the melting point of polylactic acid in a fiber sample, placing the fiber sample at one end of the polyester fabric strip, covering the other polyester fabric strip on the sample when the fiber sample begins to deform, applying 13N pressure to enable the polyester fabric strip and the fiber sample to be bonded together by using a circular columnar body, and then rapidly cooling to room temperature to achieve the effect of hot melt bonding; in order to facilitate the subsequent calculation of the bonding area, the contact surface of the fiber sample and the terylene cloth sample strip is kept to be round as much as possible, the bonding strength of the full-biodegradable fiber is tested by using a universal testing machine, each fiber sample is tested for five times, the average value is taken, and the stretching rate of the universal testing machine Instron5566 is 10mm/min.
Example 1
The preparation method of the full-biodegradable sheath-core composite fiber comprises the following specific steps:
(1) Preparation of raw materials:
thermoplastic starch: the manufacturer: polymeric materials, inc., of the precise family of Dongguan, trade name: THJS-7801, melting point of 120 ℃, and melt index of 20g/10min under the condition of 190 ℃/2.16 kg;
biodegradable polyesters: is polybutylene succinate, manufacturer: xinjiang blue mountain Tun river chemical industry Co., ltd., brand: TH803S, wherein the intrinsic viscosity is 1.20dL/g, and the melt index under the condition of 190 ℃/2.16kg is 20-30 g/10min;
polylactic acid: the manufacturer: anhui Feng Yuanfu Talai polylactic acid Co., ltd., brand: 6202D, the melting point is 180 ℃, and the melt index under the condition of 190 ℃/2.16kg is 15-18 g/10min;
(2) Taking biodegradable polyester mixed with thermoplastic starch as a skin layer raw material and polylactic acid as a core layer raw material, and preparing the full-biodegradable skin-core composite fiber according to a skin-core composite spinning process;
wherein the content of the thermoplastic starch in the biodegradable polyester is 0.2 weight percent; the mass ratio of the skin layer to the core layer is 4:6;
the spinning process parameters are as follows: the spinning temperature is 190 ℃, the spinning speed is 500m/min, and the total draft ratio is 3.5 times.
The fineness of the prepared full-biodegradable sheath-core composite fiber is 0.5dtex, the composting biological decomposition rate is 60%, the disintegration degree is 94%, the breaking strength is 2cN/dtex, the fiber modulus is 40cN/dtex, the elastic recovery rate is 84%, and the sheath bonding strength of the full-biodegradable sheath-core composite fiber is improved by 20% compared with a comparison sample, and the comparison sample is basically the full-biodegradable sheath-core composite fiber except that the biodegradable polyester does not contain thermoplastic starch.
Example 2
The preparation method of the full-biodegradable sheath-core composite fiber comprises the following specific steps:
(1) Preparation of raw materials:
thermoplastic starch: the manufacturer: polymeric materials, inc., of the precise family of Dongguan, trade name: THJS-7801, melting point of 120 ℃, and melt index of 20g/10min under the condition of 190 ℃/2.16 kg;
biodegradable polyesters: polybutylene adipate-co-terephthalate, manufacturer: the product has the characteristics that the product has the intrinsic viscosity of 1.10dL/g and the melt index of 15-25 g/10min under the condition of 190 ℃/2.16kg, and is manufactured by Xinjiang blue mountain Tunyan chemical industry Co., ltd, brand TH 801T;
polylactic acid: the manufacturer: anhui Feng Yuanfu Talai polylactic acid Co., ltd., brand: 6202D, the melting point is 180 ℃, and the melt index under the condition of 190 ℃/2.16kg is 15-18 g/10min;
(2) Taking biodegradable polyester mixed with thermoplastic starch as a skin layer raw material and polylactic acid as a core layer raw material, and preparing the full-biodegradable skin-core composite fiber according to a skin-core composite spinning process;
wherein the content of the thermoplastic starch in the biodegradable polyester is 0.5 weight percent; the mass ratio of the skin layer to the core layer is 5:5;
the spinning process parameters are as follows: spinning temperature is 195 ℃, spinning speed is 800m/min, and total draft ratio is 4 times.
The fineness of the prepared full-biodegradable sheath-core composite fiber is 1.7dtex, the composting biological decomposition rate is 67%, the disintegration degree is 92%, the breaking strength is 2.3cN/dtex, the fiber modulus is 47cN/dtex, the elastic recovery rate is 87%, and the sheath bonding strength of the full-biodegradable sheath-core composite fiber is improved by 22% compared with a comparison sample, and the comparison sample is basically the full-biodegradable sheath-core composite fiber, except that the biodegradable polyester does not contain thermoplastic starch.
Example 3
The preparation method of the full-biodegradable sheath-core composite fiber comprises the following specific steps:
(1) Preparation of raw materials:
thermoplastic starch: the manufacturer: polymeric materials, inc., of the precise family of Dongguan, trade name: TPS-7012 with a melting point of 125 ℃ and a melt index of 12g/10min at 190 ℃/2.16 kg;
biodegradable polyesters: the manufacturer: xinjiang blue mountain Tun river chemical company Limited,
polybutylene succinate with the brand TH901T, the intrinsic viscosity of 0.80dL/g and the melt index of 15-25 g/10min under the condition of 190 ℃/2.16 kg;
polylactic acid: the manufacturer: zhejiang sea Zhengsheng biological materials Co., ltd., brand: REVODE110 with a melting point of 160 ℃ and a melt index of 20-23 g/10min at 190 ℃/2.16 kg;
(2) Taking biodegradable polyester mixed with thermoplastic starch as a skin layer raw material and polylactic acid as a core layer raw material, and preparing the full-biodegradable skin-core composite fiber according to a skin-core composite spinning process;
wherein the content of the thermoplastic starch in the biodegradable polyester is 1wt%; the mass ratio of the skin layer to the core layer is 6:4;
the spinning process parameters are as follows: spinning temperature is 200 ℃, spinning speed is 1000m/min, and total draft ratio is 4.5 times.
The fineness of the prepared full-biodegradable sheath-core composite fiber is 2.6dtex, the composting biological decomposition rate is 74%, the disintegration degree is 93%, the breaking strength is 2.5cN/dtex, the fiber modulus is 62cN/dtex, the elastic recovery rate is 83%, and the sheath bonding strength of the full-biodegradable sheath-core composite fiber is improved by 34% compared with a comparison sample, and the comparison sample is basically the full-biodegradable sheath-core composite fiber except that the biodegradable polyester does not contain thermoplastic starch.
Example 4
The preparation method of the full-biodegradable sheath-core composite fiber comprises the following specific steps:
(1) Preparation of raw materials:
thermoplastic starch: the manufacturer: polymeric materials, inc., of the precise family of Dongguan, trade name: TPS-7012 with a melting point of 125 ℃ and a melt index of 12g/10min at 190 ℃/2.16 kg;
biodegradable polyesters: is polybutylene succinate, manufacturer: xinjiang blue mountain Tun river chemical industry Co., ltd., brand: TH803S, wherein the intrinsic viscosity is 1.20dL/g, and the melt index under the condition of 190 ℃/2.16kg is 20-30 g/10min;
polylactic acid: the manufacturer: zhejiang sea Zhengsheng biological materials Co., ltd., brand: REVODE110 with a melting point of 160 ℃ and a melt index of 20-23 g/10min at 190 ℃/2.16 kg;
(2) Taking biodegradable polyester mixed with thermoplastic starch as a skin layer raw material and polylactic acid as a core layer raw material, and preparing the full-biodegradable skin-core composite fiber according to a skin-core composite spinning process;
wherein the content of the thermoplastic starch in the biodegradable polyester is 1.5wt%; the mass ratio of the skin layer to the core layer is 6:4;
the spinning process parameters are as follows: spinning temperature is 200 ℃, spinning speed is 1500m/min, and total draft ratio is 5 times.
The fineness of the prepared full-biodegradable sheath-core composite fiber is 3.8dtex, the composting biological decomposition rate is 77%, the disintegration degree is 95%, the breaking strength is 2.5cN/dtex, the fiber modulus is 65cN/dtex, the elastic recovery rate is 80%, and the sheath bonding strength of the full-biodegradable sheath-core composite fiber is improved by 38% compared with a comparison sample, which is basically the same as the full-biodegradable sheath-core composite fiber, except that the biodegradable polyester does not contain thermoplastic starch.
Example 5
The preparation method of the full-biodegradable sheath-core composite fiber comprises the following specific steps:
(1) Preparation of raw materials:
thermoplastic starch: the manufacturer: polymeric materials, inc., of the precise family of Dongguan, trade name: TPS-7012 with a melting point of 125 ℃ and a melt index of 12g/10min at 190 ℃/2.16 kg;
biodegradable polyesters: polybutylene adipate-co-terephthalate, manufacturer: the product has the characteristics that the product has the intrinsic viscosity of 1.10dL/g and the melt index of 15-25 g/10min under the condition of 190 ℃/2.16kg, and is manufactured by Xinjiang blue mountain Tunyan chemical industry Co., ltd, brand TH 801T;
polylactic acid: zhejiang sea Zhengsheng biological materials Co., ltd., brand: REVODE190, melting point 125 ℃, melt index 21-25 g/10min under 190 ℃/2.16kg condition;
(2) Taking biodegradable polyester mixed with thermoplastic starch as a skin layer raw material and polylactic acid as a core layer raw material, and preparing the full-biodegradable skin-core composite fiber according to a skin-core composite spinning process;
wherein the content of the thermoplastic starch in the biodegradable polyester is 1.8wt%; the mass ratio of the skin layer to the core layer is 4:6;
the spinning process parameters are as follows: the spinning temperature is 205 ℃, the spinning speed is 1800m/min, and the total draft ratio is 5.5 times.
The fineness of the prepared full-biodegradable sheath-core composite fiber is 4.6dtex, the composting biological decomposition rate is 85%, the disintegration degree is 93%, the breaking strength is 2.6cN/dtex, the fiber modulus is 77cN/dtex, the elastic recovery rate is 86%, and the sheath bonding strength of the full-biodegradable sheath-core composite fiber is improved by 45% compared with a comparison sample, which is basically the same as the full-biodegradable sheath-core composite fiber, except that the biodegradable polyester does not contain thermoplastic starch.
Example 6
The preparation method of the full-biodegradable sheath-core composite fiber comprises the following specific steps:
(1) Preparation of raw materials:
thermoplastic starch: the manufacturer: suzhou and plastic technologies Co., ltd., brand: TPS-7801, melting point 130 ℃, melt index 10g/10min at 190 ℃/2.16 kg;
biodegradable polyesters: polybutylene succinate terephthalate, manufacturer: the product has the characteristics that the intrinsic viscosity is 0.80dL/g, and the melt index is 15-25 g/10min under the condition of 190 ℃/2.16kg, wherein the brand of the product is TH 901T;
polylactic acid: the manufacturer: zhejiang sea Zhengsheng biological materials Co., ltd., brand: REVODE190, melting point 125 ℃, melt index 21-25 g/10min under 190 ℃/2.16kg condition;
(2) Taking biodegradable polyester mixed with thermoplastic starch as a skin layer raw material and polylactic acid as a core layer raw material, and preparing the full-biodegradable skin-core composite fiber according to a skin-core composite spinning process;
wherein the content of the thermoplastic starch in the biodegradable polyester is 2wt%; the mass ratio of the skin layer to the core layer is 5:5;
the spinning process parameters are as follows: spinning temperature 210 ℃, spinning speed 2000m/min and total draft ratio 6 times.
The fineness of the prepared full-biodegradable sheath-core composite fiber is 5.5dtex, the composting biological decomposition rate is 90%, the disintegration degree is 90%, the breaking strength is 2.7cN/dtex, the fiber modulus is 80cN/dtex, the elastic recovery rate is 84%, and the sheath bonding strength of the full-biodegradable sheath-core composite fiber is improved by 50% compared with a comparison sample, which is basically the same as the full-biodegradable sheath-core composite fiber, except that the biodegradable polyester does not contain thermoplastic starch.
Claims (9)
1. A fully biodegradable sheath-core composite fiber, characterized in that: the skin layer is biodegradable polyester, thermoplastic starch is mixed in the biodegradable polyester, and the core layer is polylactic acid;
the content of the thermoplastic starch in the biodegradable polyester is not more than 2wt%;
the fineness of the full-biodegradable sheath-core composite fiber is 0.5-5.5 dtex, the composting biological decomposition rate is more than or equal to 60%, the disintegration degree is more than or equal to 90%, the breaking strength is more than or equal to 2.0cN/dtex, the fiber modulus is 40-80 cN/dtex, and the elastic recovery rate is more than or equal to 80%; the sheath bonding strength of the fully biodegradable sheath-core composite fiber is improved by 20-50% compared with a comparison sample, and the comparison sample is basically the same as the fully biodegradable sheath-core composite fiber, except that the biodegradable polyester does not contain thermoplastic starch.
2. The fully biodegradable sheath-core composite fiber according to claim 1, wherein the thermoplastic starch content of the biodegradable polyester is 0.2-2 wt%.
3. The fully biodegradable sheath-core composite fiber according to claim 1, wherein the thermoplastic starch has a melting point of 120-130 ℃ and a melt index of 10-20 g/10min at 190 ℃/2.16 kg.
4. The fully biodegradable sheath-core composite fiber according to claim 1, wherein the intrinsic viscosity of the biodegradable polyester is 0.80-1.20 dL/g and the melt index at 190 ℃/2.16kg is 15-30 g/10min.
5. The fully biodegradable sheath-core composite fiber according to claim 4, wherein the biodegradable polyester is polybutylene succinate, polybutylene adipate/terephthalate or polybutylene succinate terephthalate.
6. The fully biodegradable sheath-core composite fiber according to claim 1, wherein the polylactic acid has a melting point of 125-180 ℃ and a melt index of 15-25 g/10min at 190 ℃/2.16 kg.
7. The fully biodegradable sheath-core composite fiber according to claim 1, wherein the mass ratio of sheath to core is 4:6-6:4.
8. A method for preparing a fully biodegradable sheath-core composite fiber according to any one of claims 1 to 7, characterized in that: the biodegradable polyester mixed with thermoplastic starch is used as a skin layer raw material, polylactic acid is used as a core layer raw material, and the full-biodegradable skin-core composite fiber is prepared according to a skin-core composite spinning process.
9. The method for preparing the full-biodegradable sheath-core composite fiber according to claim 8, wherein the spinning process parameters are as follows: the spinning temperature is 190-210 ℃, the spinning speed is 500-2000 m/min, and the total draft ratio is 3.5-6.0 times.
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